Journal of Chromatography A, 1355 (2014) 193–205 Contents lists available at ScienceDirect Journal of Chromatography A j o ur na l ho me page: www.elsevier.com/locate/chroma Simultaneous determination of polar pharmaceuticals and personal care products in biological organs and tissues Rumi Tanoue a , Kei Nomiyama a,∗ , Haruna Nakamura b , Terutake Hayashi c , Joon-Woo Kim a,d , Tomohiko Isobe a , Ryota Shinohara b , Shinsuke Tanabe a a Center for Marine Environmental Studies (CMES), Ehime University, 2-5, Bunkyo-cho, Matsuyama, Ehime 790-8577, Japan b Graduate School of Environmental and Symbiotic Sciences, Prefectural University of Kumamoto, 3-1-100, Tsukide, Kumamoto 862-8502, Japan c Tochigi Prefectural Museum, 2-2 Mutsumi-cho, Utsunomiya, Tochigi 320-0865, Japan d Monitoring and Analysis Division, Seamangeum Regional Environmental Office, 100 Seogok-ro, Wansan-gu, Jeonju-si, Jeollabuk-do 560-870, South Korea a r t i c l e i n f o Article history: Received 11 March 2014 Received in revised form 2 June 2014 Accepted 3 June 2014 Available online 10 June 2014 Keywords: Pharmaceuticals Personal care products Birds Fish Liver Brain a b s t r a c t In the present study, a sensitive and accurate isotope dilution method was developed for the simultaneous determination of 17 polar pharmaceutical and personal care product (PPCP) residues (log K ow = 1.40–5.74), including 14 pharmaceuticals and 3 personal care products, in biological organs and tissues. The proposed method involved enzymatic hydrolysis, followed by sequential clean-up using silica gel chromatography and gel permeation chromatography, and analysis via ultra-high-performance liquid chromatography with tandem mass spectrometry. This method yielded acceptable absolute recov- eries (48–88%) and internal standard-corrected recoveries (90–130%) for 17 PPCPs. Method detection limits were between 0.0092 and 3.2 ng g −1 wet weight, and the limits of quantification were between 0.020 and 8.7 ng g −1 wet weight. The method can be used to readily detect the target compounds at trace levels while minimizing the required sample volume. The developed method was applied to the deter- mination of 17 PPCPs in the liver and kidney of 17 birds collected from Japan and also in the plasma, liver, and brain of 7 cyprinoid fish from an effluent-dominated stream in Japan. Triclosan was detected in 5 of 11 fish-eating birds but not in non-fish-eating birds, suggesting the contamination of prey fish by the chemical. Non-steroidal anti-inflammatory drugs, antibacterial agents, and psychotropic agents were frequently detected in the fish tissues. In addition, 7 of the target compounds were found in fish brain. The median brain/plasma ratios of the psychotropic agents ranged from 1.6 (carbamazepine) to 12 (diphenhydramine), indicating high transportability to fish brain. © 2014 Elsevier B.V. All rights reserved. 1. Introduction Pharmaceuticals and personal care products (PPCPs) are con- stantly introduced into the environment through human activities and thus have been detected in various environmental media such as surface water and sediments. Because of their continuous loading to the aquatic environment through effluent discharges from wastewater treatment plants (WWTPs), PPCPs are consid- ered as “pseudo-persistent” contaminants. In fact, various PPCPs have been detected in wild fish inhabiting wastewater discharge areas, reflecting their constant exposure [1–4]. Among PPCPs, per- sonal care products (PCPs) with high lipophilicity, such as synthetic ∗ Corresponding author. Tel.: +81 89 927 8196; fax: +81 89 927 8196. E-mail addresses: keinomi@agr.ehime-u.ac.jp, keinomiyama@gmail.com (K. Nomiyama). musks and organic UV filters, have been detected in not only fish but also marine mammals and waterfowls [5,6]. In contrast, the bioaccumulation potential of polar PPCPs including pharmaceutical chemicals has been considered insignificant. However, in vitro and in vivo studies [7–9] recently showed that certain pharmaceuticals, such as antidepressants and antihistamines, have greater bioac- cumulation potentials in fish and shrimp than those in terrestrial mammalian species. These results suggest that bioaccumulation of pharmaceutical chemicals is not determined only by their chemi- cal lipophilicity. Considering the fact, continuous exposure to PPCP residues and their adverse effects on fish and fish-eating birds (top predators of the freshwater food web) may become a great concern. It has been reported that diclofenac (DF), a non-steroidal anti- inflammatory drug (NSAID), is the principal cause for the marked decrease in endemic vulture species in India, Pakistan, and Nepal [10]. Although DF was detected at relatively low concentrations (51–643 ng g −1 ) in the kidney of wild vultures, these levels were http://dx.doi.org/10.1016/j.chroma.2014.06.016 0021-9673/© 2014 Elsevier B.V. All rights reserved.