Chemistry of Europe's Agricultural Soils Part A + B (2 Volume set)
Synopsis
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/2500 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 consists of two parts (Part A: Methodology and Interpretation of the GEMAS Data Set and Part B: General Background Information and Further Analysis of the GEMAS Data Set) and provides information also valuable research and 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 clear- ly 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.
Table of contents Part A / Part B
PART A
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
PART B
General Background Information 19
1 A Short Guide to Soil Formation and the Soils of Europe 21
(Edith Haslinger, Clemens Reimann & Manfred Birke)
1.1 Introduction 21
1.2 Soil – what is it? 21
1.3 Soil – an eco-friendly chemical factory 27
1.4 Does soil always stay the same? 30
1.5 How many soil types are there? 36
1.6 Use of GEMAS data 42
2 Geology of Europe 47
(Fabian Jähne)
2.1 Introduction 47
2.2 The European plate tectonic evolution
in the Phanerozoic 49
2.3 The crustal framework of Europe – distribution of terranes and tectonic plates 50
2.4 Igneous rocks of Europe 56
2.5 Sedimentary basin evolution in Europe from the Palaeozoic to the Caenozoic 61
2.6 Major faults and fracture zones of Europe 64
2.7 Impact structures of Europe 66
2.8 Quaternary development of Europe 69
3 Mineral Deposits of Europe 71
(Alecos Demetriades & Clemens Reimann)
3.1 Introduction 71
3.2 Mineral deposit and mineralisation maps 71
Applied Geochemistry of Selected Elements 79
4 Arsenic Anomalies in European Agricultural and Grazing Land Soil 81
(Timo Tarvainen, Manfred Birke, Clemens Reimann,
Michal Poňavič & Stefano Albanese)
4.1 Introduction 81
4.2 Materials and methods 81
4.3 Results 82
4.4 Discussion 83
4.5 Conclusions 88
5 Distribution of Cadmium in European Agricultural and Grazing Land Soil 89
(Manfred Birke, Clemens Reimann, Uwe Rauch, Benedetto De Vivo,
Josip Halamić, Volodymyr Klos, Mateja Gosar & Anna Ladenberger)
5.1 Introduction 89
5.2 Occurrence and sources 90
5.3 Production and use 92
5.4 Vegetation and aquatic biota 93
5.5 Health implications and ecotoxicology 93
5.6 Survey area 94
5.7 Results 94
5.8 Discussion 108
5.9 Conclusions 114
6 Carbon Concentrations in European Agricultural and Grazing Land Soil 117
(Rainer Baritz, Vibeke Ernstsen & Dietmar Zirlewagen)
6.1 Introduction 117
6.2 Materials and methods 118
6.3 Results 122
6.4 Discussion 127
6.5 Conclusions 128
7 Distribution of Selenium in European Agricultural and Grazing Land Soil 131
(Michal Poňavič & Andreas Scheib)
7.1 Introduction 131
7.2 Selenium 131
7.3 Results 135
7.4 Discussion 138
7.5 Conclusions 144
8 Natural Radioactive Elements Uranium, Thorium and Potassium in European Agricultural and Grazing Land Soil 145
(Domenico Cicchella, Stefano Albanese, Manfred Birke,
Benedetto De Vivo, Walter De Vos, Enrico Dinelli, Annamaria Lima,
Patrick J. O’Connor, Ignace Salpeteur & Timo Tarvainen)
8.1 Introduction 145
8.2 Geochemical features 146
8.3 Health effects 147
8.4 Uses 148
8.5 Results and discussion 150
8.6 Conclusions 156
9 Distribution of Aeolian Deposits in Europe and Their Influence on Soil Geochemistry 161
(Andreas Scheib)
9.1 Introduction 161
9.2 Aeolian deposits in Europe 161
9.3 Influence of aeolian deposits on soil geochemistry 163
9.4 Conclusions 168
10 Distribution of Boron, Chlorine and Fluorine in European Topsoil and Subsoil
(based on samples from the FOREGS project) 169
(Reijo Salminen, Manfred Birke, Clemens Reimann,
Virgilija Gregorauskiene & Xueqiu Wang)
10.1 Introduction 169
10.2 Methods 172
10.3 Results 174
10.4 Discussion 176
10.5 Conclusions 180
10.6 Mobility and Risk Assessment of Metals 181
11 Prediction of Metal and Metalloid Partitioning Coefficients (Kd) in Soil Using Mid-Infrared Diffuse Reflectance Spectroscopy 183
Les J. Janik, Sean Forrester, Jason K. Kirby, Michael J. McLaughlin,
Jose M. Soriano-Disla & Clemens Reimann)
11.1 Introduction 183
11.2 Partial-least-squares models 184
11.3 Prediction of Kd values from DRIFT+pH models 185
11.4 Conclusions 188
12 Use of Monitoring Data for Risk Assessment of Metals in Soil under the European REACH Regulation 189
(Koen Oorts & Ilse Schoeters)
12.1 Introduction 189
12.2 Materials and methods 191
12.3 Results 194
12.4 Discussion 199
12.5 Conclusions 202
13 Mobile Metal Ion Analysis of European Agricultural Soil 203
(Alan Mann, Clemens Reimann, Patrice de Caritat & Nicholas Turner)
13.1 Introduction 203
13.2 Analysis and quality control 204
13.3 Results 205
13.4 Comparison of results with other data sets 220
13.5 Discussion and conclusions 227
Regional Interpretation of GEMAS Data 233
14 Elemental Patterns in Agricultural and Grazing
Land Soil in Norway, Finland and Sweden:
What Have We Learned from Continental-Scale Mapping? 235
(Anna Ladenberger, Jo Uhlbäck, Madelen Andersson, Clemens Reimann,
Timo Tarvainen, George Morris, Martiya Sadeghi, Mikael Eklund &
Peter Filzmoser)
14.1 Introduction 235
14.2 Topography and climate 235
14.3 Geology 236
14.4 Human impact on agricultural land 239
14.5 Sampling and methodology 240
14.6 Discussion 240
14.7 Conclusions 251
15 Geochemical Characteristics of Ukrainian Soil Using Landscape-Geochemical Regionalisation Based on the GEMAS Data 253
(Volodymyr Klos, Manfred Birke, Grygorii Akinfiev & Yulia Amashukeli)
15.1 Introduction 253
15.2 Materials and methods 254
15.3 Results and discussion 256
15.4 Conclusions 270
References 273
Acronyms and Abbreviations 295
Appendices 297
A Soil Guideline Values (SGVs) for Agricultural
and Grazing Land Soil in Different European Countries 299
B GEMAS Project: Statistical Parameters for All of Europe
(Ap and Gr samples) 307
C GEMAS Project: Statistical Parameters of Northern
and Southern Europe (Ap samples) 327