环境水中有机污染物检测方案

Sampling sitesFigure 4： Occurrence of fetracyce antitiorics in the A" niver per sileFlow Determination of antibiotic compounds in water by on-line solidphase extraction - liquid chromatography mass spectrometry Keun-Joo Choi*，Sang-Goo Kim*，Hee-jong Son*，Pyung-jong You*，Chang-won Kim**， Seung-Hyun Kim***， Sook-Hwa Kweon**** a method for antibiotics was deve oped e method shou d quarantee high recovery regard ess of the hydrophobicity of the antibigbics The applicability of the method was investigated for monitoring antbiptics contamination in river sewage. and agricultural wastewate INTRODUCTION Antibiotics pose a threat to water quality management due to their potertial adverse effects on humansand the environment. In Korea aquaculture and livestock farming use substantial amount of antibiotics fordisease control as well as for feed addilives to promole fast growth of fish and liveslock. These anlibioticsare eventualy discharged into receiving streams， which are main drinking water sources. However，veryfew information is avalabe on analylical methods of the antbiotics in wate EXPERIMENTAL CONDITIONS ANTIBIOTICS Sulfonamides (SAs) Tetracyclines [TCs]5) sufamonomethoxine (SMMX)sufadimethoxine (SDMX) oxytetracycineHC (OXTC) minacycineHCI(MCLN) sufamethoxazole (SMXZ)sufathiazol (STZL)sufachloropyndazine (SCPD) doxycycine-Hyclale (DOXN)meclocycline-su fosa icy ate (MECN)chjortetracycfine -HC (CTCL) sufamerazine (SMRZ)sufamethazine (SMTZ) democ peyc ine-HCI(DEMN)tetracycine (TCLN) SAMPLING CONDITIONS . al water samples were fltered through a D 2 pm g ass fter (Millipore]el.·0.2 mL of 5%NazEDTA was added to 50 mL of the fitered watetlef sampe ph was adusted to s 3.0 by adding 40 % sulfuric acid so ution.’ 10 mL of sample was analyzod by SPE.LOMSDto minimize matrix effects， the samples were reanalyzed using the standard addition method (0.2pg/L compound). ON-LINE SPE-LC (SYMBIOSIS ENVIRON) Cartridoe： 10x2 mm， Prospekt Oasis HLBCondilioning 1 mL methyl alcohol 1 mL 0.5N HCI 1 mL waterSampe extraclion 10 ml 2mLmin iulinon-line with LC mobile phase LC/MSD Aqilent 1100 LC/MSD SL operated in Es positive modeColumn： Waters At antis dC18 2.1x50mm， 3un0.1% formic acid in water0.1% formic acid in acetonitrlle Mobile phase B： Gradient run Time Suronan Tteetracyeinines0mi AB=95/4 A/B-96/4AB-75/25AB3-70/30 AB-701301001 AE-204 0.4 mL/min Figure1： TTypyicaf chromatogram for the deferrmnation of sulfonamides a Figure 2. 1Typicel chromatogram for thedetermination of tebracyclnes af VE Figure f and 2 show an efficient seperation of he the seven TCs and SAs using a short C18 co umn and simple gradient Table 1： Online SPE recovery dafa for deionized and surface water Comooundds MW taa.ionns Ficovery，XtSD (3 Detorized watee Surac water P94 Sulfonamides (SAs) TMMX 281 104 107.5±16 103.463 98.9±8.2 84.2±6.4 SDMX 311，156.108 142 94.4±35 96.822 97.6±1.0 96.7±5.6 5MXZ 254，156，108 117 107-9193 83.1*15 74.3+4.0 STZL 256 90.9±32 96.846 97.9±0.8 96.7 ±4.4 SCPD 285.156 85.4±114 85.8±121 99.7±1.9 194141 SMRZ 265.156 96.2±31 104511 101.1±1.4 106.7 +5.1 SMTZ 279156.108 107.6±51 108.9±30 98.94.6 97.2±5.1 Tetracyclines (TCs) OXTC 461，444.426 77 1165±32 1119±29 992±42 1124143 MCLN 458441 64 1012±76 894±118 1022±09 1008±57 DOXN 117 140 1116±39 103446 995±15 1006±12 MECN 477 165 1122±36 1032±10 999±33 102 9±10 CTCL 479.462.444 2 1149±15 1042±23 106 9±36 12011 DEMN 15410077 191 1029±04 17111 105 8±33 1017125 TCLN 4455.42288.410 11 1156±38 1069±26 959±46 1125±41 198 ( . T he d el onized w at e r s amp les indic a t e t hat recov er y is ind e pen d e nt of a na yte c o n ce n trat io r on ， S imia r r e co ver i e s ar e fo u n d fo r the s ur f ace waler samp l es ( s it e 1 ) i n d i c a t in g abs e n c e o f ma tr i x harinffi C alibration curves were developed for TCs and SAs in the 005-1 Po m l range · Good linearity was observed for al compounds (r099) ) Figure 3： Ocourre of sulonemide antibiotics in the "A" river per site. ·Ony several SAs were found in the "A" nver mainstream， whereas most TCs were present at considerable leve s· Site 6， which is near the effluent discharge point of the sewage treatment plant shows contaminationof the river An indication is STZL which is detected at highest concentration in both the "A" river and thesewagelagriculture wasteweterEr Table 3. Antibiodics contamwiatiovi of sewage and egnicuttiwal wastewater (jg) per sife. Sampling sts OXTC MCLN (ungygl)DOXN MECN CTCL DEMN TCLN Stte 9 024 038 022 050 097 027 011 Site 10 ND. ND 003 018 004 0 03 ND Site 11 2362 890 ND 107 1710 3.15 098 Site 12 653 ND ND 037 80 90 270 141 SMMX SOMO SMXZ STZL SMTZ Site9 0.46 0 10.57 1.56 1.53 4.01 Site 10 ND 0.18 0.06 N Site 11 12，23 1158.58 6.53 3.45 9721 Site 12 17 ND 427 ND ND +The results show that sewage and agricu tural waste water is extensively contaminated withaintbioticeCS · All 14 antibiotics (both SAs and TCs) were detected in the sewage sample (site 9)The agricultura waste water samp es contained substantielly higher antibiotic concentrations than ttsewage samples， which indicates the substantial use of antibiotics by the agricultural industrycompared to household and hospitalsThe sewage treatment plant cou d remove 64-100% of the incoming TCs and 96-100% of the SA： · Also the agricultura wastewater treatment plant removed most TCs (44-100%) and SAs (99%)Evidenty the more hydrophobic SAs can be more easily removed by both treatments comparedmore hydrophlic TCs CONCLUSIONS ( A new on ine S P E L C M S D me th o d for the d et e r m i n atio n o f an t i bi o ti cs in l ive s to c k d r i n ki n g wa ter s o u r ces h a s b e en d e ve o pe d . + . The on ine SPE method seived analyticel time and improved recovery compared to off line pro ce o ures . · The aopication revealed that several antibiotics were presentThe Nakdong nv e r s e wa g e and agricu tural w a st e warer were m ot respons i ble f or the a ntibiotics c o n t am i na t ion o f the r iver .+ In aonicultural wastewater much higher concentrations were detected compared to the seweggindicating subst antia l u s e of a n t ibiotics in the a oricultural indust r y . Wa stewate r tr eatm e n t was g ener a l l y eff ec t iv e i n r e m ova l o f th e ant i b i ot ic s t e st e d Th e ex t e n t o f the tr ea t men t dep e nde d on t he type of a nt ibi o t i cs； t he hy droph obic a n tib iot ics were mo r e ) effectivaly removed than hydrophilic antibiotics