Characterization of estrogenic receptor agonists and evaluation of estrogenic activity in the sediments of Liaohe River protected areasby Xin Ke, Chunyong Wang, Haijun Zhang, Yun Zhang, Shaofeng Gui

Marine Pollution Bulletin


Aquatic Science / Pollution / Oceanography


Conservation and land management

The Viscount of Arbuthnott

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by Members of the Centre of African

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ni ea g b a men -de ght 3), s)w , 23 , in we ed t ts in © 2015 Elsevier Ltd. All rights reserved.

Cs), wh disrup (Bicch emicals s even 012). gen rec

Marine Pollution Bulletin xxx (2015) xxx–xxx

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Marine Pollut l sesynthetic estrogens (e.g. 17α-ethynylestradiol (EE2), 4-nonylphenols (4-NP), bisphenol A (BPA), and organochlorine pesticides (OCPs)) (McKinlay et al., 2008; Barnabé et al., 2009; Combalbert and

Hernandez-Raquet, 2010). They can affect the reproductive system of the organism and cause some diseases such as cancers or skin diseases (Hu et al., 2012). In rivers, sediments can accumulate and preserve the contaminants which are produced by anthropogenic activities (Karlsson et al., 2008; Taylor and Owens, 2009). This means that sediments can act as a sink for these ER agonists. Meanwhile, recent studies have demonstrated that sediments have obvious potency to induce esdue to its high sensitivity and low requirements to equipment (Svobodová et al., 2009; Kinani et al., 2010). For instance, the recombinant yeast bioassays have been fully validated and constructed to evaluate estrogenic activity (Luo et al., 2011). Although in vitro bioassays can provide a comprehensive measurement of estrogenic activity of thewholemixture of chemicals, it cannot reveal the contributions of different chemicals or class of chemicals. The fractionation of sample extracts can resolve chemical mixtures into simple component (Nakada et al., 2004; Weiss et al., 2009), helpful for identification of the different components that are responsible for estrogenic activity.trogenic activity by E1, E2, E3, EE2, 4-NP, BP et al., 2008; Kinani et al., 2010; Zhang et al., 2 in sediments can induce negative effects in aq ⁎ Corresponding author at: College of Land and Envir

University, No 120 of Dongling Street of Shenhe district, C

E-mail address: (Y. Zhang). 0025-326X/© 2015 Elsevier Ltd. All rights reserved.

Please cite this article as: Ke, X., et al., Chara

Liaohe River protected ..., Marine Pollution Beptors and can act as esists include natural estro, and estriol (E3)) and used to study estrogenic activity (Jeffries et al., 2011; Galluba and

Oehlmann, 2012). Especially, in vitro bioassays have been proved as a quite useful method to screen and quantify the estrogenic potency,trogenic receptor (ER) agonists. These ER agon gens (e.g. estrone (E1), 17β-estradiol (E2)1. Introduction

Endocrine disrupting chemicals (ED crine function and lead to the endocrine life, are widespread in the environment et al., 2012). EDCs, including natural ch have significant impacts on organism et al., 2012; Galluba and Oehlmann, 2

EDCs have high binding affinity to estroich can change the endotion in humans andwildi et al., 2009; Venkatesan and synthetic chemicals, at a low dose (Froehner

In particular, estrogenic reproductive and physiological abnormalities. Thus, the potential ecological risk of ER agonists in sediments should be urgently investigated.

In recent decades, chemical analysis by gas chromatography–mass spectrometry (GC–MS) and high performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) techniques are being applied. However, chemical analysis lacks the information of potential adverse effects to the organisms. In vivo and in vitro bioassays that can reflect the biological effects in complex environmental mixtures areIn vitro bioassaysCharacterization of estrogenic receptor ago the sediments of Liaohe River protected ar

Xin Ke a, Chunyong Wang a, Haijun Zhang a, Yun Zhan a College of Energy and Environment, Shenyang Aerospace University, Shenyang 110136, Chin b College of Land and Environment, Shenyang Agriculture University, Shenyang 110161, China a b s t r a c ta r t i c l e i n f o

Article history:

Received 10 August 2015

Received in revised form 31 August 2015

Accepted 2 September 2015

Available online xxxx



Estrogen receptor (ER) agonists

Polarity-based fractionation

Chemical analysis

Estrogenic activity of 12 sedi yeast bioassays. The bioassay 52.2 and 207.6 pg/g dry wei 17β-estradiol (E2), estriol (E ganochlorine pesticides (OCP up to 203.3 pg/g, 185.8 pg/g polarity-based fractionation predominant ER agonists and

Meanwhile, this study show ical risk caused by ER agonis j ourna l homepage: www.eA, and OCPs (Villaverde 011). These ER agonists uatic organisms, such as onment, Shenyang Agriculture hina. cterization of estrogenic recep ulletin (2015), http://dx.doi.osts and evaluation of estrogenic activity in s ,⁎, Shaofeng Gui a t samples from Liaohe River protected areas was evaluated by the recombinant rived 17β-estradiol equivalents of crude extracts (Bio-EEQcrudes) were between . The most concerned estrogenic receptor (ER) agonists including estrone (E1), 17α-ethynylestradiol (EE2), 4-nonylphenols (4-NP), bisphenol A (BPA), and orere determined. The concentrations of E1, E2, E3, EE2, BPA, andΣ10OCPs ranged 7.7 pg/g, 188.5 pg/g, 51.0 ng/g, and 3.6 ng/g, respectively. Taken together with vitro bioassay and chemical analysis, it indicated that E1, E2, and EE2 were the remainly from the discharge of domesticwastewater and breedingwastewater. hat the establishment of protected areas had not obviously reduced the ecologLiaohe River protected areas sediments. ion Bulletin v ie r .com/ locate /marpo lbu lLiaohe River, which situates in the southwestern part of Northeast

China andflows through Liaoning Province, belongs to one of the largest rivers and one of the most polluted rivers in China. Liaohe River protected areas which cover most parts of Liaohe River were located in Liaoning province and were established in 2010. In this study, 12 sediment samples fromupstream,midstream and downstreamwere collected. This study also made a comparison with the previous study of tor agonists and evaluation of estrogenic activity in the sediments of rg/10.1016/j.marpolbul.2015.09.008