Journal of Chromatography A, 1328 (2014) 26–34
Contents lists available at ScienceDirect
Journal of Chromatography A
j our nal homep age: www.elsevier.com/locate/chroma
Simultaneous determination of seven bisphenols in environmental
water and solid samples by liquid chromatography–electrospray
tandem mass spectrometry
Yunjia Yang
a
, Libin Lu
a
, Jing Zhang
a
, Yi Yang
a
, Yongning Wu
b
, Bing Shao
a,∗
a
Beijing Key Laboratory of Diagnostic and Traceability Technologies for Food Poisoning, Beijing Research Center for Preventive Medicine,
Beijing 100013, China
b
Key Laboratory of Food Safety Risk Assessment, Ministry of Health and China National Center for Food Safety and Risk Assessment, Beijing 100021, China
a r t i c l e i n f o
Article history:
Received 12 August 2013
Received in revised form
21 December 2013
Accepted 24 December 2013
Available online 30 December 2013
Keywords:
Bisphenols
Liquid chromatography–tandem mass
spectrometry
Environmental water
Sludge
Solid-phase extraction
a b s t r a c t
This article presents a simple and universal analytical method for the simultaneous analysis of bisphenol S
(BPS), bisphenol F (BPF), bisphenol A (BPA), bisphenol B (BPB), bisphenol AF (BPAF), tetrachlorobisphenol
A (TCBPA), and tetrabromobisphenol A (TBBPA) in environmental water (river water, sewage) and solid
samples (sediment, sludge) based on liquid chromatography–electrospray tandem mass spectrometry
(LC–MS/MS). Analytes were extracted from water samples using hydrophilic lipophilic balanced (HLB)
solid-phase extraction (SPE) cartridges, and the extracts were further purified using MAX SPE cartridges.
For the solid samples, a combination of ultrasonic extraction with the same SPE clean-up procedures
used for the water samples was employed. The absolute recoveries for all analytes in the water and solid
samples ranged from 57.1 to 114.3%. Good method reproducibility was achieved in terms of intra- and
inter-day precision, yielding relative standard deviations (RSDs) less than 16.9 and 18.1%, respectively.
The method limits of quantitation (MLOQ) for the seven compounds in environmental water and solid
samples ranged from 0.05 to 4.35 ng/L and from 0.06 to 2.83 ng/g (dry weight, d.w.), respectively. Finally,
this method was successfully applied to real environmental sample analysis, which revealed that all of
the tested BPs were present, with the exception of BPB.
© 2014 Elsevier B.V. All rights reserved.
1. Introduction
Bisphenol A (BPA), a high-production volume industrial chemi-
cal used to make polymers, is recognized as an endocrine disruptor
[1–3]. Faced with growing concern that exposure to BPA has a wide
range of adverse health issues, Health Canada, Denmark, and Euro-
pean Union have banned BPA use in baby bottles [4–6]. Since July
2013, BPA use in the coating of infant formula packaging has been
prohibited by the United States FDA [7]. Unfortunately, a group of
chemicals that are structurally similar to BPA is also utilized in the
manufacture of resins and plastics. These chemicals, which consist
of two phenolic rings joined through a bridging carbon or other
chemical structures, are called BPA-related compounds or bisphe-
nols (BPs), and some are considered able to partially replace BPA
in industrial applications. Recently, the limitations regarding the
use of BPA have led some manufacturers to replace it with bisphe-
nol S (BPS) in thermal paper and other products [8,9]. Bisphenol
F (BPF) and bisphenol B (BPB) maybe developed as alternatives to
∗
Corresponding author. Tel.: +86 10 64407191.
E-mail address: shaobingch@sina.com (B. Shao).
BPA in the production of epoxy resin and polycarbonate for food
contact materials [10,11] and have been detected in canned foods
and soft drinks [11–14]. In addition to these analogs, bisphenol AF
(BPAF) has broad application in the manufacture of phenolic resins
or fluoroelastomers, with an annual production of approximately
10,000–500,000 pounds in the USA [15]. Tetrabromobisphenol A
(TBBPA) and tetrachlorobisphenol A (TCBPA) are organic flame
retardants, and the former was reported to comprise approximately
60% of the total brominated flame retardant market [16,17]. The
molecular structures of selected bisphenol analogs are shown in
Fig. 1.
Of more significant concern is the fact that these BPs do not seem
to be safer than BPA. Limited studies have shown that BPS, BPB,
and BPF possess estrogenic activity similar to that of BPA [21–23].
Our recent study demonstrated that BPAF can cause testosterone
reduction by directly affecting testis function in adult male rats
[24]. TBBPA and TCBPA are candidate thyroid hormone-disrupting
chemicals [25]. In addition, some BPs are much less biodegradable
than BPA, which renders them more hazardous to humans [26].
The widespread occurrence of BPA in the environment has
inspired significant research interest in other BPs. In the past few
years, TCBPA and TBBPA have been investigated in water [27,28],
0021-9673/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chroma.2013.12.074