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1 214,34(9) 2273~2278 China Environmental Science, *,,, (,, 184) (SPE UPLC/MS/MS), 9, 27.5~131.8ng/L, 72.8%~12.2%;,, 4, 7.6,12.9,5.6,91.6μg/L, 4.2,5.2,2.2,37.4μg/L, 2.,2.7,.6,24.4μg/L;. SPE UPLC/MS/MS X832;X82.4 A (214) Residue analysis method and environmental risk assessment of cephalosporin antibiotics in pharmaceutical wastewater. TANG Xin-yao, ZUO Jian-e *, YU Xin, YANG Bo, WANG Kai-jun (State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 184, China). China Environmental Science, 214,34(9) 2273~2278 Abstract Based on solid phase extraction (SPE) and ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), a testing method for 9 cephalosporin antibiotics, i.e., cefaclor, ceftriaxone, cephalexin, cefotaxime, cefazolin, cefuroxime, cefoxitin, cefalotin and cefradine, in pharmaceutical wastewater was established. The limit of quantitation was from 27.5 to 131.8ng/L, and the recovery efficiencies for different analytes ranged from 72.8% to 12.2%. With this method, cephalosporin antibiotics in the effluent of each processing unit of a pharmaceutical wastewater treatment plant (P-WWTP), which adopted two-stage biological oxidation processes, were tested. Ceftriaxone, cefazolin, cefotaxime and cefuroxime were found in the pharmaceutical wastewater. Their average concentrations in influents were 7.6, 12.9, 5.6 and 91.6μg/L, in effluents of first-stage oxidation unit were 4.2, 5.2, 2.2 and 37.4μg/L, and in effluents of second-stage oxidation unit were 2., 2.7,.6 and 24.4μg/L, respectively. Risk quotient method was utilized to evaluate the environmental risks of these four antibiotics in the effluents, and all the results were high risk levels. Key words cephalosporin antibiotics SPE-UPLC/MS/MS pharmaceutical wastewater environmental risk assessment, [1]. [1],.,,, [2 5], (PPCPs) [5]., PPCPs, [6]. PPCPs [7] [8 11],. (LC MS/MS) (29ZX7529 6, 212ZX725 1) *,, jiane.zuo@tsinghua.edu.cn

2 ,(SPE), [12,16] [9,11 13,] [1,16] [12,14 ].. (SPE UPLC/MS/ MS,),, (USP), Dr. Ehrenstorfer. 91.8%, 92.4%, 93.7%, 94.7%, 98%., J. T. Baker ;, DikmaPure ;. Millipore Mili Q., 9 (5mg/L) (5mg/L),, 2. Supelco 24 Waters Oasis HLB (6cc/5mg) (5mL ),, (5mL ), Waters (Quattro Premier XE), MassLynx V4.1. (ESI+) (MRM);( 99.99%), ( 99.99%).,,. ESI(+) [14,17],,, 9 ( 1 g/l, 5μg/L) 2 L/min., ;,,,,. 1. ACQUITY UPLC Waters BEH C μm(2.1 5mm Column); 35..1%(A).1% (B);.4mL/min, A B 1%; ~1.9min,A 5.% 14.5%; 1.9~4.4min,A 14.5% 2.%; 4.4~5.54min,A 2.% 3.%; 5.54~5.541min,A 3.% 5.%, 2min. 1.3, 1, 3 (1 2 3) , 3, 8h 1 ; 1 1mL, 2 3 3mL.,4,48h. (1μg/L ).22μm, ; 1.2 UPLC MS/MS : ( 1μg/L),. 2.5kV, 12, 4, 9L/h, 5L/h,.1mL/min, 1 L; 1.4 (RQ).RQ

3 (PEC)(MEC) (PNEC). RQ, 3, RQ.1~.1,.1~1., 1 [6]. SPE UPLC/MS/MS, MEC, PNEC, RQ Fig.1 Process of the pharmaceutical wastewater treatment plant ,,, [17]., +.1%+.1%.1%+.1% 3. 5μg/L,.4mL/min. 4.,.1%,9 8min,,, ( 3).,, 9,.1%.1% min 2.37min 2.27min TIC 1.52e6 lg () %+.1%.1%+.1% (%) min 1.68min 2.61min 2.72min 3.2min 5.26min (min) 3 9 (5μg/L) Fig.3 Chromatogram of the 9 cephalosporin standards (5μg/L) 2 Fig.2 Mobile phase s effect on targets peak area 2,, 5 (Peak Area), 2.2,, [18],,.,,. 3%

4 % ;, Na 2 EDTA [4]. 8%. ph [18]. Oasis HLB, ph,,. ph, Oasis HLB, HLB (5mL 5mL ) ( 5mL/min)(5mL ) (2h)(5mL )(37 ) (1mL ), ph ,pH=5,, 72.8%~12.2%, 9.51%. SPE UPLC/MS/MS (LOQ) : IQL 1 LOQ (1) R(%) C :IQL, S/N 1:1,μg/L;R SPE, ;C. IQL, 1 ;C 1( 5ng/L). IQL 1μg/L,9 (R 2 >.99)., 27.5~ 131.8ng/L. 1 Table 1 Optimized parameters for MS/MS and method assessment (V) (m/z) (ev) (m/z) ± (n=6) (%) IQL (μg/l) LOQ (ng/l) a 9.2± b 74.9± ± ± ± ± ± ± ± a 8.5 a a 8.5 a a a 2.7 a a b b b b b b b 3.7 b : a, b 2.3,. 4, 4. (42.4~119.μg/L), (1.6~ 14.5μg/L) (5.1~1.μg/L) (5.~6.3μg/L).,.

5 ,37.4, 24.4μg/L; ,5.2,2.7μg/L; 3 7.6,4.2,2.μg/L; 3 5.6,2.2,.6μg/L., 59.2% 59.8% 44.8% 6%; % 47.% 52.5% 75.1%; % 78.7% 73.8% 9.%.,,. ( g/l) (a) ( g/l) (b) ( g/l) (c) (d) n.d. n.d. 4 4 Fig.4 The 4kinds of cephalosporin residue concentration in pharmaceutical wastewater n.d.: ( g/l) %,, (1.6~35.1μg/L),(.8~4.2μg/L) 1.~3.8μg/L) (n.d.~1.5μg/l). [14,19]. 4. RQ, 2, RQ 1.,.,.,,.

6 Table 2 Environmental risk assessment of cephalosporin residues in pharmaceutical wastewater PNEC [2] Max MEC (μg/l) (μg/l) RQ > > > > SPE UPLC/MS/MS,, , 73%. 3.3, 4, ppb,. [1],. [J]., 211,36(2): [2] Sui Q, Huang J, Deng S, et al. Occurrence and removal of pharmaceuticals, caffeine and DEET in wastewater treatment plants of Beijing, China [J]. Water Research, 21,44(2): [3] Kim J W, Yoon S M, Lee S J, et al. Occurrence and fate of PPCPs wastewater treatment plants in Korea [C]//TheSecond International Conference on Environment and Industrial Innovation, IPCBEE, Singapore, LACSIT Press, 212,35: [4],,,.SPE UPLC MS/MS [J]., 213,36(7): [5] Kummerer K. Antibiotics in the aquatic environment A review Part I [J]. Chemosphere, 29,75(4): [6] Hernando M D, Mezcua M, Fernandez Alba A R, et al. Environmental risk assessment of pharmaceutical residues in wastewater effluents, surface waters and sediments [J]. Talanta, 26,69(2): [7] Yu X, ZuoJ, Tang X, et al. Toxicity evaluation of pharmaceutical wastewaters using the alga Scenedesmusobliquus and the bacterium Vibrio fischeri [J]. J. Hazard. Mat., 214,266: [8],,,. [J]., 213,33(12): [9],,,. [J]., 213,33(1): [1] Wang F, Qiao M, Lv Z, et al. Impact of reclaimed water irrigation on antibiotic resistance in publi parks, Beijing, China [J]. Environmental Pollution, 214,184: [11],,,. [J]., 28,28(1): [12] Petrovic M, Skrbic B, Zivancev J, et al. Determination of 81pharmaceutical drugs by high performance liquid chromatography coupled to mass spectrometry with hybrid triple quadrupole linear ion trap in different types of water in Serbia [J]. Sci. Tot. Environ., 214, : [13] Zhang R, Tang J, Li J, et al. Antibiotics in the offshore waters of the Bohai Sea and the Yellow Sea in China: Occurrence, distribution and ecological risks [J]. Environmental Pollution, 213,174: [14] Li B, Zhang T, Xu Z, et al. Rapid analysis of 21 antibiotics of multiple classes in municipal wastewater using ultra performance liquid chromatography tandem mass spectrometry [J]. Analytica Chimica Acta, 29,645(1/2): [] Al Aukidy M, Verlicchi P, Jelic A, et al. Monitoring release of pharmaceutical compounds occurrence and environmental risk assessment of two WWTP effluents and their receiving bodies in the Po Valley, Italy [J]. Sci. Tot. Environ., 212,438: 25. [16] Estevez E, Cabrera M C, Molina Diaz A, et al. Screening of emerging contaminants and priority substances (28//EC) in reclaimed water for irrigation and groundwater in a volcanic aquifer (Gran Canaria, Canary Islands, Spain) [J]. Sci. Tot. Environ., 212,433: [17] Becker M, Zittlau E, Petz M. Residue analysis of penicillins and cephalosporins in bovine muscle, kidney and milk by liquild chromatography tandem mass spectrometry [J]. Anlytica Chimica Acta, 24,52(1/2): [18],. [M]. :, 21,29 3, [19] Sim W J, Lee J W, E. Lee S, et al. Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra high performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry [J]. J. Chromatography A, 213,1292: [2] Kummerer K, Henninger A. Promoting resistance by the emission of antibiotics from hospitals and households into effluent [J]. Clinical Microbiology and Infection, 23, 9(12): (1989 ),,,,.

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