NIER-RP MC-ICP/MS 를이용한환경오염물질의 안정동위원소분석기법정립 환경기반연구부환경측정분석센터,,,,,,,,, Jaeseon Park, Yongjae Nam, Ji-Young Kim, 2011

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11-1480523-000985-01 NIER-RP2011-1442 MC-ICP/MS 를이용한환경오염물질의

1 NIER-RP MC-ICP/MS 를이용한환경오염물질의 안정동위원소분석기법정립 환경기반연구부환경측정분석센터,,,,,,,,, Jaeseon Park, Yongjae Nam, Ji-Young Kim, 2011

2 목 차 i iii iv Abstract v Ⅰ Ⅱ i

3 목 차 Ⅲ Ⅳ ii

4 목 차 iii

5 목 차 iv

6 Abstract The stable isotope analytic technique of environmental pollutants is established by using MC-ICP/MS, a high-tech analytical instrument in the environmental forensic field of heavy metals and stable isotopes to offer a clue about the cause and effect relationship of environmental damages by pollutants. The performance of a newly-purchased MC-ICP/MS was checked on the basis of the performance standard. Valuation factors are 1 Sensitivity : 148~578 Vppm -1, 2 Resolution : 8.352, 3 Faraday Detector Noise : 1.5~ SD, 4 Ion Counting Multiplier Dark Noise : 0.01~0.1 cps, 5 Mass stability : 30ppm, and 6 Isotope Ratio Precision : 0.086~ % RSD. As a result, all of the items met the performance standard. After the performance of MC-ICP/MS was checked, analytical conditions such as interference and mass correction were established for items including Pb, Cd and Hg. To keep using these analytical conditions, a program was established and saved. Also, 204,206,207,208 Pb were set as the stable isotopes of Pb, their mass correction was calibrated with 203/205 Tl. For the stable isotopes of Cd 106,108,110,111,112,113,114,116 Cd were set, and their mass correction was calibrated with 107/109 Ag. The stable isotopes of Hg were set as 196,198,199,200,201,202,204 Hg(0.15) before their mass correction was calibrated with 203/205 Tl. Based on the results, their analytical conditions were established. For environmental samples, the stable isotope ratio of Pb items was measured with asian dust and sediments transported into abandoned metal mines downstream. The result of measuring the stable isotope ratio of Pb to asian dust showed a difference between asian dust period and normal state: the ratio of 206/204 Pb was ~ during the non-asian dust period while the 206/204 Pb ratio of particulates was The source that occurred asian dust was checked through the trajectory analysis. In case of the stable isotope ratio of the harmful v

7 Abstract heavy metal (Pb) to sediments in the abandoned metal mines downstream, the 206/204 Pb ratio was ~ at ID mine downstream while the 206/204 Pb ratio of tributary sediments was At the confluence area, the ratio turned out to be The 206/204 Pb ratio at the confluence was , which is heavier than that of tributary ( ) or main stream ( ). At ID mine, on which agricultural land has relatively few effects, the results were what has been theoretically expected (tributary>confluence>main stream). The results of the agriculturally affected DJ mine, on the other hand, showed no sign that heavy metals from the main stream and tributaries were put together at the confluence. In conclusion, the possibility of tracing discharge sources was confirmed based on the fact that Pb isotope ratios of asian dust and sediments at abandoned metal mines downstream are different depending on their discharge sources. Moreover, a QA/QC checklist was completed based on factors such as gas pressure of MC-ICP/MS, vacuum conditions, gas flow, torch location, RF generator, chiller, plasma light and IC operating, which have an effect on the stability and precision of the high-tech instrument. Since Korea has lately begun to use MC-ICP/MS, it is urgent to establish a library on stable isotope ratios of environmental pollutants. Therefore, it is necessary to focus on data collection as well as direct use of study results. vi

8 Ⅰ. 서론 Ⅰ 1

9 Ⅰ. 서론 <Fig. 1> Research promotion system. 2

10 Ⅱ. 연구내용및방법 Ⅱ. <Table 1.> Trend of stable isotope research in Korea Reference Li Li Min Seok Choi et. al Pb Man-Sik Choi et. al Pb

11 Ⅱ. 연구내용및방법 <Table 2.> Trend of stable isotope research in foreign country Reference, Pb Alain Cocherie and Michele Robert 2007, Pb M. Conkova and J. Kubiznakova 2008,,, Hg Runsheng Yin et. al. 2010,, Si Isabelle Basile-Doelsch 2006 Cu, Zn Moritz Bigalke et. al. 2010, Mg Edward T. Tipper et. al Si R. B. Georg et. al Ca J. Fietzke et. al. 2004, B Bo-Shian Wang et. al Cd S. Ripperger et. al. 2007, Tl Sune G. Nielsen et. al. 2004,,, Pb Dominik J. Weiss et. al ( ) Cd Frank Wombacher et. al Os G. M. Nowell et. al Hf and Lu Arnaud Goolaerts et. al Pb, Cu, Sr Jugdeep Aggarwal et. al S Paul R. Craddock et. al (fossilteeth ) Sr Sandi R. Copeland et. al Se Thomas M. Johnson 2004 Pb Joel Baker et. al ( ) Hg Run-Sheng YIN et. al

12 Ⅱ. 연구내용및방법 <Table 3.> Application for stable isotope research in Korea and Abroad H, C, N, Pb, Sr Phillips and Gregg 2003 Pb, Cu, Sr Aggarwal et. al Hg Yin et. al Sr Copeland et. al Cu, Zn Bigalke et. al Evans et. al Hg Estrade et. al Yin et. al S Craddock et. al Hf, Lu Goolaerts et. al Os Nowel et. al Cd Ripperger and Rehkamper 2007 Cocherie and Robert 2007 Pb Weiss et. al Baker et. al White et. al Cr, Ni, Cu, Zn Makishima et. al Li Choi et. al Willigers et. al Pb Bellucci et. al Cu Asael et. al Se Johnson et. al Cd Wombacher et. al Fe Rouxel et. al Si Georg et. al Pb Choi et. al

13 Ⅱ. 연구내용및방법. <Table 4.> Pre-treatment methods for stable isotope analysis Methods of pre-treatment Acid digestion Microwave digestion High pressure-high temperature digestion Laser ablation Vapor preconcentration technique by amalgam Anion exchange chromatography Cold vapor gas chromatography Reduction by SnCl 2 Element Heavy metal Heavy metal Heavy metal Heavy metal Hg Hg Hg Hg 6

14 Ⅱ. 연구내용및방법. MC-ICP/MS <Fig. 2> Installation of MC-ICP/MS in clean room. 7

15 Ⅱ. 연구내용및방법.. 8

16 Ⅱ. 연구내용및방법 <Table 5.> Sampling conditions of dust in ambient air ~ (9, 24 ) , 30 1, 8, 9, 29, 30 1 ( ), 6 ( ) High Volume Air Samper (Pb ) 36.44, <Fig. 3> Sampling site of dust in ambient air. 9

17 Ⅱ. 연구내용및방법 ID ( : ) - ( ), ( ), ( ) 12 <Fig. 4> Sampling site of abandoned metal mine ID. DJ ( : ) - ( ), ( ), ( ) 6 <Fig. 5> Sampling site of abandoned metal mine DJ.. 10

18 Ⅱ. 연구내용및방법 <Asian dust Sample> Add 5 ml mixed acid (HNO 3 :HClO 4 =4:1) and 1 ml HF to quartz filter <Sediment Sample> Add 5 ml mixed acid (HNO 3 :HClO 4 =4:1) to 0.2g Sample Add 5 ml mixed acid (HF:HClO 4 =3:1) Add 2 ml HNO 3 and 0.5 ml HF Add 2 ml HCl Add mixed acid (HClO 4 :HBr=4:1) Dilute with 1% HNO 3 Spike Tl solution (SRM997) Inject into MC-ICP/MS <Fig. 6> Pre-treatment procedure of each sample. 11

19 Ⅱ. 연구내용및방법. MC-ICP/MS <Table 6> Operation conditions of Nu plasma II Plasma RF generator[w] : 1300 Cool gas flow (L/min): 13 12

20 Ⅱ. 연구내용및방법 Aux gas flow (L/min): 0.8 Nebulizer gas: Nebulizer: 30 psi for DSN DSN(100um) Vacuum Analyzer Transfer Backing < 3e-9 mbar < 2e-7 mbar < 1e-1 mbar Acquisition parameter Multicollection Detector Total 19 Integration time(s) 10 No. of Blocks 2 Cycle/Block 25 Evaluation parameter Outlier test Mass bias correlation 2 sigma 203Tl/205Tl <Table 7> Operation conditions of Neptune Plasma Extraction [V] Focus [V] Cool gas flow (L/min) 15.2 Aux gas flow 1.5 Sample gas flow

21 Ⅱ. 연구내용및방법 Nebulizer: pray chamber 100 um teflon Dual spray chamber Beam tuning X Pos [mm] 1.2 X Pos [mm] 0.5 X Pos [mm] -1.2 Acquisition parameter Multicollection Detector Total 9 Integration time (s) No. of Blocks 1 Cycle/Block 15 Evaluation parameter Outlier test Mass bias correlation 2 sigma 203Tl/205Tl 14

22 Ⅲ. 연구결과및고찰 Ⅲ. Sensitivity <Table 8> Sensitivity of MC-ICP/MS (Nu plasma II) Isotope Abundance (%) Mesured Sensitivity(V) Wet Dry Wet plasma system(100 μg /L) Spec. (Vppm -1 ) Achieved (Vppm -1 ) Dry plasma system(10 μg /L) Spec. (Vppm -1 ) Achieved (Vppm -1 ) 7 Li >15 15 > Sr >25 43 > Nd >35 48 > Pb >45 48 > U >40 47 > Achieved sensitivity(vppm -1 )=Measured sensitivity(v) Conc./Abundance 15

23 Ⅲ. 연구결과및고찰. Resolution <Table 9.> Results of resolution test using 142 Nd Low Pseudo High Specification Achieved Specification Achieved Specification Achieved > > > Faraday Detector Noise 16

24 Ⅲ. 연구결과및고찰 <Table 10.> Noise values of 16 faraday detectors F.C Spec. F. Identifier F. Noise ( 10-5 SD) H9 H8 H7 H6 H5 H4 H3 H2 H1 Ax L1 L2 L3 L4 L5 L <3. Ion Counting Multiplier <Table 11.> Dark noise, Stability and Gain values of 3 Ion Counting Multipliers Multiplier Dark Noise Spec. (cps) Achieved (cps) Multiplier Stability (U) Spec. (%/hour) Achieved (%/hour) Spec. (RSD%) Multiplier Gain(U) Achieved (RSD%) IC0 < < < IC1 < < < IC2 < < <

25 Ⅲ. 연구결과및고찰. Mass Stability <Table 12.> Mass stability and abundance sensitivity using 238 U Peak Side Stability (U) Spec. Achieved Spec. < 50 mg/l over 30 min 30 mg/l Abundance Sensitivity (U) < 5 mg/l at 1 amu Achieved (%/hour) 2.7 mg/l Mass Stability in 30 min M = 8/163( ) = M.S. = M/M/2 = (0.0084/142)/2 mg/l mg/l 18

26 Ⅲ. 연구결과및고찰 mg/l. Isotope Ratio Precision <Table 13.> Precision of stable isotope ratio with some elements Element Ratio Spec. (%RSD) Achieved (%RSD) Natural Mean Ratio Measured Li (100 μg /L) Sr (100 μg /L) Nd (75 μg /L) 7 / / / / / / Pb (45 μg /L) 208 / / U (100 μg /L) 235 / /

27 Ⅲ. 연구결과및고찰. Pb (4 isotopes) 7 (Pb) (Tl), (Hg) block, 2 block. 206 Pb axial, 208 Pb, 207 Pb, 204 Pb high-2, High-1, low-2, 205 Tl, 203 Tl, 202 Hg low-1, low-3, low Tl/ 203 Tl , 204 Pb 204 Hg mercury factor

Ⅲ. 연구결과및고찰 <Fig. 7> Method development of Pb isotopes.. Cd (8 isotopes) 14 (Cd) (Ag), (Pd), (In), (Sn). 1 500 10 25 2 block, 2 block.

28 Ⅲ. 연구결과및고찰 <Fig. 7> Method development of Pb isotopes.. Cd (8 isotopes) 14 (Cd) (Ag), (Pd), (In), (Sn) block, 2 block. 110 Cd axial, 116 Cd, 114 Cd, 113 Cd, 112 Cd, 111 Cd, 108 Cd, 106 Cd, high-6, high-4, high-3, high-2, high-1, low-2, low Ag, 107 Ag low-1, low-3, 104 Pd low-5, 115 In high-5, 120 Sn, 118 Sn high-8, high Pd, 108 Pd, 106 Pd , , , 113 In , 116 Sn, 114 Sn, 112 Sn , ,

29 Ⅲ. 연구결과및고찰 <Fig. 8> Method development of Cd isotopes.. Hg (7 isotopes) 22

30 Ⅲ. 연구결과및고찰 <Fig. 9> Method development of Hg isotopes. 23

31 Ⅲ. 연구결과및고찰 <Table 14> Comparison of published Pb stable isotopic ratios of NIST-SRM 981 by MC-ICP/MS Authors 206/204 Pb 207/204 Pb 208/204 Pb 208/206 Pb 207/206 Pb Certificate Todt et al.(1996) Thirlwall(2000) Hirata(1996) Belshaw et al.(1998) Rehkamper and Halliday(1998) White et al.(2000) Rehkamper and Mezger(2000) M.S.Choi(2001) This study(1) [Neptune] This study(2) [Neptune] This study [Nu Plasma II]

32 Ⅲ. 연구결과및고찰. ( / ) <Table 15.> Pb stable isotope ratio in ambient air Classi-fi cation 206/204 Pb 207/204 Pb 208/204 Pb 208/206 Pb 207/206 Pb A-1 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-2 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-3 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-4 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-5 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-6 (Stdev.) ( ) ( ) ( ) ( ( ) A-7 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-8 (Stdev.) ( ) ( ) ( ) ( ) ( ) A-9 (Stdev.) ( ) ( ) ( ) ( ) ( ) 25

33 Ⅲ. 연구결과및고찰 <Fig. 10> Comparison of Pb isotope ratios in asian-dust period /normal state 26

Ⅲ. 연구결과및고찰 <Asian dust period> <Normal state> (A8 : 2011.05.1~2) (A9 : 2011.05.6~7) <Fig.

34 Ⅲ. 연구결과및고찰 <Asian dust period> <Normal state> (A8 : ~2) (A9 : ~7) <Fig. 11> Trajectory Analysis during asian dust period and normal state at background ambient air.. 27

35 Ⅲ. 연구결과및고찰 <Table 16.> Pb stable isotope analytical results of sediments at the main stream, tributary and confluence of ID mine Classification 206/204 Pb 207/204 Pb 208/204 Pb 208/206 Pb 207/206 Pb Main (ID1~10) Ave Tributary(ID 12) Confluence(ID 11)

36 Ⅲ. 연구결과및고찰 <Fig. 12> Correlation of Pb stable isotope ratio of sediments at the main stream, tributary and confluence of ID mine. 29

37 Ⅲ. 연구결과및고찰 <Table 17.> Pb stable isotope analytical results of sediments at the main stream, tributary and confluence of DJ mine Classification 206/204 Pb 207/204 Pb 208/204 Pb 208/206 Pb 207/206 Pb Main (DJ 1~4) Ave Tributary(DJ 5) Confluence(DJ 6)

38 Ⅲ. 연구결과및고찰 <Fig. 13> Correlation of Pb stable isotope ratio of sediments at the m ain stream, tributary and confluence of DJ mine. 31

39 Ⅲ. 연구결과및고찰 <Table 18.> QA/QC checklist of MC-ICP/MS Items Parameters Criteria Unit 1 Temp, Humidity (at room) 2 Gas Pressure 3 Vacuum system 4 Gas flow setting 5 Torch position Temp.: Temp 22 ± 1 Humidity: Humility < 60% % Compress air: 5 bar bar Argon: 5 bar bar 5 turbo pump speed: all > 95% % 2 rotary pump: run or stop Analyzer vacuum: <3e-9 mbar mbar Transfer vacuum: <2e-7 mbar mbar Backing vacuum: <1e-1 mbar mbar Cool Gas flow: 13 L/min L/min Aux Gas flow: 0.8 L/min L/min Neb Gas pressure: 30~35 psi for DSN and wet Plasma sample corn tip, distance: 1~3 mm mm psi 32

40 Ⅲ. 연구결과및고찰 6 All electronic Units Bonnet position ELECTRONICS PLASMA SERVICE MAGNET SLAVE 1KV UNIT SOURCE HV SUPPLY IC SUPPLY push back to the RF coil switched on by the order switched on by the order switched on by the order switched on by the order switched on by the order switched on by the order 7 RF Generator Set Forward power: 1300W W 8 Plasma chiller 9 Vacuum Capacitor 10 Probe temp. Water flow rate: around 2.0 L/min L/min HV1 current: < 3e-1 ma ma HT1: 6000V V Temp.: < 20 Lighting: around 1620 μf to 1640 μf μf Temp.: 44±2 33

41 Ⅳ. 결론 Ⅳ 34

42 Ⅳ. 결론 35

43 36 Ⅳ. 결론

44 Ⅳ. 결론 37

45 Ⅳ. 결론 38

46 Ⅳ. 결론 Ⅱ 39

47 Ⅳ. 결론 40

48 Ⅳ. 결론 41

49 Ⅳ. 결론 42

50 Ⅳ. 결론 43

유해중금속안정동위원소의 분석정밀 / 정확도향상연구 (I) 환경기반연구부환경측정분석센터,,,,,,,, 2012

11-1480523-001163-01 유해중금속안정동위원소의 분석정밀 / 정확도향상연구 (I) 환경기반연구부환경측정분석센터,,,,,,,, 2012 목 차 ⅰ ⅲ ⅳ Abstract ⅵ Ⅰ Ⅱ Ⅲ i 목 차 Ⅳ ii 목 차 iii 목 차 iv 목 차 v Abstract vi Abstract σ ε vii Abstract viii Ⅰ. 서론 Ⅰ. 1 Ⅰ. 서론.