Stable hydrogen and oxygen isotopic composition of bottled waters in Poland: Characterization in the context of different market categories and implications for the origin authentication and natural isotopic quality preservation

https://doi.org/10.1016/j.gexplo.2020.106684Get rights and content

Highlights

  • Bottled waters are food product and must comply with certain quality standards.

  • O and H isotopic composition of bottled water reflects its natural origin.

  • Bottling and storage may influence the natural isotopic composition of water.

  • Commercially useful authentication of bottled water refers to identification of its market brand.

  • Isotopic authentication is effective only for waters of unique isotopic composition and origin.

Abstract

The hydrogen (δ2H) and oxygen (δ18O) isotopic composition of 45 Polish brands of bottled waters was analysed and evaluated in the context of two areas of its potential application in bottled water industry: (i) the origin authentication, and (ii) the quality monitoring in context of preservation of natural physicochemical parameters and isotopic composition. Three main market categories of bottled waters were analysed: natural mineral waters, spring waters and medicinal waters. The results obtained showed that isotopic composition for domestic bottled waters varied in wide range from −11.0‰ to −0.6‰ for δ18O and from −76.8‰ to −50.2‰ for δ2H. The bottled waters generally preserve the natural isotopic composition of their source of origin and discharge. However, the influence of the bottling process on the natural isotopic composition of water may be observed in relation to medicinal waters of higher salinity and natural CO2 content. The physicochemical parameters and isotopic composition of waters stored in PET-made bottles may change over time indicating deterioration of the water quality. The application of H and O isotopic composition for bottled water brand authentication among natural mineral waters and spring waters is very limited due to similar climatic factors controlling formation of meteoric groundwaters in hydrogeological systems in local or global scale. However, it is possible to differentiate and authenticate bottled waters which have specific isotopic composition resulting from unique origin connected first of all with geological factors like water-rock interaction or admixture of water of non-meteoric origin. Among Polish brands of bottled waters such unique H and O isotopic composition is associated usually with some medicinal waters.

Introduction

The beginnings of water bottling in Europe date back to the XVI century. The necessity for bottling the water was connected with the use of mineral and thermal waters and the conscious recognition of their medicinal, curative and therapeutic benefits (LaMoreaux and Tanner 2001; EFBW 2019; Porowski 2019). The Holy Well Bottling Plant in Malvern, UK, is believed to be the first bottling plant in the world where in 1622 the first time water was bottled for the consumer market (MHDC 2008; Smart 2009).The first water bottling plant in Poland was built in Krynica Zdrój Spa in 1808: the water extracted from Main Spring was packed in the stoneware bottles which were susceptible for breaking (Kucharski and Franczukowski 2009; Rajchel, 2009, Rajchel, 2017; PIG-PIB 2019).

Today, the bottled water industry accounts for significant part of a global economy. The water in a bottle is readily available healthy beverage being an important component of human dietary. All bottled waters intended for drinking belong to food market and must comply with special quality standards set in the bottled water legal regulations (Directive 2009/54/EC; Directive 98/83/EC; Dz. U. 2011 Nr 85 poz. 466; compilation see in Porowski 2019).

In this study three categories of bottled waters were identified in beverage market in Poland, namely: natural mineral water, spring water and medicinal water; each of these categories is strictly defined by regulations. Such “market” classification of bottled waters does not refer to chemical type of water or its total mineralization but relates rather to standards of water extraction, production and protection in the context of preservation of water's natural physicochemical properties.

The natural medicinal water is a very specific category of bottled water in Poland as well as global market. In Poland, such waters generally belong to the category of natural mineral waters but additionally must comply with the regulations of the Act of 9 June 2011 of Geological and Mining Law. According to this Act, the medicinal water is the groundwater which contains at least 1000 mg/L of total dissolved solids or at least one of the following pharmacologically active chemical compounds in concentration above the agreed lower limits: ferrous ion – 10 mg/L, fluoride ion – 2 mg/L, iodine ion – 1 mg/L, bivalent sulfur ion – 1 mg/L, meta-silicic acid – 70 mg/L, radon – 74 Bq, and free carbon dioxide – 250 mg/L. Moreover, the medicinal waters have a status of mineral resource and their extraction requires concession, whereas other bottled waters are extracted based on the water-legal permit. Some of the medicinal waters have special certificate of drug granted by the National Institute of Public Health – National Institute of Hygiene based on many years detailed investigations directed on the medical demonstration of healing properties of at least one pharmacologically active compound contained in such water. There are only four spas in Poland which have certification for extraction and bottling of mineral medicinal waters, namely: Krynica Zdrój, Wysowa Zdrój, Szczawnica Zdrój and Szczawno.

Nowadays, global consumption of bottled water is growing in almost every region of the world.

The bottled waters available on the market differ among each other not only by categories, brands, labels and package types, but also by its natural origin, the total mineralization, the unique chemical composition which determine the taste of water and its edible and refreshing qualities. The bottled waters may come from natural sources (e.g. groundwater) or straight from a tap (drinking water from municipal source or community water systems). About 97% of bottled waters in Europe come from natural sources. Different sources of bottled waters in context of the place of its origin are directly connected with the water quality (i.e. chemical properties) and marketed brands and their authenticity (Guillou and Reniero 1999; Rossmann 2001; Brenčič and Vreča 2006; Spangenberg and Vennemann 2008; Raco et al. 2013). The monitoring and evaluation of bottled water quality and authentication of its origin represent an increasingly important issues for bottling industry worldwide, national bottle water market regulators and consumers (Bowen et al. 2005; Brenčič and Vreča, 2006, Brenčič and Vreča, 2007; Spangenberg and Vennemann 2008; Dotsika et al. 2010; Raco et al. 2013; Salomon and Regulska-Ilow 2013). The producers of high quality bottled waters needs to have some reliable tools to assure the quality of the water, and protect the brand authenticity on the market. The consumers want to be sure about the declared quality of the bottled water in the context of preservation of all natural physicochemical properties which the natural water possesses at the source. Up to date the questions of the quality control of bottled water or reliable ways of authentication of their origin are still challenging problem (Brenčič and Vreča, 2006, Brenčič and Vreča, 2007, Brenčič and Vreča, 2014; Dotsika et al. 2010; Raco et al. 2013; Porowski et al. 2018). The application and implementation of methods connected with isotope hydrogeology and stable hydrogen (δ2H) and oxygen (δ18O) isotopic composition of water seems to be promising and was described and discussed in several papers in last decades (Bowen et al. 2005; Brenčič and Vreča, 2006, Brenčič and Vreča, 2007, Brenčič and Vreča, 2010, Brenčič and Vreča, 2014; Dotsika et al. 2010; Raco et al. 2013; Porowski et al., 2018, Porowski et al., 2019).

In this work, we present a dataset of hydrogen (δ2H) and oxygen (δ18O) isotopic compositions for 45 brands of bottled waters randomly collected on the Polish market between April 2018 and June 2019. The primary goal of this study is to present the first comprehensive characterization of H and O isotopic composition of bottled waters in Poland in the light of the main bottled water categories found in Polish and European beverage market. In this context the work fills the gap on the European map of countries where such studies have been already done before. The focus is made on the presentation of specific category of medicinal bottled waters, which usually demonstrate the unique isotopic and chemical composition connected with their characteristic provenance. The problem of the isotopic demonstration of natural origin of bottled waters in the context of brands authentication and the potential influence of the bottling processes and the storage time on the preservation of natural physicochemical and isotopic qualities of bottled waters were discussed on the basis of obtained experimental results.

Section snippets

Materials and methods

A total of 45 brands of bottled waters commercially available from supermarkets around Poland were collected between April 2018 and June 2019 in order to determine their stable hydrogen (δ2H) and oxygen (δ18O) isotopic compositions (see Fig. 1). Among different bottled waters collected to this study, 22 waters belong to natural mineral waters, 16 to spring waters and 7 to medicinal waters. The majority of collected waters were originally packed in 0.5 L PET bottles; two waters (Ostromecko and

Results

Bottled waters collected to this study belong to three market categories: natural mineral waters (22 brands), spring waters (16 brands), and medicinal waters (7 brands). All bottled waters in Poland are groundwaters in origin. They are extracted from underground resources from different geological formations by means of wells or springs (including self-flowing springs). The geographical distribution of bottled water brands collected to this study in Poland is presented in Fig. 1. The basic

Geochemical characteristic of bottled waters

The marketed bottled waters differ among each other not only by brands, labels and package types, but first of all by the chemical composition and the total mineralization which both, seem to be the primary factors determining the taste of water and its edible and refreshing qualities. The chemical composition of all bottled waters coming from natural sources (i.e. mineral waters, spring waters and medicinal waters) is formed through the water – rock interaction and depends on many factors,

Concluding remarks

The hydrogen (δ2H) and oxygen (δ18O) isotopic composition of 45 Polish brands of bottled waters was analysed and evaluated in the context of two areas of its potential application in bottled water industry: (i) the origin authentication – including differentiation between bottled water brands, marketed types or unique hydrogeological origin, and (ii) the quality monitoring – to monitor the quality of the packaged water in the context of preservation of natural physicochemical features, and to

CRediT authorship contribution statement

Adam Porowski: Conceptualization, Investigation, Methodology, Software, Writing - original draft, Writing - review & editing, Funding acquisition. Anastasiia Romanova: Investigation, Data curation, Validation, Visualization, Software, Writing - original draft. Beata Gebus-Czupyt: Validation, Investigation, Formal analysis, Data curation, Writing - review & editing. Bartosz Wach: Formal analysis, Resources, Validation, Writing - review & editing. Magdalena Radzikowska: Formal analysis, Writing -

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This research received funding in the framework of the internal research project of the Stable Isotope Laboratory of the Institute of Geological Sciences, Polish Academy of Sciences (ING PAN). Part of the analytical studies and field sampling was supported by the National Science Center Poland, grant No. UMO-2015/17/B/ST10/03295.

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