Clemens ReimannManfred Birke (eds.)

Geochemistry of Geochemistry of European Bottled WaterEuropean Bottled Water

Borntraeger Science Publishers

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Geochemistry of European Bottled WaterEdited by:Clemens ReimannGeological Survey of Norway (NGU)EuroGeoSurveys Geochemistry Expert Group, Norway

and

Manfred BirkeFederal Institute for Geosciences and Natural Resources (BGR), Germany

Back cover������������� ���� ������

ISBN 978-3-443-01067-6

Information on this title: www.borntraeger-cramer.com/9783443010676

© 2010 Gebr. Borntraeger Verlagsbuchhandlung, Stuttgart, Germany©

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted,in any form or by any means, electronic, mechanical photocopying, recording, or otherwise, without the prior written permission of Gebr. Borntraeger Verlagsbuchhandlung.

Bottled waters (=groundwaters) are natural substances and as such subject to numerous infl uences. There-fore their compositions may be subject to change with time.yThe water compositional data published in this book were determined with utmost care, using state-of-the-artanalytical equipment and refl ect the water compositions at the time of analysis.

Publisher: Gebr. Borntraeger VerlagsbuchhandlungJohannesstr. 3A, 70176 Stuttgart, Germanymail@borntraeger-cramer.dewww.borntraeger-cramer.de

� Printed on permanent paper conforming to ISO 9706-1994

Typesetting DTP + TEXT Eva Burri, Stuttgart, GermanyPrinted in Germany by Gulde Druck GmbH, Tübingen, Germany

1: The growth of the bottled water market in Germany, Hungary, Italy and Sweden from 1950–2010, see p. 7.

2: A well-dressing at the Derbyshire village of Barlow, England see p. 9. 3: ICP-QMS 7500 used for several analyses, © 2010 Agilent Technologies, Inc.

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III

Table of ContentsProject Staff ............................................................................................................................................... VForeword by the Secretary General of EuroGeoSurveys .......................................................................... IXForeword by the President of the Federal Institute for Geosciences and Natural Resources,

Germany and the Director of the Geological Survey of Norway .................................................... XIAbstract ..................................................................................................................................................... 1

1 Introduction............................................................................................................................... 31.1 The Concept of the “Geochemistry of European Bottled Water” Project ....................................... 31.2 What is Groundwater? ................................................................................................................... 41.3 What is Mineral Water? .................................................................................................................. 51.3.1 From Mineral Water Springs and Spas to the Bottled Water Market.............................................. 61.4 The Legal Framework: Bottled Waters, Spring Waters and Mineral Waters................................... 71.4.1 Natural Mineral Water .................................................................................................................... 81.4.2 Spring Water .................................................................................................................................. 111.4.3 Other Bottled Water / Table Water.................................................................................................. 111.4.4 Medicinal Waters ........................................................................................................................... 111.5 What does this Atlas Represent? .................................................................................................. 11

2 The Hydrochemistry of Groundwater............................................................................... 132.1 The Infl uence of Rainfall ................................................................................................................ 132.2 The Infl uence of Vegetation ........................................................................................................... 132.3 The Infl uence of Soil ...................................................................................................................... 132.4 Acid-Base Reactions ..................................................................................................................... 142.5 Dissolution Reactions .................................................................................................................... 142.6 Redox Reactions ........................................................................................................................... 142.7 Mixing with deep Saline Waters ..................................................................................................... 152.8 Carbon Dioxide .............................................................................................................................. 152.9 Water Types ................................................................................................................................... 15

3 Background Information....................................................................................................... 173.1 Topography .................................................................................................................................... 173.2 Geology ......................................................................................................................................... 173.2.1 Mineral Deposits of Europe ........................................................................................................... 223.2.2 Hydrogeological map of Europe .................................................................................................... 233.3 Soil ................................................................................................................................................. 233.4 Climate ........................................................................................................................................... 243.5 Vegetation and Land Use .............................................................................................................. 253.6 Human Activities ............................................................................................................................ 25

4 Methods...................................................................................................................................... 294.1 Sampling ........................................................................................................................................ 294.2 Analyses ........................................................................................................................................ 294.2.1 Sample preparation ....................................................................................................................... 334.2.2 ICP-QMS analyses ........................................................................................................................ 334.2.3 ICP-AES analyses ......................................................................................................................... 344.2.4 Atomic fl uorescence spectrometry (AFS) ...................................................................................... 354.2.5 Ion Chromatography (IC) ............................................................................................................... 354.2.6 Photometric analyses .................................................................................................................... 354.2.7 Titration .......................................................................................................................................... 354.2.8 Potentiometry................................................................................................................................. 354.2.9 Conductometry .............................................................................................................................. 35

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IV Table of Contents

4.3 Quality Control ............................................................................................................................... 354.3.1 International Reference Materials .................................................................................................. 364.3.2 The in-house MinWas project standard ......................................................................................... 364.3.3 Sample blanks ............................................................................................................................... 364.3.4 Detection limits .............................................................................................................................. 364.3.5 Duplicate analyses ......................................................................................................................... 434.3.6 Comparison of analytical results with the water composition provided on the labels .................... 434.3.7 Re-analyses of selected samples .................................................................................................. 444.4 Possible Problems with the Data in Terms of Representing True “Groundwater Quality”

or being able to Refl ect “Geology” ................................................................................................. 464.4.1 Bottle leaching ............................................................................................................................... 464.4.2 The effect of carbonatisation ......................................................................................................... 484.4.3 Other forms of water treatment ...................................................................................................... 484.4.4 Further possible disturbing factors................................................................................................. 514.5 Data Analysis and Mapping ........................................................................................................... 51

5 Datasets ..................................................................................................................................... 525.1 Bottled Water ................................................................................................................................. 525.2 European Tap Water ...................................................................................................................... 525.3 Other Datasets............................................................................................................................... 52

6 Comparing Bottled Water with European Tap Water, Hardrock Groundwater from Norway and European Surface Water .................................................................... 53

7 Maps and their Interpretation ............................................................................................. 63

8 Health Implications................................................................................................................. 2018.1 Elements with established MAC-Values for Mineral Water

(EU Directive 2003/40/EC Mineral Water) ..................................................................................... 202Antimony, p. 202; Arsenic, p. 202; Barium, p. 203; Cadmium, p. 203; Chromium, p. 203; Copper, p. 203; Fluoride, p. 204; Lead, p. 204; Manganese, p. 204; Mercury, p. 204; Nickel, p. 205; Nitrate, p. 205; Nitrite, p. 205; Selenium, p. 205

8.2 Elements (Parameters) with Established MAC (or Guideline)-Values for Drinking Water (EC Directive 98/83/EC) but not for Mineral Water ........................................................................ 205Aluminium, p. 205; Ammonium, p. 206; Boron, p. 206; Chloride, p. 206; Electrical conductivity (EC), p. 206; Iron, p. 206; pH-value, p. 206; Sodium, p. 206; Sulphate, p. 207

8.3 Elements with non-EU Drinking Water MAC Values ...................................................................... 207Silver, p. 207; Beryllium, p. 207; Molybdenum, p. 207; Strontium, p. 207; Thallium, p. 207; Uranium, p. 207; Vanadium, p. 208; Zinc, p. 208

8.4 Other Health-Relevant Elements ................................................................................................... 208Iodine, p. 208; Lithium (Rubidium, Caesium), p. 208; Rare Earth Elements, p. 209;Thorium, p. 209

8.5 Additional Remarks ....................................................................................................................... 209

9 Conclusions .............................................................................................................................. 211

References ................................................................................................................................................ 213

Appendix A (Table of Water Action Levels as defi ned by the EU and for the majority of Countries from which water samples are included in this study) ................................................................... 221

Appendix B (Statistical summary table for the datasets used in this Atlas) ............................................... 251

Contents included on the Data CD-ROM .................................................................................................. 268

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V

Project Staff

Project management:Manfred Birke, Federal Institute for Geosciences and Natural Resources (BGR), GermanyClemens Reimann, Geological Survey of Norway (NGU), Chairman EuroGeoSurveys Geochemistry Expert Group, Norway

Preparation of Atlas Manuscript:Clemens Reimann, NGUDavid Banks, Holymoor Consultancy Ltd., Chesterfi eld, U.K.Manfred Birke, BGRAlecos Demetriades, IGME

Analyses:Manfred Birke, Hans Lorenz, Wolfgang Glatte, Bodo Harazim, Fred Flohr, Anna Degtjarev, Jürgen Rausch,Federal Institute for Geosciences and Natural Resources, Germany

Statistics and R-Scripts:Peter Filzmoser, Institute of Statistics and Probability Theory, Vienna University of Technology, Austria

Geology:Fabian Jähne, Federal Institute for Geosciences and Natural Resources, Germany

General information maps:Ola Eggen, NGU; Marianthi Stefouli, IGME (digital processing of Global Land cover map), Uwe Rauch, BGR(topography)

Hydrogeology:David Banks, Holymoor Consultancy Ltd., Chesterfi eld; Christophe Innocent, BRGM; Bjørn Frengstad, NGU, Carla Lourenço, LNEG ex-INETI; Pauline Smedley, BGS

With input (sampling and interpretation) from the following Country Teams:

AlbaniaFriedrich Koller, University of Vienna (sampling)Kujtim Onuzi, Institute of Geoscience, Technical University of Tirana

AustriaGerhard Hobiger, Albert Schedl, Geological Survey of Austria (GBA)Edith Haslinger, Austrian Institute of Technology (AIT)Peter Filzmoser, Vienna University of TechnologyFriedrich Koller, University of Vienna

BelarusPeter Filzmoser, Vienna University of Technology (sampling)Virgilija Gregorauskiene, Lithuanian Geological Survey (sampling)

BelgiumWalter De Vos, Geological Survey of Belgium (interpretation)Ilse Schoeters, Rio Tinto Minerals (sampling)Clemens Reimann, NGU (sampling)

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VI Project Staff

Bosnia & HerzegovinaHazim Hrvatovic, Neven Miosic, Ferid Skopljak, Natalija Samardzic, Geological Survey of the Federation ofBosnia and Herzegovina

BulgariaValeri Trendavilov, Dept. of Geology and Permits for Exploration, Subsurface and Underground Resources Offi ce, Ministry of Environment and Water

CroatiaJosip Halamić, Ajka Šorša, Croatian Geological Survey

Czech RepublicMiloslav Duris, Czech Geological Survey

CyprusAlecos Demetriades, Hellas for Cyprus Geological Survey Department

DenmarkRolf Tore Ottesen and Clemens Reimann, NGU (sampling)

EstoniaJaan Kivisilla, Valter Petersell, Geological Survey of EstoniaLiida Bityukova, Institute of Geology at Tallinn University of Technology, Estonia

FinlandTimo Tarvainen, Jaana Jarva, Geological Survey of Finland

Former Yugoslavian Republic of Macedonia (F.Y.R.O.M.)Trajce Stafi lov, Sts. Cyril and Methodius University, Skopje

FranceIgnace Salpeteur, Christophe Innocent, BRGM

GermanyManfred Birke, Uwe Rauch, Lars Kaste, Hans Lorenz, Federal Institute for Geosciences and Natural Resour-ces (BGR), Germany

HellasAlecos Demetriades, Institute of Geology and Mineral Exploration (IGME)

HungaryGyozo Jordan, Ubul Fugedi, Laszlo Kuti, Geological Institute of Hungary (MAFI)

IcelandBørge Johannes Wigum, Mannvit hf

IrelandRaymond Flynn, Queen’s University Belfast, Northern IrelandManfred Birke, BGR (sampling)

ItalyBenedetto De Vivo, Annamaria Lima, Stefano Albanese, University of Napoli Federico II;Domenico Cicchella, University of Sannio; Enrico Dinelli, University of Bologna; Paolo Valera, University ofCagliari

LatviaAivars Gilucis, Latvian Environment, Geology and Meteorology Agency

LithuaniaVirgilija Gregorauskiene, Lithuanian Geological Survey

LuxembourgRobert Maquil, Service Géologique du Luxembourg (SGL)

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Project Staff VII

MoldovaMaria Titovet, Ministry for Ecology and Nature of Republic Moldova, Department of Hydrogeology

MontenegroNeda Devic, Geological Survey of Montenegro

Netherlands, TheRolf Tore Ottesen, Clemens Reimann, NGU (sampling)

NorwayBjørn Frengstad, Rolf Tore Ottesen, Clemens Reimann, Geological Survey of Norway (NGU)

PolandLech Smietanski, Polish Geological Institute, Warsaw

PortugalCarla Lourenço, Maria Joao Batista, Laboratório Nacional de Energia e Geologia, I. P. (LNEG ex-INETI)

RomaniaAdriana Ion, Geological Institute of Romania Corina Ionesco, University of Cluj-Napoca

RussiaNikolay Phillipov, SC MineralOlga Karnachuk, Tomsk State UniversityReijo Salminen, Geological Survey of Finland (sampling)

SerbiaMilena Zlokolica-Mandic, Tanja Petrovic, Aleksandra Gulan, Geological Institute of Serbia; Nebojsa Veljkovic, Serbian Environmental Protection Agency

SlovakiaPeter Malik, State Geological Institute of Dionyz Stur, Bratislava

SloveniaMateja Gosar, Geological Survey of Slovenia

SpainJuan Locutura, Alejandro Bel-lan, Mar Corral, Instituto Geologico y Minero de Espana (IGME).

SwedenKaj Lax, Madelen Andersson, Geological Survey of Sweden (SGU)

SwitzerlandPeter Hayoz, Federal Offi ce of Topography, Swiss Geological Survey

TurkeyManfred Birke, BGR (sampling), Clemens Reimann, NGU (sampling)

UkraineBoris I. Malyuk, Volodymyr Klos, Maryna Vladymyrova, Geological Survey of Ukraine

United KingdomDee Flight, Shaun Reeder, Pauline Smedley, British Geological SurveyDavid Banks, Holymoor Consultancy Ltd.

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IX

Foreword by the Secretary General of EuroGeoSurveys

the Soil Map of Europe (Jones et al., 2005) or theresults of the Corine Land Cover project (GLC2000database, 2003).

From 1996 to 2006 twenty-six European Geolo-gical Surveys cooperated to produce the “Geoche-mical Atlas of Europe” (Salminen et al., 2005; DeVos et al., 2006), presenting for the fi rst time directlycomparable data of the chemical composition of top-and sub-soil, stream water, stream sediment andfl oodplain sediment at the European scale. With thepublication of the two atlas volumes, the datasetswere made publicly available and are now used in awide variety of applications by diverse organisationsthroughout Europe, including European Commissi-on institutions. Although each country has its ownnational database on groundwater quality with whichit makes management and regulatory decisions, adirectly comparable dataset on natural groundwa-ter quality at the European scale is not available.A pan-European harmonised dataset of naturalgroundwater quality would contribute signifi cantlyto an understanding of groundwater quality across Europe and may support implementation of the EU Water Framework Directive.

Collecting representative groundwater samp-les at the European scale is not an easy task (see discussion in this atlas), and may be prohibitively expensive, if done at a high sample density. It was because of this that one of the members of the Euro-GeoSurveys Geochemistry Expert Group, Dr. Man-fred Birke, put forward the idea that “groundwater” can be sampled by purchasing bottled waters from supermarkets over all of Europe, and suggested to use the EuroGeoSurveys’ network to collect bottled water as a fi rst proxy for groundwater.

Though the idea met some resistance, it was inthe end decided that it was worth a try. The present atlas is the result of this rather unusual, and some-what innovative, project. This volume could be con-sidered as the third in the EuroGeoSurveys series of “Geochemical Atlases of Europe”. Results show the enormous variation of many chemical elements in bottled water derived from groundwater at the Eu-ropean scale, usually 3 to 4 and up to 7 orders of magnitude. The importance of geology in controlling natural water chemistry is clear – a fact that needs

EuroGeoSurveys (EGS) represents 32 European Geological Surveys with a staff of over 20,000 spe-cialists working in numerous applications of geosci-ences for EU society and economy. EuroGeoSur-veys is a not-for-profi t association working solely for the public interest. EGS aims at providing the European Institutions with expert, neutral, balanced and practical pan-European advice and information as an aid to problem-solving, policy, regulatory and programme formulation in areas such as:• the use and the management of on- and off-shore

natural resources related to the subsurface of theEarth, (energy, including the renewable geother-mal energy; minerals and water, soils, under-ground space and land);

• the identifi cation of natural hazards of geological origin, their monitoring and the mitigation of their impacts (depletion or excess of trace elementsin soils and waters, earthquakes, natural emissi-ons of hazardous gases, landslides and rockfalls,land heave and subsidence, shrinking and swel-ling clays;

• environmental management, waste management and disposal; land-use planning;

• sustainable urban development and safe const-ruction;

• e-government and the access to geoscientifi c metadata and data;

• the development of interoperable and harmo-nised geoscientifi c data at the European scale.

The portal of EGS (http://www.eurogeosurveys.org/)provides access to geoscientifi c metadata, informa-tion and knowledge at European and national sca-les, following the links on the thematic pages. It alsopresents information on EuroGeoSurveys its activi-ties and Member Organisations.

Geology knows no borders. However, up todate most investigations of the national Geological Surveys stop at political country borders. Yet, at the same time the administration of the EU urgently re-quires for its policy directly comparable data and in-formation at the European scale, an overview for the whole continent. For some issues, overview maps at the continental scale already exist; examples arethe Geological Map of Europe (Asch, 2003), the Hy-drogeological Map of Europe (IHME1500, 2008),

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X Foreword by the Secretary General of EuroGeoSurveys

to be considered in all discussions about “contami-nation” and when managing groundwater.

The analytical results are made available to-gether with this atlas, and we hope that they will beof general interest across Europe and, may be forresearch and teaching purposes at universities. Un-

til now, there has not been a “groundwater” datasetcovering such a large area in Europe where all sam-ples were analysed in just one laboratory and which delivers directly comparable results for so many pa-rameters.

Luca DemicheliEuroGeoSurveys Secretary GeneralEuroGeoSurveys Offi ceRue Joseph II 36–381000 Brussels, BelgiumTel : +32 2 888 75 52; +32 2 888 75 53Fax : +32 2 503 50 25E-mail: luca.demicheli@eurogeosurveys.orginfo@eurogeosurveys.org URL: http://www.eurogeosurveys.org/

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XI

Foreword by the President of the Federal Institute for Geo-sciences and Natural Resources, Germany and the Director of the Geological Survey of Norway

The Science of geochemistry aims to quantitativelydetermine the chemical composition of the Earth andits parts and to discover the factors that control the distribution of the individual elements (Goldschmidt,1937, 1954). Applied geochemistry is the application of this knowledge to societal benefi t, whether for dis-covering mineral resources, protecting the surfaceenvironment that sustains life, improving the effi ci-ency of agriculture and animal husbandry, or study-ing the behaviour of elements in the food-chain and their health effects on humans (epidemiology) andother biota.

Traditionally geochemical surveys have beencarried out at a very high density, based on the argu-ment that natural variation is very high even in smallareas. Only during the last decade, has low-density geochemistry (1 sample site per several hundred toten thousand km2) covering whole continents seena breakthrough (Garrett et al., 2008; Smith and Rei-mann, 2008), delivering much needed information about the processes dominating the geochemicaldistribution of elements at the Earth’s surface at the continental scale.

Working at the continental scale is still not a tri-vial task in Europe; geochemical surveys are mostoften carried out at the national scale and are notcomparable across political borders. At the same time the political landscape in Europe is rapidlychanging and databases that are directly compara-ble at the European scale are needed for important political decisions. High quality geochemical data-bases are an essential component of environmentalknowledge; they provide pertinent information for administrative and legal issues. Sustainable ma-nagement of European resources depends on re-liable databases like those provided in the Geoche-mical Atlas of Europe series (Salminen et al., 2005; De Vos et al., 2006) and continued with this volume.

The statistics and maps provided in this book are stimulating and prove the importance of geolo-gy in controlling the natural chemical composition ofgroundwater. For many elements the natural variati-on in element concentration is enormous and surpri-singly clear distribution patterns emerge that can bedirectly linked to certain bedrock types or geologicalprocesses.

Hans-Joachim Kümpel, President, Federal Institute for Geosciencesand Natural Resources, Hannover

Morten Smelror, Director,Geological Survey of NorwayTrondheimTrondheim

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1

AbstractAs of the start of the year 2010, 1916 “mineral water” brands are offi cially registered in Europe. Bottled water (usually derived from groundwater) is rapidlydeveloping into the main drinking water supply for the general population in large parts of the conti-nent. Analysis of bottled water may thus provide a cheap possibility to gain an idea about groundwa-ter chemistry at the European scale. For this study,1785 bottled water “samples” were purchased, rep-resenting 1247 wells at 884 locations and analyzed for more than 70 parameters. The dataset is used to gain a fi rst impression about the natural concentra-tions of, and variations in, the determined chemicalelements and additional parameters in groundwater at a European scale.

Many processes affect the hydrochemical fi n-gerprint of groundwater – important factors include:rainfall chemistry, climate, vegetation and soil zone processes, mineral-water interactions, groundwater residence time and the mineralogy and chemistryof the aquifer (and contamination). The infl uence of geology in determining element concentrationsin bottled water can be observed for a signifi cantnumber of elements. Examples include: high values of chromium (Cr) clearly related to the occurrence of ophiolites; beryllium (Be), caesium (Cs), germanium (Ge), potassium (K), lithium (Li) and rubidium (Rb) showing unusually high values in areas underlain by Hercynian granites while high values of aluminium

(Al), arsenic (As), fl uorine (F), potassium (K), ru-bidium (Rb) and silicon (Si) in the bottled water are related to the occurrence of alkaline volcanic rocks. A further key observation is that knowledge of geol-ogy alone is inadequate to predict the hydrochem-istry of bottled water: natural variation is enormous, usually three to four and for some elements up to seven orders of magnitude. Such variation may re-fl ect, among other factors, groundwater residence time and mixing with deep brackish formation wa-ters. It has also been found that bottle materials can have an infl uence on bottled water chemistry. For antimony (Sb), leaching from the bottle material is so serious that the results for bottled water cannot be used as an indication of natural concentrations in groundwater.

Some elements, as observed in the bottled wa-ter, are clearly not representative of typical, shal-low, fresh groundwater; rather, they tend to exhibit unusually high concentrations, typical for “mineral water”: examples are boron (B), beryllium (Be), bro-mine (Br), caesium (Cs), fl uorine (F), germanium (Ge), lithium (Li), rubidium (Rb), tellurium (Te), and zirconium (Zr).

Very few analysed samples (in general less than 1%) returned values exceeding maximum admissi-ble concentrations (MACs) for “mineral water”, as defi ned by the European Commission.

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3

1 Introduction

1.1 The Concept of the “Geochemistry of European Bottled Water” Project

In 2005 the Forum of European Geological Surveys(FOREGS), now EuroGeoSurveys (EGS), published the Geochemical Atlas of Europe (Salminen et al., 2005), followed in 2006 by an interpretation volume (De Vos et al., 2006). These volumes presented for the fi rst time directly comparable chemical analy-ses (more than 50 elements) in fi ve principal sam-ple materials (surface (stream) water, stream andfl oodplain sediments, top- and sub-soil) at the Eu-ropean scale. The Atlas clearly demonstrated that the geochemical patterns observed at a continen-tal scale are, contrary to common opinion, almostcompletely governed by natural sources and proc-esses. One of the great surprises observed was amajor discontinuity in concentration levels for the majority of chemical elements along the border ofthe last glacial maximum, with much lower element concentrations (often by a factor of ca. 3) observed in most sample materials and for the majority ofelements in Northern Europe when compared toSouthern Europe. Thus at least two strongly differ-ent geochemical background regimes (Reimannand Garrett, 2005) are observed at the Europeanscale. Comparable geochemical background data at the European scale are urgently needed by regula-tors for setting action levels or for judging the impactof contamination on the natural environment. In the FOREGS atlas (Salminen et al., 2005; De Vos et al., 2006) a missing, but rather important, sample mate-rial is groundwater.

Groundwater is a diffi cult sample material for geochemical mapping projects for a variety of rea-sons:(1) The location of wells is irregular, depending on

where people live and population density and permeability of underlying aquifers – geochemi-cal maps with a high sample density in smallareas and large gaps in between will never beaesthetically “pleasing” and the data are often not suitable for the construction of smoothed surface maps (Reimann, 2003).

(2) Different groundwater chemistry may be ob-served at different depths at one and the samesite, depending on well depth (several aquifersmay exist at one and the same location). For example groundwater may be abstracted from

shallow springs or deep boreholes; from shallow Quaternary glaciofl uvial sedimentary aquifers or from deep crystalline hard rock aquifers, at one and the same location.

(3) The residence time of the groundwater can dif-fer substantially from well to well. Even the waterabstracted from a single well can represent a mixture of groundwaters with differing residence times, derived from different fl ow horizons or fractures.

(4) Groundwater chemistry can vary seasonally and from year to year.

(5) Water wells can be differently constructed, ac-cording to local culture and perceived best practice; the groundwater may thus come intocontact with different construction materials, wa-ter pipes and installations. It is therefore almost inevitable that the water will be, in some sense, contaminated already before sampling.

(6) Access to many wells can often be quite diffi cult.

Many of the above difficulties appear to have no ob-fivious solution, and one might be tempted to give up on the idea of constructing a comparable ground-water geochemistry database at the European scale. Such a database would, however, be highly desirable and is actually required, for example, in connection with the European Water Framework Directive (EU directive 2000/60/EC) and the new groundwater directive (EU directive 2008/32/EC). At present, natural variation in groundwater qual-ity is not well understood due to lack of compatible groundwater data across Europe. Water legislation is dominantly focussed on regulating contamina-tion, while natural variation and natural risks may not always be suffi ciently recognized. Though many surveys of groundwater quality exist at the country scale (see Edmunds and Shand, 2008 for a general overview and: Edmunds et al., 1989; Lahermo et al., 1990; Schleyer and Kerndorff, 1992; Aastrup et al., 1995; Rapant et al., 1996; Frengstad et al., 2000; Tarvainen et al., 2001; Serra et al., 2003; Roux and Pointet, 2005; Brenot et al., 2007; Shand et al., 2007 for examples of detailed studies), good and directly comparable data at the European scale are missing. It is a central task of Geological Surveys to docu-ment the natural variation of chemical elements in a wide selection of sample materials, starting with bedrock, but including stream and fl oodplain sedi-

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4 Introduction

ments, marine sediments, surface and groundwater, soils and even vegetation.

At a meeting of the EGS Geochemistry Expert Group, it was suggested that it might be very easyand relatively cheap to obtain a first overview of fi“European Groundwater Geochemistry”, elementconcentrations and variation at the European scale,by purchasing and analysing commercially availablebottled water (i.e. mineral water and spring water). Almost 2000 (1916) natural mineral water brands are named in the offi cial list recognized by the Member fiStates of the European Union (see http://ec.europa.eu/food/food/labellingnutrition/water/mw_eulist_en.pdf – last accessed: 05.03.2010). During thepast 20 years it has become highly fashionable todrink bottled water and never before have so many groundwater sources (wells and springs) been in production and on the market. Hence groundwater “as drunk” can be easily sampled because it is sold “pre-packaged and analysis-ready” in supermarketsall over Europe. The EGS Geochemistry Expert Group has representatives in all European countries. It was decided to use this network to buy as many dif-ferent water samples as possible throughout Europe and to ship all samples to one central laboratory,yyequipped and capable to analyze these samples with the required low detection limits for many of the trace elements. There exist already numerous publications on the chemical composition of mineral (bottled) wa-ter (e.g., Misund et al., 1999; Dabecka et al., 2002; Lau and Luk, 2002; Van der Aa, 2003; Rosborg etal., 2005; Karamanis et al., 2007; Shotyk et al., 2006;Soupioni et al., 2006; Shotyk and Krachler, 2007a,b;Baba et al., 2008; Naddeo et al., 2008; Güler and Al-paslan, 2009; Krachler and Shotyk, 2009; Bertoldi et al., 2010), but the focus of the vast majority of these studies was on MACs and health issues and not onthe importance of geology for the observed elementconcentrations. Furthermore none of these studies presents data for as many samples analyzed for asmany parameters as provided here.

Of course, a number of additional problems were subsequently identifi ed when planning to use water sold in a variety of different bottle types forultra trace element analysis:(1) Bottled water may be treated (though only rather

limited treatment is allowed by law for springand mineral water); for example, carbon dioxide may be added (or removed), certain “unstable” elements such as iron, manganese, arsenic andsulphur may be removed (and, with the remov-al of these, a range of minor elements may be scavenged from the water). Water from severalsources may, occasionally, be mixed to dilutethe concentrations of certain critical elements. Treatment should be, but is not necessarily, indi-cated on the labels.

(2) Geochemists are well aware that bottle material may contaminate the water stored in the bottles (e.g. Hall, 1998; Reimann et al., 1999, 2007). Contamination may differ from bottle type to bottle type – European bottled waters are sold in soft polyethylene terephthalate (PET) bottles, in hard PET bottles, in glass bottles and even in Al-containers or tetrapacks. All these bottles are in addition marketed in a variety of colours and sizes.

(3) Mineral and spring water must be produced froma protected source (and such sources are often relatively deep) and may thus not refl ect the real extent of contamination, especially of shallow groundwater aquifers.

(4) Mineral water may quite often be “special water”; for example, geothermal water (see Serra et al., 2003) or water abstracted at great depth. Itcould thus be unusually “salty” in comparison to “normal” shallow groundwater. The preference for such “salty” bottled water may even be cul-turally determined.

Again, all these problems can be used as strong ar-guments against the approach of using bottled water as a proxy for European groundwater quality. Howev-er, it is diffi cult to evaluate beforehand how seriouslyfiany of these potential problems will affect the varia-tion in water chemistry at a European scale. Some of the effects can be tested beforehand (e.g. the infl uence of different bottle types – see Chapter on fl“Bottle leaching”). Moreover, the bottled water can be compared to European surface water (from Salminenet al., 2005) or tap water, representing drinking wa-ter, collected at the European scale. On balance, the EGS Geochemistry Expert Group decided that the approach was potentially valuable and informative:it proceeded to collect and analyze as many of the bottled waters on the European market as possible,in an attempt to assess the variation of bottled water quality across Europe and its relationship to geology. This atlas presents the results, maps the data and evaluates whether the attempt was justified.fi

1.2 What is Groundwater?

Groundwater is the water that exists in pore spac-es, fractures, fi ssures and caverns in the rocks and sediments beneath our feet. Below the groundwater table all voids are entirely fi lled with groundwater while above, in the so-called vadose zone, cavitiesare partly fi lled with air. Groundwater is usually ul-timately derived from rainfall soaking through thesoils and then into the rocks, although sometimes itmay have its origin in sea water or river water seep-ing into an aquifer. During its passage through a wa-

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What does this Atlas Represent? 11

be of such high microbiological quality that no disin-fection is required. Its composition and temperaturemust remain stable within the limits of natural fl uc-tuation and must not vary with fl ow rate. The water must not be treated or disinfected at all, except for the limited application of simple processes such as (ozone-enriched) aeration, decanting and fi ltrationto remove certain unstable elements such as iron(Fe), manganese (Mn), arsenic (As) and sulphur (S).The carbon dioxide content of a natural mineral wa-ter may be manipulated, and the sold product can bedesignated as one of the following: “Uncarbonated”,“Carbonated”, “Naturally carbonated”, “Fully decar-bonated” or “Partially decarbonated” natural mineralwater or as natural mineral water “fortifi ed with gas from the spring”.

A natural mineral water source must have been fully characterized in terms of its geology and chem-istry and should be protected against pollution. A single natural mineral water source cannot supply more than one mineral water product. The sourceand the water composition must be clearly identifi edon the label. Natural mineral waters do not neces-sarily need to satisfy normal drinking water qualityrequirements: they need only satisfy the limits estab-lished by EC Directive 2003/40/EC. All the maximum admissible concentrations refer to natural contents: the contents should not be the result of “contamina-tion at source”.

1.4.2 Spring Water

According to Directive 96/70/EC, the term “springwater” shall be reserved for a groundwater which isintended for human consumption in its natural state,and bottled at source, which satisfi es many of the same conditions as for mineral waters regardingmicrobiological purity, source protection, labellingand treatment. However, the term spring water doesnot imply the same requirement for a characteris-tic mineral composition, or for the same degree of stability of composition. Finally, the requirements forsource characterization are not as strict as for natu-ral mineral waters and there may be slightly more scope for treatment of the water. However, spring waters must satisfy the normal limits for the qualityof drinking water (EU Directive 80/778/EEC, subse-quently replaced by 98/83/EC), which may be more stringent than the “Mineral Water” limits (see Table of European quality constraints in the different watertypes in the Appendix).

1.4.3 Other Bottled Water / Table Water

Products that are marketed simply as bottled wateror table water are not subject to any specifi c require-ments other than that they must satisfy the normal

limits for the quality of drinking water. They can sim-ply be normal tap water or treated and disinfected river water.

1.4.4 Medicinal Waters

The fi nal, and rather unusual, category of bottled water is that of “Medicinal Water”. The criteria for this designation are rather stringent and are governed by EU Directive 65/65/EEC. In brief, this Directiveeffectively subjects “Medicinal Waters” to the sametesting and labelling regimes as other pharmacolog-ical products that claim to have a health effect. In this connection it may appear surprising that several me-dicinal waters can be purchased in the supermarket and from the same shelves as non medicinal bottled water in many EU countries.

1.5 What does this Atlas Represent?

This Atlas documents the quality of bottled springand mineral waters across Europe, based on an un-evenly geographically distributed dataset of samplespurchased on the available market in 2008/2009. Itprovides an excellent starting point for answeringsome of the concerns raised towards the end of theprevious section, with regards to the possible healthimpacts of basing a diet on the consumption of bot-tled water.

But, is it possible to go any further? Can one dare to hope that this Atlas is in some way repre-sentative of European groundwater quality? Cer-?tainly, the patterns seen on the maps for some ele-ements do indeed seem to refl ect large scale naturalfeatures, where water chemistry is systematically af-fected by regional climate, geology or other factorssuch as land use or vegetation cover – as, for exam-ple, the maps for As, Cr and V clearly demonstrate.Moreover, the authors of this Atlas believe that the range of element concentrations represented in thiseAtlas (from the very “dilute” bottled waters of Nor-way to the mineral-rich waters of Eastern Europe) isreasonably representative of the range of elementsenaturally present in European groundwater (though for some specifi c elements, the mineral waters mayrepresent the “high end” of this range).

The Atlas is thus an excellent starting point for gaining some impression of European groundwaterchemistry. If one looks with a rigorous sceptic’s eyeat the dataset, however, there are good reasons why one should be reluctant to claim that the bottledwater dataset is truly statistically representative (in eterms of intricacies of means, medians and percen-tile distributions!) of overall groundwater quality for all the elements presented. These reasons are men-tioned at several occasions throughout this atlas but

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12 Introduction

are summarized here once more in small print to clearly state the limitations of the chosen approach.

Some of the reasons for possible non-representativity are obvious:• Bottled spring and mineral water is, by defi nition

(one would hope!), protected from point source pol-lution and from the worst excesses of diffuse pollu-tion (although a glance at the map for nitrate would suggest that the diffuse impact of intensive agricul-ture can be discerned even in sources used for bot-tling). The bottled water dataset thus tells very little about the impact of human activity on groundwater.

• Although legislation restricts permitted treatment of spring and mineral waters, some treatments are allowed. Thus, the iron (Fe), manganese (Mn) and arsenic (As) contents of bottled waters may be de-pleted relative to the original groundwater, due to treatment by aeration and settlement of iron and manganese oxyhydroxides. Some waters may have been legitimately diluted to reduce elevated concen-trations of uranium.

• Some bottled water brands have been artifi cially gasifi ed with carbon dioxide. This should not signifi -cantly alter the elemental composition of the water,but will affect its pH and alkalinity signifi cantly (Fig-ures 21 and 24).

• The bottle material itself may have an infl uence on water quality. For example, this study has clearly shown that glass bottles have a tendency to leach lead (Pb) into the water, while many plastic (PET – polyethylene terephthalate) fl asks have a tendency to leach antimony (Sb). It should be stressed that the quantities leached are well below health-related drinking water standards, but the effect is signifi cant in the context of natural groundwater chemistry (Fig-ure 22).

While other reasons are more subtle:• The very idea of a truly representative European

groundwater dataset is highly elusive. What does “representative” mean when one is talking about a three-dimensional, dynamic medium? Groundwater quality varies with time and depth – how could one ever hope to pin it down on a 2-dimensional map?

At any given point on a map, for example, the chem-istry of deep groundwater may be very different from that of shallow groundwater.

• It has been mentioned that, in some cultures, min-eral water will be attractive because it is atypical – for example, because consumers prize its very high mineral content or its dissolved gas content (true “mineral” water, which continues to be popular in Central and Eastern Europe). Alternatively, bottled water may be atypical because of its purity or its low mineral content (many Western European bot-tled waters). The maps for some elements in bottled water may refl ect cultural preferences rather than natural variation: this can be very clearly seen on the map for sodium (Na), where the salt content of bottled water increases strongly to the South and East of Europe. This is opposite to what one would expect intuitively from geography (i.e. highest salt contents near the open Atlantic), and is possibly due to a strong cultural preference for mineral-rich wa-ters in Eastern Europe (but may also be due to the deep sedimentary basins in these regions and thus quite representative of “geology”).

However, it is possible to compare the results of thisstudy (bottled water) to other studies on groundwa-ter or general water quality at a European or a morelocal scale. To answer the most obvious question,“How does the European bottled water compare to European tap water?”, no suitable dataset was ”available. The EGS Geochemistry Expert Groupthus decided to collect a number of tap water sam-ples from all over Europe (n=579), again utilizing thenetwork of colleagues and friends, and to analyze these tap water samples in the same laboratory thatcarried out the bottled water analyses (see belowfor details). Furthermore, the European surface wa-ter data presented in Salminen et al. (2005), as wellas a dataset from Norwegian crystalline bedrock groundwater wells (Banks et al., 1998; Frengstad etal., 2000), can be used for comparison with the bot-tled water. For all these datasets almost the entiresuite of elements reported for the bottled water wasanalyzed.sa

mple pa

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13

2 The Hydrochemistry of GroundwaterThus, already when rainfall hits the ground, it

contains up to several mg/l of inorganic solutes fromnatural and anthropogenic sources.

2.2 The Infl uence of Vegetationfl

When the rain drops fall on leaves, they may par-tially evaporate. When they seep into the shallow soilthey may be sucked up by the roots of plants andtranspired to the atmosphere via the leaves. Suchevapotranspirative processes return water to the at-mosphere, but leave the dissolved salts behind. Thenet effect is to increase the concentration of many solutes in newly infiltrated rainfall, sometimes by a factor of three to four or more.

A few types of solute are removed by plantsand consumed as nutrients. Ions such as potassium(K+), nitrate (NO3

–) and phosphate (PO43–) fall into

this category. The concentration of these may thus decrease as they pass through the vegetation and soil layer.

2.3 The Influence of Soil

The soil usually contains a huge population of bacte-ria, fungi and other micro-organisms. These typicallyrespire – they consume oxygen and release carbonedioxide. Thus, while the atmosphere contains about10-3.5 atm. of CO2, the partial pressure of CO2 in soil gas can be as high as 10-1.5 atm. (100 times ashigh) and soil water is consequently somewhat moreacidic than rainfall.

The water that seeps out of the base of the soil zone therefore contains:• higher contents of solutes than rainfall, due to

evaporation• strongly elevated contents of acidic CO2• some residual atmospheric oxygen (O2)

Very hydrochemically young and immature ground-water may have a chemical composition that closely refl ects this recharge water (i.e. acidic pH, low sol-ute content dominated by atmospheric and marinesalts).

This oxidizing, acidic recharge water now en-rters the geological environment, which is typically dominated by basic, reduced minerals. It is thus not

2.1 The Influence of Rainfall

Groundwater typically begins its hydrological jour-ney as rainfall, which falls from the sky and seeps into the ground. Rainfall may be distilled water, butit is not “pure” water. Even at this stage it containssome dissolved chemicals, or “solutes”. For exam-ple, it contains dissolved oxygen (O2), nitrogen (N2),carbon dioxide (CO2) and other gases that it haspicked up from the atmosphere. Even if the world had been untouched by human activity, the pH ofrainfall would be slightly acidic, somewhere around pH = 5.2 to 5.6, because carbon dioxide forms aweakly acidic solution when it is dissolved (carbonic acid). However, for hundreds of years, human ac-tivities have been emitting gases such as nitrogen oxides, sulphur dioxide and hydrogen chloride tothe atmosphere. All of these dissolve in rainfall and make it even more acidic (hence the term “acid rain”, which is applied to contaminated rainfall over much of Europe). Moreover, the gases increase the con-tent of nitrate, sulphate and chloride in rainfall by afew mg/l.

HCl → H+ + Cl– (1)–

Hydrogen chloride gas → acid + chloride

O2 + 2SO2 + 2H2O → 4H+ + 2SO42– (2)

Oxygen + sulphur dioxide → acid + sulphate + water

Storms at sea and waves along the coast will whip up salty sprays of sea water, which may become en-trained by strong winds. These “marine aerosols” of sea spray may then become dissolved in rainfall near the coast, adding a content of marine salts (for ex-ample, sodium and chloride) to the rainfall. The con-tent of sodium and chloride in rainwater and, hence, also in river water and groundwater, often decreases with increasing distance from the coast (see e.g. Rei-mann et al., 2000; Banks et al., 2001).

Other processes may infl uence rainfall chemis-try. Areas with large expanses of ploughed agricul-tural land or of desert may be vulnerable to strong winds blowing fi ne particles of soil or salt into theatmosphere, where they may become dissolved in rainfall. Alternatively, some industries, such as ce-ment factories, may emit particles of basic oxideswhich will “neutralize” the acid rainwater in their sur-roundings.

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As

Ars

enic

76

Arsenic is a trace element with a predominantlynon-metallic character (atomic number 33). It occursin oxidation states -3, +3 and +5 in nature. Arseno-pyrite (FeSAs) is a common As mineral. Many ore minerals (e.g. galena, pyrite, sphalerite) contain highconcentrations of As, but also common silicates (like feldspars) can contain traces of As. Because of the possible substitution of PV by AsV phosphate mine-rals can also contain As.

Many As-minerals are relatively soluble, howe-ver, the mobility of As in the secondary environmentis limited because of its strong tendency to sorb to clays, secondary hydroxides (especially ferric oxy-hydroxides) and organic matter. Hydrothermal pro-cesses lead to an enrichment of As. It is, together with Sb, a typical element enriched in hydrothermalwaters and an indicator of hydrothermal alterationzones (Banks et al., 2004). It is also often enrichedin coal and black shales. Arsenic can be released to the groundwater environment as ferric oxyhydroxi-des (with a possible loading of sorbed arsenic) areconverted by reductive dissolution to dissolved fer-rous iron under chemically reducing conditions. Thisprocess is believed to be one of the dominant me-chanisms for the evolution of arsenic-rich ground-water in some aquifers in Bangladesh. Conversely, when oxidation causes the precipitation of ferric hy-droxides from solution, arsenic can also be removedfrom solution by sorption to the precipitate (this ae-ration process is one of the few permitted treatmentsof mineral / spring waters, in order to remove ironand manganese, and it would be expected to also remove arsenic from the water, if present).

As-compounds are used in many herbicides,insecticides and fungicides, combustion processes, ore roasting and even pig and poultry farming canlead to an anthropogenic load of As. However, dueto the strong redox- and pH-dependence of As so-lubility, the question of whether such contaminationwill reach groundwater will be very dependent on local conditions. The many incidences of high As in drinking water wells reported in literature (e.g. Smithet al., 2002; Smedley and Kinniburgh, 2002) are in-variably connected to special redox- and geological conditions, are usually natural, and no “contamina-tion”.

The mean concentration of As in surface wa-ter has been estimated to be 4 μg/l (see Koljonen,

1992), a value that is likely to be too high in the light of the results for European surface water (0.63 μg/l – Salminen et al., 2005) and the values presented here (0.24 μg/l) for bottled water.

The map of As in bottled water shows quite anumber of areas with enhanced As-values. Of the interesting patterns observed for As in the geoche-mical atlas of Europe were generally the higher concentrations in Southern than in Northern Euro-pe (a factor 3 difference in the median value). The same can be seen for the bottled water, As values are clearly higher in the Southern European coun-tries (see boxplots, median Northern Europe = 0.07,Southern Europe = 0.28 μg/l). Many of the high values displayed on the map occur in parts of Eu-rope that are known for the occurrence of sulphide mineralization. Furthermore, the alkaline volcanicprovinces in Italy are marked by higher than usual As values. The highest value (89.8 μg/l) was repor-ted in a Polish mineral water, abstracted in an areawith known mineralization. Even four samples from Germany are above the drinking water standards,one is abstracting the water from Palaeozoic rocks, another drawing water from a major fault zone. It isimportant to mention what is not seen on the map: in the Southern parts of the Great Hungarian Plain occurs groundwater with high natural concentrations of As (e.g. Smedley and Kinniburgh, 2005), whichare of course not bottled, but would add on anotherorder of magnitude to the natural variation observedfor As. Bedrock groundwater with high As concent-rations from Finland and Sweden are also not seen in this low density sample map.

Bottle leaching should have no infl uence on the observed As concentrations (up to 0.09 μg/l from glass bottles).

The water standard defi ned for As in mineral water and drinking water in general is 10 μg/l in theEU. Nine samples exceed this level. In the CP-dia-gram in Figure 26 all samples show very comparab-le As values and variation, with a slight enrichment of As in the European surface water in the lower and middle concentration range. The CP-diagram sug-gests that the natural variation of As concentrationin European bottled water (and European water in general) covers four orders of magnitude (+2 orders of magnitude from natural As-provinces).

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As

Ars

enic

77

89.85.152.780.7460.090< 0.03

μg/lAs

0 500 1000 km

N

μg/l

Pro

babi

lity

%

0.1 1 10 100

0.1

1

510

305070

9095

99

99.9

Drinking water standard:10 μg/lEU Directive 2003/40/EC Mineral Water

μg/l

Rel

ativ

e fr

eque

ncy

0

0.2

0.4

0.6

0.01 0.1 1 10 100

SW

SE

NE

NW

μg/l

0.1 1 10 100

Analytical Method: ICP−QMSDetection limit: 0.03 μg/l

45 (5.09%) < detection limit

n:

Minimum:

5%:

25%:

Median:

75%:

95%:

Maximum:

884

< 0.03

< 0.03

0.090

0.235

0.746

5.15

89.8

μg/l

μg/l

μg/l

μg/l

μg/l

μg/l

μg/l

Reimann & Birke (Eds.) (2010): Geochemistry of European Bottled WaterISBN 978-3-443-01067-6

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Appendix A 221

Appendix A

Table of Water Action Levels as defi ned by the EU and for the majority of Countries fifrom which water samples are included in this study

much as possible during the period needed to achie-ve compliance with the parametric value.When implementing the measures to achieve com-pliance with that value Member States must pro-gressively give priority where lead concentrations inwater intended for human consumption are highest.

N4: Member States must ensure that the conditionthat [nitrate]/50 + [nitrite]/3 # 1, the square bracketssignifying the concentrations in mg/l for nitrate (NO3) and nitrite (NO2), is complied with and that the va-lue of 0.10 mg/l for nitrites is complied with ex watertreatment works.

F.A.O.(1) If the product contains more than 1 mg/l of fl u-oride, the following term shall appear on the labelas part of, or in close proximity to, the name of the product or in an otherwise prominent 5 Codex Stan-dard 108–1981 position: “contains fl uoride”. In addi-tion, the following sentence should be included on the label: “The product is not suitable for infants andchildren under the age of seven years” where the product contains more than 1.5 mg/l fl uorides.

W.H.O.* Short-term exposure** Long-term exposureC = concentrations of the substance at or below

the health-based guideline value may affectthe appearance, taste or odour of the water,resulting in consumer complaints

L = Large water treatment facilitiesN = No health-based guideline value for Cl– in–

drinking water; >250 mg/l is detectable by tas-te

O = pH value – Optimum required rangeP = provisional guideline value, as there is evi-

dence of a hazard, but the available informati-on on health effects is limited

S = Small water treatment facilitiesT = provisional guideline value because calcula-

ted guideline value is below the level that can be achieved through practical treatment me-thods, source protection, etc.

Notation

European Union Directives* Suitable for low Na diet

(A) The maximum limit for boron will be fi xed, whe-re necessary, following an opinion of the European Food Safety Authority and on a proposal from the Commission by 1 January 2006.

(B) Natural mineral waters with a fl uoride concen-tration exceeding 1.5 mg/l shall bear on the labelthe words ‚contains more than 1.5 mg/l of fl uoride:not suitable for regular consumption by infants and children under 7 years of age‘

N1: Where possible, without compromising disinfec-tion, Member States should strive for a lower value.For the water referred to in Article 6(1)(a), (b) and(d), the value must be met, at the latest, 10 calendaryears after the entry into force of the Directive. The parametric value for bromate from fi ve years afterthe entry into force of this Directive until 10 yearsafter its entry into force is 25 μg/l.

N2: The value applies to a sample of water intended for human consumption obtained by an adequatesampling method (1) at the tap and taken so as to berepresentative of a weekly average value ingested by consumers. Where appropriate the sampling and monitoring methods must be applied in a harmo-nized fashion to be drawn up in accordance with Ar-ticle 7(4). Member States must take account of the occurrence of peak levels that may cause adverse effects on human health.

N3: For water referred to in Article 6(1)(a), (b) and(d), the value must be met, at the latest, 15 calendaryears after the entry into force of this Directive. The parametric value for lead from fi ve years after the entry into force of this Directive until 15 years afterits entry into force is 25 μg/l.Member States must ensure that all appropriatemeasures are taken to reduce the concentration oflead in water intended for human consumption as

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226 Appendix A

Parameter Name Unit European Union F.A.O.

[a] [b] [c]

Drinking water (EU Directive

98/83/EC)

Mineral water (EU Directive2003/40/EC)

Natural mineral water (EU Directive

2009/54/EC)

Mineral water (1997)

Ag Silver μg/l – – – – –

Al Aluminium μg/l 200 (guide value) – – – –

As Arsenic μg/l 10 10 – – 10

B Boron μg/l 1000 under evaluation (A) – – 5000 (borate)

Ba Barium mg/l – 1 – – 0.7

Be Beryllium μg/l – – – – –

Bi Bismuth μg/l – – – – –

Br Bromine μg/l – – – – –

BrO3- Bromates μg/l 10 (N1) 3 – – –

Ca Calcium mg/l – – >150 – –

Cd Cadmium μg/l 5 3 – – 3

Ce Cerium μg/l – – – – –

Cl- Chloride mg/l 250 (g.v.) – >200 – –

Co Cobalt μg/l – – – – –

CO32- Carbonates μg/l – – – – –

CN- Cyanides μg/l 50 70 – – 70

Cr Chromium μg/l 50 50 – – 50

Cr6+ Chromium VI μg/l – – – – –

Cs Caesium μg/l – – – – –

Cu Copper μg/l 2000 (N2) 1000 – – 1000

Dy Dysprosium μg/l – – – – –

EC at 20oC Electrical Conductivity μS/cm 2500 (g.v.) – – – –

Er Erbium μg/l – – – – –

Eu Europium μg/l – – – – –

F Fluorides mg/l 1.5 5 (B) >1 – See note 1

Fe Iron μg/l 200 (g.v.) – – – –

Fe2+ Ferrous iron mg/l – – >1 – –

Ga Gallium μg/l – – – – –

Gd Gadolinium μg/l – – – – –

Ge Germanium μg/l – – – – –

HCO3- Alkalinity mg/l – – >600 – –

Hf Hafnium μg/l – – – – –

Hg Mercury μg/l 1 1 – – 1

Ho Holmium μg/l – – – – –

I Iodine μg/l – – – – –

K Potassium mg/l – – – – –

La Lanthanum μg/l – – – – –

Li Lithium μg/l – – – – –

Lu Lutetium μg/l – – – – –

Mg Magnesium mg/l – – >50 – –

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Contents included on the Data CD-ROM

4.) FOREGS_SURFACEWATER_EUROPE.xls – European scale surface water data from theFOREGS Atlas (Salminen et al., 2005).

5.) NORWEGIAN_BEDROCKWELLS.xls – the ori-ginal data used in Frengstad et al. (2000).

6.) tif fi les of the element maps suitable for presen-tations or lectures.

7.) Table of Contents of Reimann/Birke (Eds.): Geo-chemistry of European Bottled Water.

8.) Flyer with additional information on the originalpublication “Geochemistry of European BottledWater” (the fl yer may and shall be distributedamong researchers and colleagues).

Terms and conditions for the usage ofthe fi les included on the CD:

No fi le of this CD (except the fl yer) may be distribu-ted or reproduced without written permission of thepublisher. No storage or publication on any website(private, institutional or commercial) is allowed. Dis-tributing any of these fi les through mailing lists orother means is prohibited.

When using the data or fi les of this CD, pleasealways cite the source as follows: File/data originallypublished in Reimann/Birke (Eds.) “Geochemistry ofEuropean Bottled Water” (2010), copyright Gebrü-der Borntraeger Science Publishers Stuttgart, Ger-many, www.borntraeger-cramer.de/9783443010676

The data fi les used to produce the graphics, stati-stical tables and maps presented in this atlas areincluded on the CD-ROM accompanying this atlas in the form of windows Excel “.xls”-fi les. All data re-present the values as found in bottles bought in Eu-ropean supermarkets at the time of purchase. Note that water chemistry can change over time (although the European regulations require for mineral water a“stable” composition).

The data fi les contain the necessary auxiliary information (Header, remarks, analytical method,detection limits, unit etc. on top of the fi le). Atten-tion: the brand names of the bottled water are only provided in the data fi le containing all results (1785 bottles). Values below the detection limit (DL) are set to ½ of the value of the DL in all fi les.

The CD-ROM contains the following fi les: 1.) EGG_BOTTLEDWATER_EUROPE_884.xls –

this is the dataset used for mapping and statisti-cal graphics throughout the atlas – 1 sample per well, 884 sites from all of Europe.

2.) EGG_EuropeanBottledWater_AllSamples_with_source_identifi cation.xls – this dataset contains results from all 1785 bottles that were analyzed for this project. This is the dataset that provides the brand names of the bottled water. Note that when a water is sold in different bot-tle materials or as a still and carbonated variety there may exist several samples from the samewell.

3.) EGG_TapWater_Europe.xls – results for Euro-pean tap water samples collected for this pro-ject.

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Borntraeger Science Publishers, StuttgartDistributor: Schweizerbart Science Publishers, Johannesstrasse 3 A, 70176 Stuttgart, Germanyph.: +49 (711)351456-0 fax: +49 (711)351456-99 order@schweizerbart.de, www.borntraeger-cramer.comUSA: Balogh International, 1911 N. Duncan Rd., Champaign, IL 61822, USA. ph. (217) 355 9331, balogh@balogh.comB

Reimann & Birke (eds.)Geochemistry of European Bottled Water

2010. XII, 268 p., 28 fig., 6 tab., 2 app., 67 element maps,data CD, 27×21cmISBN 978-3-443-01067-6, bound € 78. –

sample pages/order form: borntraeger-cramer.com/9783443010676

In Europe, ca. 1900 "mineral water" brands are officially registeredand bottled for drinking. Bottled water is groundwater and is ra-pidly developing into the main supply of drinking water for the ge-neral population of large parts of Europe.

This book is the first state of the art overview of the chemistry ofgroundwaters from 40 European countries from Portugal toRussia, measured on 1785 bottled water samples from 1247wells representing 884 locations plus additional 500 tap watersamples acquired in 2008 by the network of EuroGeoSurveys ex-perts all across Europe.

In contrast to previously available data sets, all chemical data weremeasured in a single laboratory, under strict quality control withhigh internal and external reproducibility, affording a single highquality, internally consistent dataset.

More than 70 parameters were determined on every sample usingstate of the art analytical techniques with ultra low detection limits(ICPMS, ICPOES, IC) at a single hydrochemical lab facility.

Because of the wide geographical distribution of the watersources, the bottled mineral, drinking and tap waters character-ized herein may be used for obtaining a first estimate of "ground-water geochemistry" at the scale of the European Continent, a da-taset previously unavailable in this completeness, quality and co-verage.

Geochemistry of EuropeanBottled Water

This new data set allows, for the first time, to present a comprehensive in-ternally consistent, overview of the natural distribution and variation of thedetermined chemical elements and additional state parameters of ground-water at the European scale.

Most elements show a very wide range – usually 3 to 4 but up to 7 orders ofmagnitude – of natural variation of their concentration.

Data are interpreted in terms of their origin, considering hydrochemi-cal parameters, such as the influence of soil, vegetation cover and mi-xing with deep waters, as well as other factors (bottling effects,leaching from bottles). Chapters are devoted to comparing the bottled wa-ter data with those of European tap water and previously published data-sets and discussing the implications of water chemistry for health.

The authors also provide an overview of the legal framework, that any bott-led water sold in the European Union must comply with. It includes a com-prehensive compilation of current drinking water action levels inEuropean countries, limiting values of the European Drinking/Mineral/Natu-ral Mineral Water directives (1998/83/EC, 2003/40/EC, 2009/54/EC) and le-gislation in effect in 26 individual European Countries, and for comparisonthose of the FAO and in effect in the US (EPA, maximum contaminant le-vels [MCA]).

The accompanying CD contains the complete data set, sampleidentification and two previously published European water chemistrydata sets.

groundwater chemistry

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______ cop. Reimann & Birke (eds.): Geochemistry of European Bottled Water2010. 280 p., 28 figs, 6 tab., 2 app., 67 element maps, data CD. 27 x 21cm.ISBN 978-3-443-01067-6, bound, € 78.–

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Geochemistry of European Bottled Water

Contents

Forewords IX1 Introduction 3

(The concept of the European groundwater geochemistry:Bottled water (EGG) project — What is groundwater? —What is mineral water? — From mineral water springs andspas to the bottled water market — The legal framework:bottled waters, spring waters and mineral waters — NaturalMineral Water — Spring Water — Other Bottled Water / TableWater — Medicinal Waters — What does this atlasrepresent?)

2 The hydrochemistry of groundwater 13(The influence of precipitation — The influence of vegetation— The influence of soil — Acid-base reactions — Dissolutionreactions — Redox reactions — Mixing with deep salinewaters — Carbon dioxide — Water types)

3 Background information on European bedrock 17(Topography — Geology — Mineral Deposits of Europe —Hydrogeological map of Europe — Soil — Climate —Vegetation and land use — Human activities)

4 Analytical methods 29(Sampling — Analytical procedures — Sample preparation —ICP-QMS analyses — ICP-AES analyses — Atomic fluores-cence spectrometry (AFS) — Ion chromatography (IC) — Pho-tometric analyses — Titration — Potentiometry — Conducto-metry — Quality Control — International Reference Materials— Sample blanks — Detection limits — Duplicate analyses(internal reproducibility) — Comparison of analytical resultswith the water composition provided on the labels — Re-ana-lyses of selected samples — Possible problems with the datain terms of representing true “groundwater quality” or beingable to reflect "geology"Bottle leaching — The effect of carbonatisation — Otherforms of water treatment — Further possible interfering factors— Data analysis and mapping

5 Datasets 52(Bottled water — European tap water — Previously availabledata sets)

6 Comparison of bottled water data with European tapwater, hardrock groundwater from Norway andEuropean surface water data 53

7 Concentration maps and their interpretation 63(Maps for: electrical conductivity EC, pH H+(aq), AlkalinityHCO3- (and other species), silver, aluminum, arsenic, boron,barium, beryllium, bismuth, bromine, calcium, cadmium, cerium,chloride, cobalt, chromium, caesium, copper, dysprosium,erbium, europium, fluorine, iron, gallium, gadolinium, germanium,hafnium, holmium, iodine, potassium, lanthanum, lithium,lutetium, magnesium, manganese, molybdenum, sodium,niobium, neodymium, ammonium, nickel, nitrate, phosphorus,lead, praseodymium, rubidium, selenium, silicon, samarium, tin,sulphate, strontium, tantalum, terbium, tellurium, thorium,titanium, thallium, thulium, uranium, vanadium, tungsten, yttrium,ytterbium, zinc, zirconium

8 Health implications 2019 Conclusions 211References 213Appendix 221

(EU-legal framework: Compilation of current drinking water actionlevels from 26 European countries, EU Directives 1998/23/EC,2003/40/EC, 2009/54/EC and EPA MCA levels)

Contents of the enclosed CD• EGG European bottled water dataset (.xls)• EGG European tap water dataset (.xls)• FOREGS European surface water dataset (.xls)• Norwegian bedrock water dataset (.xls)