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Chemistry of Europe's Agricultural Soils, Part A: Methodology and Interpretation of the GEMAS Data Set

Series: Geologisches Jahrbuch Reihe B Volume: B 102

By: Clemens Reimann (Editor), Manfred Birke (Editor), Alecos Demetriades (Editor), Peter Filzmoser (Editor), Patrick DT O'Connor (Editor), Mart J van Bracht (Foreword By), Morten Smelror (Foreword By), Hans-Joachim Kümpel (Foreword By)

525 pages, colour & b/w illustrations , colour & b/w maps, colour tables, includes DVD-ROM

Schweizerbart Science Publishers

Paperback | Jan 2014 | #210749 | ISBN-13: 9783510968466
Availability: Usually dispatched within 1-2 weeks Details
NHBS Price: £130.00 $166/€155 approx

About this book

Language: English with bilingual summary in English and German

During 2008 and until early 2009, a total of 2108 samples of agricultural (ploughed land, 0–20 cm) and 2023 samples of grazing land (0–10 cm) soil were collected at a density of 1 site/2 500 km2 each from 33 European countries, covering an area of 5 600 000 km2. All samples were analysed for 52 chemical elements after an aqua regia extraction, 41 elements by XRF (total), and soil properties, like CEC, TOC, pH (CaCl2), following tight external quality control procedures. In addition, the agricultural soil samples were analysed for 57 elements in a mobile metal ion (MMI®) extraction, Pb isotopes and magnetic susceptibility. The GEMAS project thus provides for the first time fully harmonised data for element concentrations and soil properties known to influence the bioavailability and toxicity of the elements at the continental (European) scale. The provided database is fully in compliance with the requirements of the European REACH Regulation (Registration, Evaluation, Authorisation and Restriction of Chemicals).

The study also provides valuable information for other European pieces of legislation related to metals in soil.

The concentrations of many elements (e. g., As, Bi, Co, Cu, Li, Mn, Pb) in soils of north-eastern Europe are up to three times lower than in the South-West of Europe. The break in concentration occurs along the southern limit of the last glaciation and is thus directly related to geology. The variable geochemical background from north to south makes it impossible to define one soil background level for any chemical element that is valid for the whole of Europe. However, areas with increased metal concentrations can be clearly identified, and are most often associated with known mineral districts and mining areas. Some major cities (e.g., London, Paris) are marked by local anomalies of elements like Au, Hg and Pb, typically linked to anthropogenic activities. Element concentrations decrease rapidly towards the surrounding natural background with distance to any one anthropogenic source. For several elements (e. g., Hg, P, S, Se) the regional distribution patterns are strongly affected by climatic conditions favoring the development of organic soil. On all geochemical maps, the effect of diffuse contamination remains invisible at the chosen continental scale and sample density. To reliably detect contamination, mapping at a much higher sample density, i.e., at the local scale, is needed. Agricultural and grazing land soil samples show practically the same distribution patterns over Europe and very comparable element concentrations. This demonstrates the robustness of the low sample density geochemical mapping approach.


Contents

1 The GEMAS Project – Concept and Background 21
(Clemens Reimann, Alecos Demetriades, Manfred Birke & Ilse Schoeters)

2 REACH and GEMAS 25
(Violaine Verougstraete & Ilse Schoeters)

2.1 Regulatory background 25
2.2 REACH in practice 25
2.3 REACH implementation and the GEMAS project 26
2.4 Use of GEMAS data beyond REACH 27

3 Sample Material, Site Selection and Sampling 29
(Clemens Reimann)

3.1 Introduction 29
3.2 Sample site selection 31
3.3 Soil sampling 34


4 Preparation of GEMAS Project Samples and Standards 35
(Daniela Mackovych & Pavol Lucivjansky)

4.1 Introduction 35
4.2 Preparation of GEMAS soil samples 35
4.3 Preparation and testing of project standards 35

5 Analytical Methods used in the GEMAS Project 39
(Manfred Birke, Clemens Reimann & Karl Fabian)

5.1 Introduction 39
5.2 Analytical methods 39
5.2.1 pH (CaCl2) 39
5.2.2 Effective Cation Exchange Capacity – eCEC 39
5.2.3 Total C and S 40
5.2.4 Total Organic Carbon – TOC 40
5.2.5 Total element concentrations: XRF and LOI 40
5.2.6 Particle Size Distribution – PSD: A special story 41
5.2.7 Aqua regia extraction 42
5.2.8 Lead isotope ratios 43
5.2.9 MMI® extraction 43
5.2.10 Magnetic Susceptibility (Ms) 43

6 Evaluation of GEMAS Project Quality Control Results 45
(Alecos Demetriades, Clemens Reimann & Peter Filzmoser)

6.1 Introduction 45
6.2 Definition: What is actually ’good quality‘
for a geochemical mapping project? 46
6.3 Quality control procedures selected for the GEMAS project and selected results demonstrating the necessity of these procedures 47
6.3.1 Randomised samples 49
6.3.2 Accuracy, Trueness, Repeatability – the project standards 51
6.3.3 Precision – the project replicates 52
6.3.4 Practical detection limit and precision equation 52
6.3.5 Analysis of variance (ANOVA) 54
6.3.6 Trueness 55
6.4 Discussion and conclusion 57

7 Trueness of GEMAS Analytical Results – the Ring Test 59
(Clemens Reimann & Cornelia Kriete)

7.1 Introduction 59
7.2 Methodology 59
7.3 Results 60
7.4 Conclusions 63

8 Univariate Data Analysis and Mapping 65
(Peter Filzmoser, Clemens Reimann & Manfred Birke)

8.1 Introduction 65
8.2 Data tables 66
8.3 Data distribution 67
8.3.1 CP-plots 67
8.3.2 Boxplots 70
8.3.3 Combination of histogram, density trace, one-dimensional scattergram and boxplot 71
8.4 Comparison between data subsets 72
8.5 Scatterplots 74
8.6 Maps 76
8.6.1 Black and white symbol maps 76
8.6.2 Colour maps 77
8.6.3 clr(Element) maps 77
8.7 Conclusions 78

9 Multivariate Data Analysis 81
(Peter Filzmoser & Clemens Reimann)

9.1 Introduction 81
9.2 Cluster analysis 82
9.2.1 Variable (R-mode) clustering: Aqua regia data 83
9.2.2 Sample (Q-mode) clustering: Aqua regia data 83
9.3 Principal component analysis 85
9.3.1 PCA based on total (XRF) element concentrations 85
9.3.2 PCA based on aqua regia extraction results 87
9.4 Conclusions 89

10 Supporting Information for Interpretation of Geochemical Maps 91
(Manfred Birke, Uwe Rauch & Clemens Reimann)

10.1 Introduction 91
10.2 Maps supporting the interpretation of geochemical maps 91


11 Distribution of Elements/Parameters in Agricultural and Grazing Land Soil of Europe 101
(Clemens Reimann, Alecos Demetriades, Manfred Birke, Peter Filzmoser, Patrick O’Connor, Josip Halamić, Anna Ladenberger & the GEMAS Project Team)

11.1 Cation Exchange Capacity (CEC) 109
11.2 Chemical Index of Alteration (CIA) 113
11.3 Clay 117
11.4 Loss on ignition (LOI) 123
11.5 Soil acidity (pH) 127
11.6 Magnetic Susceptibility (MS) 131
11.7 Silver (Ag) 135
11.8 Aluminium (Al) 141
11.9 Arsenic (As) 147
11.10 Gold (Au) 155
11.11 Boron (B) 161
11.12 Barium (Ba) 167
11.13 Beryllium (Be) 173
11.14 Bismuth (Bi) 179
11.15 Carbon (C) 185
11.16 Calcium (Ca) 193
11.17 Cadmium (Cd) 199
11.18 Cerium (Ce) 205
11.19 Chlorine (Cl) 211
11.20 Cobalt (Co) 213
11.21 Chromium (Cr) 219
11.22 Cesium (Cs) 225
11.23 Copper (Cu) 231
11.24 Fluorine (F) 237
11.25 Iron (Fe) 239
11.26 Gallium (Ga) 245
11.27 Germanium (Ge) 251
11.28 Hafnium (Hf) 257
11.29 Mercury (Hg) 263
11.30 Indium (In) 269
11.31 Potassium (K) 275
11.32 Lanthanum (La) 281
11.33 Lithium (Li) 287
11.34 Magnesium (Mg) 293
11.35 Manganese (Mn) 299
11.36 Molybdenum (Mo) 305
11.37 Sodium (Na) 311
11.38 Niobium (Nb) 317
11.39 Nickel (Ni) 323
11.40 Phosphorus (P) 329
11.41 Lead (Pb) 335
11.42 Lead Isotopes (206Pb, 207Pb, 208Pb) 341
11.43 Palladium (Pd) 349
11.44 Platinum (Pt) 355
11.45 Rubidium (Rb) 361
11.46 Rhenium (Re) 367
11.47 Sulphur (S) 369
11.48 Antimony (Sb) 375
11.49 Scandium (Sc) 381
11.50 Selenium (Se) 387
11.51 Silicon (Si) 393
11.52 Tin (Sn) 399
11.53 Strontium (Sr) 405
11.54 Tantalum (Ta) 411
11.55 Tellurium (Te) 413
11.56 Thorium (Th) 419
11.57 Titanium (Ti) 425
11.58 Thallium (Tl) 431
11.59 Uranium (U) 437
11.60 Vanadium (V) 443
11.61 Tungsten (W) 449
11.62 Yttrium (Y) 455
11.63 Zinc (Zn) 461
11.64 Zirconium (Zr) 467

12 Discussion 473
(Clemens Reimann, Alecos Demetriades, Manfred Birke & Ilse Schoeters)

12.1 Influence of geology on element concentrations 476
12.2 Mineralisation 480
12.3 Further geochemical signals related to natural processes 481
12.4 Anthropogenic impact 483
12.5 Comparison between the two sample materials 485
12.6 Differences between the countries: element variation 488
12.7 Availability of the elements in the different extractions 490
12.8 Element deficiency and toxicity 490
12.9 Comparison with upper continental crust values and results from other continental-scale soil surveys 495

13 Conclusions 497

References 501

Acronyms and Abbreviations 517


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