Alkylphenols and phthalates in bottled waters

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Abstract

The aim of this study was to investigate the occurrence of endocrine disrupting compounds (EDCs) in bottled waters. The examined compounds were bisphenol A (BPA), nonylphenol (NP), tert-octylphenol (tOP), dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBP), di(2-ethylhexyl)phthalate (DEHP) and di(n-octyl)phthalate (DNOP). The presence of EDCs in bottled waters under poor storage conditions was also investigated after exposure outdoors under realistic conditions for 15 and 30 days. EDCs were recovered after liquid–liquid extraction and determined by employing Gas Chromatography–Mass Spectrometry. Most of these compounds were detected in bottled water from different brands purchased from local market. Storage at outdoor conditions had no significant effect on the concentrations of the examined compounds. Only BPA occurred at higher concentrations in polycarbonate containers exhibited an increasing trend during exposure. The estimated exposure to EDCs via consumption of drinking water was very low.

Introduction

The consumption of bottled water in Greece has been steadily growing up the last decades similarly to the trend observed worldwide. During the period 1998–2005 the consumption has tripled from 380 to 1000 millions liters that is about 100 L per capita per year. The main reasons for this increase are public concern about the quality of tap water, the presence of disinfection byproducts, the shortage of water in touristic areas, especially during warm period, in combination with the consistent quality of bottled water, efficient marketing and changes in consumer's habits last years. Current regulations for bottled water require the analysis for selected microbiological and physicochemical parameters [1], [2], [3]. However there is an anxiety about the quality of bottled water because it is stored for longer periods and not always preserved under the recommended conditions or because containers and bottles are reused without adequate cleaning or disinfection [4].

Moreover many questions have been raised about possible migration of chemicals from the bottles during long storage time especially under poor conditions (high temperatures, sun radiation, etc.). According to the European legislation any container used for packaging of natural mineral waters shall be fitted with closures designed to avoid any possibility of adulteration or contamination [1]. Therefore, the control of materials used in bottles and closures for bottled water is of special concern [4]. Bottled water is usually available in two main sorts of packaging material; glass and plastic. About 80% of the plastic bottles used is of poly(ethylene terephthalate) (PET) owing to the desirability of its physical and chemical properties such as strength, transparency, light weight and easy recycling. Containers, mainly water carboys, made of polycarbonate (PC) are also used.

Many studies reported the presence of organic compounds in bottled water that may affect the organoleptic characteristics of the water, and pose health risk to consumers. Organic compounds could be source of carbon to inherent microorganisms which also have implications on odour and taste thresholds. The presence of xenobiotics in bottled waters represents a complex problem and the origin of several substances is not clearly established and still being debated. Bottled water can be contaminated in different phases of the production process, from supplying of the materials to handling, storing and distribution [5]. This includes contamination of water source in the field, during bottling process in the plant, migration from the material of the bottle or the caps to the water (monomers, catalysts, additives or degradation products) and formation of organic compounds under deficient storage conditions [5], [6], [7], [8], [9], [10]. This study investigates the presence of compounds that can pose endocrine disruptions or are suspected for this in bottled waters. The examined compounds are bisphenol A, nonylphenol, octylphenol and phthalates.

Bisphenol A (BPA) is a monomer used in the production of polycarbonates and epoxy resins from which a variety of products are generated. Epoxy resins are used to lacquer-coat the interior of food cans, wine storage vats, water containers and water pipes. Polycarbonate plastics are used to manufacture water carboys, reusable milk containers, food storage vessels and baby bottles. It has been reported that incomplete polymerization of these products during manufacture and increased temperatures imposed during heating, can cause leaching of unreacted compounds into foods and beverages. BPA demonstrates estrogenic activity and is considered as important organic pollutant [11].

Nonylphenol (NP) is widely spread in the environment as a result of its use in industry as raw material, as additive in epoxy resins to enhance properties of polymerization, drying, plasticity, etc. Nonylphenol and octylphenol, that present endocrine response, are the main metabolites during degradation of alkylphenol ethoxylates (APEs), which are used as nonionic surfactants in cleaning agents, disinfectants and pesticides formulations. Since January 2005, there has been a restriction in Europe on the sale and use of products that contain more than 0.1% of 4-nonylphenol ethoxylates (NPEOs) or 4-nonylphenols (NPs) [12].

Phthalates (PEs) are ubiquitous pollutants in the environment, due to their widespread use for around 50 years. These compounds are used principally as plasticizers, to impact flexibility, workability and, durability to polymers but they can also be found in products such as paints, adhesives, inks and cosmetics. PEs are not chemically bounded to polymers; hence they are easily released and migrate into foods, beverages and drinking water from the packaging or bottling materials or manufacturing processes. This process accelerates as plastic products age and break down. With respect to their endocrine disrupting potential, phthalates such as BBP, DBP and DIBP have been found to elicit estrogenic responses in in vitro assays. It is possible that phthalates are a contributory factor to endocrine-mediated adverse effects observed in wildlife and humans over the past few decades [7], [13], [14].

The aim of this study was to investigate the occurrence of endocrine disrupting compounds; nonylphenol, tert-octylphenol, bisphenol A, and phthalates in bottled waters. Moreover the influence of storage of water bottles outdoors, under natural conditions, was also investigated. Finally, the exposure to EDCs via water consumption was estimated.

Section snippets

Reagents and materials

EPA phthalate esters mix (DMP, DEP, DBP, BBP, DEHP, DNOP) were supplied from Supelco (Bellefonte, PA, USA). Bisphenol A was purchased from Ceriliant (Austin, TX), 4-n-nonylphenol was obtained from Riedel de Haën (Seelze, Germany), 4-tert-octylphenol, 4-nonylphenol and N,O-bis(trimethylsilyl)-trifluoroacetamide (BSTFA) were supplied from Fluka (Buchs, Switzerland). Bisphenol A-d16 and DNOP-d4 were purchased from Aldrich (Dorset, UK).

Sample preparation

Commercially available bottled waters from randomly chosen

Concentrations of EDCs

The median concentrations of alkylphenols determined in bottled waters purchased from the market were 4.6 ng/L for BPA, 7.9 ng/L for NP and <2 ng/L for tOP. The lower concentrations were observed in water from PET bottles (samples A–E) (Fig. 1). The sample G, bottled in polycarbonate container, exhibited relatively higher concentrations of BPA (112 ng/L) (Fig. 2).

BPA is a key building block of polycarbonate materials. Kawamura et al. [17] reported that BPA on the surface or near the surface of

Conclusions

The aim of this study was to investigate the occurrence of selected EDCs (NP, OP, BPA, DMP, DEP, DBP, BBP, DEHP, DNOP) in bottled waters. The influence of environmental factors and storage time on the occurrence of chemical substances was also studied after exposure at outdoor conditions for 15 and 30 days.

The examined compounds were detected at low levels in bottled water purchased from local market. The results are within the concentration range observed by other investigators. BPA exhibited

Acknowledgements

The instrumentation used in this study was obtained through the Project AKMON 5 co-financed by E.U. – European Regional Development Fund (70%) and the Greek Ministry of Development – GSRT (30%).

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