Geochemical studies of soils in some city parks of Warsaw

Badania gleb na terenie parków położonych w centrum Warszawy miały na celu szczegółowe analizy ich stanu chemicznego, ze szczególnym uwzględnieniem wzbogacenia w pierwiastki toksyczne dla organizmów żywych. Analizowano gleby z dwóch zakresów głębokości (0,0–0,3 i 0,8–1,0 m) dla porównania zmian ich składu wywołanych czynnikami antropogenicznymi w relacji do skał macierzystych. Gęstość opróbowania wynosiła 1 próbka/0,01 km2. Oznaczenia Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Sr, Ti i Zn wykonano metodą ICP-AES, a rtęć analizowano metodą CV-AAS. Stwierdzono wzbogacenie warstwy powierzchniowej gleb w miedź, ołów i cynk, wiążące się wyraźnie z oddziaływaniem czynników antropogenicznych. Na obrzeżach parków zaznaczają się anomalie miedzi (>28 mg/kg), ołowiu (>70 mg/kg) i cynku (>206 mg/kg), których źródłem są głównie emisje z zakładów przemysłowych oraz środków transportu. Przeciętne zawartości baru (68 mg/kg), strontu (21 mg/kg) i siarki (0,028%) są również wyraźnie zwiększone w stosunku do wartości regionalnego tła geochemicznego. Zawartości tych pierwiastków są związane przede wszystkim z opadem pyłów z elektrociepłowni miejskich. Przestrzenne rozmieszczenie glinu, kobaltu, chromu, żelaza, niklu i tytanu jest związane ze składem chemicznym skał podłoża. Punktowe anomalie metali w glebach parków są związane z historycznym funkcjonowaniem na ich terenie obiektów wojskowych oraz wykorzystywaniem materiałów pochodzących z odgruzowywania Warszawy po II wojnie światowej do budowy alejek parkowych.The main purpose of the studies on soils of Warsaw parks was to assess the level of metal pollution and especially enrichment of elements toxic for organisms. Samples were taken from two depth intervals (0.0–0.3 and 0.8–1.0 m) for comparison between anthropogenic changes and natural background. Sample density was 1 sample/0.01 km2. Elements were determined using ICP-AES method. Mercury was determined with CV-AAS method. The enrichment of copper, lead and zinc in the topsoil is related to urbanization factors. Cu (>28 mg/kg), Pb (>70 mg/kg) and Zn (>206 mg/kg) concentrations found at the boundaries of the parks are due to atmospheric falls of industrial and traffic origin. The medians of barium (68 mg/kg), strontium (21 mg/kg) and sulphur (0.028%) in park soils are definitely higher than the geochemical background. The source of the enrichment seams to be emissions released from local power plants. Spatial distribution of aluminum, cobalt, chromium, iron, nickel and titanium is related to the geological structure. Spotty anomalies of metals in park soils are related to the long-term existence of polluting objects on their areas and to the use of ruins from Warsaw buildings after World War II as a building material for park footpaths

GEMAS: Cobalt, Cr, Cu and Ni distribution in agricultural and grazing land soil of Europe

Available online 26 January 2015In the framework of the GEMAS project, 2211 samples of agricultural soil (Ap, 0-20cm, regularly ploughed fields), and 2118 samples from land under permanent grass cover (Gr, 0-10cm, grazing land soil) were collected across almost the whole European continent, at a density of 1 sample site/2500km2, in accordance with a common sampling protocol.Among many other elements, the concentrations of Co, Cr, Cu and Ni in European soil were determined by ICP-MS after a hot aqua extraction, and WD-XRFS analytical methods, and their spatial distribution patterns generated by means of a GIS software.The presence of mafic and ultramafic rocks, ophiolite complexes and mineralisation, is widespread across the European continent, and seems to explain most of the variability of the elements studied in this paper. A large belt, north of the last glaciation maximum limit, is generally dominated by lower concentrations compared with central European and Mediterranean areas and to some areas in Northern Europe where higher Co, Cr, Cu and Ni values also occur.The application of the guideline value set for Cu and Ni by the EU Directive 86/278/EEC to the Ap soil samples of the GEMAS data set highlighted that at the continental scale the use of a unique reference interval is a tool of limited effectiveness; the lithological variation, occurring across a whole continent, generates changes in the geochemistry of soil, which cannot be accommodated by using a single reference interval even if it is very wide. The GEMAS data set should form the sound basis to set at the European scale the geochemical background reference intervals, at least, for regions sharing common lithological settings and a common geological history. •Geochemistry of Co, Cr, Cu and Ni•Mineral deposits in Europe with Co, Cr, Cu and Ni•Distribution of Co, Cr, Cu and Ni in European agricultural and grazing land soil•Comparison of aqua regia extractable and total element concentrations in soil•Comparison of Cu and Ni concentrations with European guideline values.Stefano Albanese, Martiya Sadeghi, Annamaria Lima, Domenico Cicchella, Enrico Dinelli, Paolo Valera, Marco Falconi, Alecos Demetriades, Benedetto De Vivo, The GEMAS Project Team (M. Andersson ... M. McLaughlin ... et al.

Geochemical fingerprinting and source discrimination of agricultural soils at continental scale

Available online 13 December 20142108 agricultural soil samples (Ap-horizon, 0-20cm) were collected in Europe (33 countries, area 5.6 million km2) as part of the recently completed GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil mapping project. GEMAS soil data have been used to provide a general view of element origin and mobility with a main focus on source parent material (and source rocks) at the continental scale, either by reference to average crustal abundances or to normalized patterns of element mobility during weathering processes. The survey area covers a large territory with diverse types of soil parent materials, with distinct geological history and a wide range of climate zones, and landscapes.To normalize the chemical composition of European agricultural soil, mean values and standard deviation of the selected elements have been compared to model compositions of the upper continental crust (UCC) and mean European river suspended sediment. Some elements are enriched relative to the UCC (Al, P, Pb, Zr,) whereas others, such as Mg, Na and Sr are depleted. The concept of the UCC extended normalization pattern has been applied to selected elements. The mean values of Rb, K, Y, Ti, Al, Si, Zr, Ce and Fe are very similar to the values from the UCC model, even when standard deviations indicate slight enrichment or depletion. Zirconium has the best fit to the UCC model using both mean value and standard deviation. Lead and Cr are enriched in European soil when compared to the UCC model, but their standard deviation values span a large, particularly towards very low values, which can be interpreted as a lithological effect.GEMAS soil data have been normalized to Al and Na, taking into account the main lithologies of the UCC, in order to discriminate provenance sources. Additionally, sodium normalization highlights variations related to the soluble and insoluble behavior of some elements (e.g., K, Rb versus Ti, Al, Si, V, Y, Zr, Ba, and La, respectively), their reactivity (e.g, Fe, Mn, Zn) and association with carbonates (e.g., Ca and Sr). Maps of Europe showing the spatial distribution of normalized compositions and element ratios reveal difficulties with the use of classical element ratios because of the large lithological differences in compositions of soil parent material. The ratio maps and color composite images extracted from the GEMAS data can help to discriminate the main lithologies in Europe at the regional scale but need to be used with caution due to the complexity of superimposed processes responsible for the soil chemical composition.Philippe Négrel, Martiya Sadeghi, Anna Ladenberger, Clemens Reimann, Manfred Birke, the GEMAS Project Team (S. Albanese ... M. McLaughlin ... et al.

New soil composition data for Europe and Australia: demonstrating comparability, identifying continental-scale processes and learning lessons for global geochemical mapping

Abstract not availableClemens Reimann, Patrice de Caritat ... R. Hoffmann ... M. McLaughlin ... [et. al] [GMAS Project Team, NGSA Project Team

Geochemical evidence of aeolian deposits in European soils

M. McLaughlin and R. Hoffmann are members of the GEMAS Project TeamHafnium (Hf) and zirconium (Zr) concentrations measured in over 4100 agricultural soil samples from Europe were assessed with the focus on their relationship to the distribution of aeolian deposits, such as loess and coversands. Comparison of extractable (aqua regia; ICP-MS) and total (XRFS) concentrations shows that only 1.0 to 1.7% of the total Hf and Zr is chemically extractable because of the resistant nature of their host minerals. Resistate minerals, such as zircon, are commonly found in the predominantly silty fraction of loess deposits. In this study a statistical analysis of total Hf and Zr soil data from areas with and without loess was carried out to derive threshold values of 10 mg kg⁻¹ (Hf) and 318 mg kg⁻¹ (Zr). These values were subsequently applied across the project area in an attempt to indicate the presence of aeolian deposits. The spatial distribution of above-threshold concentrations suggests a more extensive and coherent loess belt across central and eastern Europe, providing additional evidence of loess across Brittany, Aquitaine and near the Vosges mountains in France as well as in the basins of central and northern Spain. Above-threshold concentrations were also detected in loess regardless of its thickness, emphasising the importance of the abundance of zircon in the upper part of the soil profile rather than the actual thickness of the deposit. Soil data however, failed to indicate various loess facies within most of the Pannonian Basin, suggesting that this approach only works where deposits contain a sufficient amount of zircon. This may also explain why the extensive coversands across northern Germany and Poland were largely undetected. This study demonstrates that continental-scale soil geochemical data can help identify and map the distribution of zircon-rich loess and coversand, and subsequently enhance and improve current knowledge of the extent of these deposits.Andreas J. Scheib, Manfred Birke, Enrico Dinelli, GEMAS Project Tea

GEMAS: Geochemical background and mineral potential of emerging tech-critical elements in Europe revealed from low-sampling density geochemical mapping

The demand for ‘high-tech’ element resources (e.g., rare earth elements, lithium, platinum group elements) has increased with their continued consumption in developed countries and the emergence of developing economies. To provide a sound knowledge base for future generations, it is necessary to identify the spatial distribution of critical elements at a broad-scale, and to delineate areas for follow-up surveys. Subsequently, this knowledge can be used to study possible environmental consequences of the increased use of these resources. In this paper, three critical industrial elements (Sb, W, Li) from low-sampling density geochemical mapping at the continental-scale are presented. The geochemical distribution and spatial patterns have been obtained from agricultural soil samples (Ap-horizon, 0–20 cm; N ¼ 2108 samples) collected at a density of 1 site per 2500 km2 and analysed by ICP-MS after a hot aqua regia digestion as part of the GEMAS (GEochemical Mapping of Agricultural and grazing land Soil) soil-mapping project in 33 European countries. Most of the geochemical maps show exclusively natural background element concentrations with minor, or without, anthropogenic influence. The maximum extent of the last glaciation is marked as a discrete element concentration break, and a distinct difference occurs in element concentration levels between the soil of northern and southern Europe, most likely an effect of soil genesis, age and weathering. The Sb, W and Li concentrations in soil provide a general overview of element spatial distribution in relation to complexity of the underlying bedrock and element mobility in the surface environment at the continental-scale. The chemical composition of agricultural soil represents largely the primary mineralogy of the source bedrock, the effects of pre- and post-depositional chemical weathering, formation of secondary products, such as clays, and element mobility, either by leaching or mineral sorting. Observed geochemical patterns of Li, W and Sb can be often linked with known mineralisation as recorded in the ProMine Mineral Database, where elements in question occur either as main or secondary resources. Anthropogenic impact has only been identified locally, predominantly in the vicinity of large urban agglomerations. Unexplained high element concentrations may potentially indicate new sources for high-tech elements and should be investigated at a more detailed scale.Philippe Négrel, Anna Ladenberger, Clemens Reimann, Manfred Birke, Alecos Demetriades, Martiya Sadeghi, The GEMAS Project Tea

EuroGeoSurveys geochemical mapping of agricultural and grazing land soil of Europe (GEMAS). Field manual.

REACH (Registration, Evaluation and Authorisation of Chemicals), the new European Chemicals Regulation was adopted in December 2006. It came into force on the 1st June 2007. REACH, as well as the pending EU Soil Protection Directive, require additional knowledge about "soil quality" at the European scale. The GEMAS (geochemical mapping of agricultural soils and grazing land of Europe) project aims at providing harmonized geochemical data of arable land and land under permanent grass cover at the continental, European scale. Geological Surveys in 34 European countries, covering an area of 5.6 million km2, have agreed to sample their territory at a sample density of 1 site each, arable land (0-20 cm) and land under permanent grass cover (0-10 cm), per 2500 km2. Sampling will take place during 2008, following a jointly agreed field protocol which is presented in this report. All samples will be prepared in just one laboratory, a strict quality control procedure has been established and all samples will always be jointly analyzed in just one laboratory for any one chemical element/parameter

The EuroGeoSurveys geochemical mapping of agricultural and grazing land soils project (GEMAS) - Evaluation of quality control results of aqua regia extraction analysis.

Rigorous quality control (QC) is one of the keystones to the success of any regional geochemical mapping programme. For the EuroGeoSurveys (EGS) GEMAS (Geochemical mapping of agricultural and grazing land soils) project 2211 samples (including field duplicates) of agricultural soil (Ap, Ap-horizon, 0-20 cm) and 2118 samples (including field duplicates) from land under permanent grass cover ("grazing land" - Gr, topsoil 0-10 cm) were collected from a large part of Europe, centrally prepared (air dried, sieved to <2 mm, homogenised and split into sub-samples) and randomised prior to being sent out to contract laboratories. QC consisted of (1) collection of a field duplicate at a rate of 1 in 20 field samples, (2) preparation of two large project standards ("Ap" and "Gr") for insertion between the routine project samples, (3) preparation of an analytical replicate from each field duplicate and (4) randomisation of all samples prior to analysis. Here QC-results covering analysis of 53 chemical elements (Ag, Al, As, Au, B, Ba, Be, Bi, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, Ge, Hf, Hg, In, K, La, Li, Mg, Mn, Mo, Na, Nb, Ni, P, Pb, Pd, Pt, Rb, Re, S, Sb, Sc, Se, Sn, Sr, Ta, Te, Th, Ti, Tl, U, V, W, Y, Zn, Zr), following an aqua regia extraction on a 15 g aliquot per sample of both sample materials, are reported. Practical detection limits and precision, as well as the analytical results for the two project standards Ap and Gr are provided for all 53 elements. All analyses were carried out within twenty days at ACME laboratories in Vancouver, Canada. No serious quality problems, other than a few occasional outliers for a number of elements (B, Ca, and Sn) were detected, and the analytical results were accepted after investigating the reasons for these outliers

GEMAS: adaptation of weathering indices for European agricultural soil derived from carbonate parent materials

Carbonate rocks are very soluble and export elements in dissolved form, and precipitation of secondary phases can occur on a large scale. They leave a strong chemical signature in soil that can be quantified and classified by geochemical indices, and which is useful for evaluating chemical weathering trends (e.g. the Chemical Index of Alteration (CIA) or the Mafic Index of Alteration (MIA)). Due to contrasting chemical compositions and high Ca content, a special adaptation of classical weathering indices is necessary to interpret weathering trends in carbonate-derived soil. In fact, this adaptation seems to be a good tool for distinguishing weathering grades of source-rock types at the continental scale, and allows a more robust interpretation of soil parent-material weathering grade and its impact on the current chemical composition of soil. An increasing degree of weathering results in Al enrichment and Mg loss in addition to Fe loss and Si enrichment, leaching of mobile cations such as Ca and Na, and precipitation of Fe-oxides and hydroxides. The relation between soil weathering status and its spatial distribution in Europe provides important information about the role played by climate and terrain. The geographical distribution of soil chemistry contributes to a better understanding of soil nutritional status, element enrichment, degradation mechanisms, desertification, soil erosion and contamination