Article pubs.acs.org/est
Bisphenol A and Its Chlorinated Derivatives in Human Colostrum Virginie Migeot,†,‡,∥ Antoine Dupuis,*,†,‡,∥ Axelle Cariot,†,‡ Marion Albouy-Llaty,†,‡ Fabrice Pierre,§ and Sylvie Rabouan† †
University of Poitiers, UMR-CNRS 7285 (IC2MP) School of Medicine and Pharmacy (Departments of Analytical Chemistry, Pharmaceutics and Epidemiology), Poitiers, France ‡ Biology−Pharmacy−Public Health Department, University Hospital of Poitiers, Poitiers, France § Woman−Mother−Child Department, University Hospital of Poitiers, Poitiers, France
ABSTRACT: The health effects related to bisphenol A (BPA) and its exposure sources have undergone extensive investigation, but no consensus has been reached. Hitherto, the major source of human BPA exposure considered in the literature remains food-contact material. However, the chlorine present in drinking water may react with BPA to form chlorinated derivatives (ClxBPA), which have indeed been shown to have a heightened level of estrogenic activity. In this study, we have evaluated colostrum concentrations of BPA and ClxBPA in order to confirm our hypothesis according to which BPA water contamination leads to ClxBPA human exposure. BPA and its ClxBPA were assessed through online solid-phase extraction coupled to ultra highperformance liquid chromatography tandem mass spectrometry (SPE-UPLC-MS/MS) using the isotope dilution method in the colostrums of 21 women who had completed a water exposure questionnaire. BPA was detected in 19 colostrums and its ClxBPA in 21 colostrums. Mean concentrations were 1.87 ± 1.38 ng mL−1 (n = 19) for BPA, 1.87 ± 1.23 ng mL−1 (n = 7) and 1.56 ± 0.74 (n = 18) ng mL−1 for 2,2′-Cl2BPA and 2,6-Cl2BPA, respectively, and 0.68 ng mL−1 (n = 1) for trichloro-BPA. These findings confirm our hypothesis that ClxBPA should be taken into account in human health risk assessment.
■
INTRODUCTION Sources of exposure to bisphenol A (BPA) have been investigated over the last 10 years. However, they have yet to be comprehensively understood, and their interpretations are at times controversial.1 As a result, the decisions taken by different governments initially appeared self-contradictory. On the one hand, Canada was the first country in the world to consider BPA as a toxic substance and to write this into its regulations; little by little, other countries have followed suit. On the other hand, the sources of BPA predominantly investigated and taken into account when drawing up rules and regulations have been food in general and food-contact material in particular.2 Even though only 5% of BPA production is used in food packaging, other sources of contamination still tend to be deemed marginal.1,3−6 It should nonetheless be recalled that BPA is an ubiquitary contaminant, and that it is continuously introduced into the aquatic environment by means of industrial, agricultural, and municipal effluents. More specifically, occurrences of BPA have been widely reported in various aqueous media throughout the world:7 surface water, drinking © 2013 American Chemical Society
water from drinking water treatment plants, bottled water, and household tap water.5,8−11 In the case of tap water, the leaching of BPA from epoxy pipe-lining has already been proven.12,13 Because the need for drinking water continues to grow, the use of surface water in its production is common in industrialized countries (63% in France 14) and more or less equal on a worldwide scale (48% groundwater, 48% surface water, 4% saltwater 15). The different steps in the treatment process are likely to yield the quality required in the regulations, and in most drinking water treatment plants, routine operations are concluded by chlorination, so that the formation of ClxBPA (mono-, di-, tri-, and tetra-chloro-biphenol A) in drinking water is to be expected.16,17 With the exception of tetra-chloro-BPA, chlorinated BPAs are not used in industrial activity.18 Consequently, chlorine-treated water is likely to be the only Received: Revised: Accepted: Published: 13791
July 11, 2013 October 31, 2013 November 1, 2013 November 1, 2013 dx.doi.org/10.1021/es403071a | Environ. Sci. Technol. 2013, 47, 13791−13797
Environmental Science & Technology
Article
Table 1. Review of Concentrations of ClxBPA and BPA in Human Biological Samples sample
BPA
adipose tissuee(woman) (ng g−1) n = 20
adipose tissuef (child) (ng g−1) n = 86
placentag (ng g−1) n = 49
placentah (ng g−1) n = 50
i
−1
urine (μg g ) adjusted with creatinine n = 31
serumi (ng mL−1) n = 14
a
b
mean ± SDd detection percentage LODa mean ± SDd detection percentage LODa min−max detection percentage LODa min−max mean detection percentage LODa min−max mean detection percentage LODa (ng mL−1) min−max mean detection percentage LODa c
ClBPA
Cl2BPA
Cl3BPA
5.83 ± 3.48 55%
3.05 ± 0.28 15%
9.21 ± 9.26 80%
0.74 ± 0.15 10%
NDb NDb
0.5 17.46 ± 14.82 62%
0.5 7.32 ± 4.25 64%
0.5 14.45 ± 9.79 99%
3.0 4.13 ± 1.35 2%
3.0 3.54 ± 1.94 12%
GC-MS
0.5 5.7−22.2 20%
0.5 5.1−21.4 51%
0.5 12.7−58.8 51%
3.0 4.0−31.2 49%
3.0 NDb NDb
LC-MS/MS
0.2 1.2−15.4 4,8 40%
0.3 NDb NDb NDb
0.3 NDb NDb NDb
0.4 NDb NDb NDb
0.6 NRc NRc NRc
UHPLC-MS/ MS
0.2
