1. Inductively Coupled Plasma Mass Spectrometry
목포대학교 화학과 남상호

2. Ideal Requirements for Methods of Elemental Analysis
1. Applicable to all elements.
2. Simultaneous or rapid sequential multielement determination capability at the major, minor, trace, and ultratrace concentration levels without change of operating conditions.
3. No interelement interference effects.
4. Applicable to the analysis of microliter- or microgram-sized samples.
5. Applicable to the analysis of solids, liquids, and gases with minimal preliminary sample preparation or manipulation.
6. Capable of providing rapid analyses; amenable to process control.
7. Acceptable precision and accuracy.

3. ICP-MS Introduction ICP-MS 분석법 소개 ICP-MS 분석기기 원리 ICP-MS 분석법의 적용 분야

4. 1. ICP-MS 분석법 소개 ICP-MS 분석기기의 개발 및 발전 역사
    
At the end of the 1960s, Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES) as an important future technique for trace and multi-elemental Analysis (Pioneer : Greenfield, Fassel)
1. In the 1974 : the first commercial ICP-AES instrument (by ARL in U.S.A)
2. In the 1970s : the problems for the analysis of trace elements in rock samples due to high matrix concentration
3. Search for alternative method with the advantages of ICP-AES by the mineral study

5. ICP-MS 분석기기의 개발 및 발전 역사 Gray : Mass Spectrometry (MS)
Advantage of simple spectra, good resolution, and high sensitivity
Spark Source Mass Spectrometry (SSMS) : for the solids
A number of problem for wide applications of SSMS
(cost, poor precision, low sample throughput rate, difficult sample preparation)

6. ICP-MS 분석기기의 개발 및 발전 역사
The limitation was mainly from the ionization source
Search for a ionization source for elemental analysis with MS
1. The complete dissociation of the sample
2. High yield of singly charged ions
3. Minimization of poly atomic and multiply charged ions
Attention : atmospheric pressure DCP and R.F. plasma (ICP) for AES

7. The expected problems ICP-MS 분석기기의 개발 및 발전 역사
1. Extraction of ions from ICP (Temp: 8,000K)
2. Transferring the ions into the vacuum system of MS, then to detector

8. ICP-MS 분석기기의 개발 및 발전 역사 A first study Further study show
DC arc source + a small quadruple mass analyzer and channeltron ion detector
The simple spectra ; Possibility of future technique, No information on potential sensitivity
Further study show
A marked advance for solutions samples : very low detection limits due to very low background level

9. ICP-MS 분석기기의 개발 및 발전 역사 DC arc plasma ICP emerging
1. Poor degree of ionization
2. Poor dissociation of the sample molecules
3. Severe matrix effect
ICP emerging
1. Sample introduction region of 7000K
2. The high degree of ionization

10. ICP-MS 분석기기의 개발 및 발전 역사 ICP-MS projects (in 1975) in USA and Canada
-The first publication :
Houk, R.S., Fassel, V.A., Flesch, G.D., Svec, H.J., Gray, A.L. and Taylor, C.E.(1980) Inductively coupled argon plasma as an ion source for mass spectrometric determination of trace elements. Anal. Chem. 52,
The existing problem
1. Interface (conc)
2. Plasma potential : secondary discharge

11. ICP-MS 분석기기의 개발 및 발전 역사 The first commercial ICP-MS in 1983 현재 우리 나라
1. VG Isotopes LTD.
2. Sciex system
현재 우리 나라
1. ICP-MS (약 500대,VG, Perkin-Elmer, H.P…)
2. ICP-AES (약 1000대)

12. ICP-MS 기본원리 What’s the difference between ICPs used in MS and AES
: The orientation and coil grounding arrangement
The two commercial ICP-MS system (Canada & the United Kingdom) are similar.
Home-made instrument (in USA) by Houk
Japan

13. ICP-MS 기본원리
The schematic diagram of typical ICP-MS

14. 분석기기들의 비교
Atomic spectroscopy detection limits

15. 분석기기들의 비교
Analytical working range

16. 분석기기들의 비교
Costs

17. 분석기기들의 비교
Comparison summary

18. ICP-MS 기본 원리
plasma

19. ICP-MS 기본 원리
Degree of ionization versus ionization energy for singly charged ions in the ICP

20. ICP-MS 기본 원리 Unique properties and advantages of ICP
1. The axial channel of the ICP
2. The robustness of the plasma
3. High gas and electron temperatures
4. High electron number density

21. 이온들이 MS 로 들어 가는 과정 1. Boundary layer
2. Plasma potential and secondary discharge
3. Supersonic jet (freely expanding region : zone of silence, surrounded by shock wave)
4. Ion lenses for ion focusing
5. Space charge effects

22. 이온들이 MS 로 들어 가는 과정
ICP and sampling interface for ICP-MS.

23. Quadrupole Mass Spectrometer
1. m/z separation of the extracted ion beam
2. If the RF and DC voltage are selected properly, only ions of a certain m/z ratio will have stable paths through the rods
3. Other ions will be deflected too much and will strike the rods and be neutralized and lost.

24. Quadrupole Mass Spectrometer
Schematic diagram of quadrupole rods showing ion trajectory and applied voltages.

25. Double Focusing MS 1. Quadrupole MS is compact and convenient.
2. The resolution is often insufficient to separate different ions with quadrupole MS.
3. Double Focusing MS : Sampler, skimmer, ion lens, electrostatic analyzer, magnetic analyzer and detector
4. Advantage : The background is very low, No photon stop is necessary, Ion counts rates are comparable to or higher than those obtained with quadrupole, Detection limits can be improved.
Better resolution and detection limit
5. Disadvantage : Slower scan speed and expensive instrument

26. Double Focusing MS Resolution required to separate interferences
Analyte
ion
Interfering
Resolution a
28Si+
14N2+
960
32S+
16O2+
1800
56Fe+
40Ar16O+
2500
80Se+
40Ar2+
9700
159Tb+ b
143Nd16O+
7800
165Ho+ b
149Sm16O+
8900
58Ni+
58Fe+
28000
148Nd+
148Sm+
77000
87Rb+
87Sr+
300000
a Resolution = M/ΔM. The numerical values reflect the resolution required to separate peaks of similar intensity.
b Mono-isotopic elements.

27. Double Focusing MS
High resolution spectra from double focusing instrument illustrating separation of polyatomic ion interferences. Reproduced with permission from VG Elemental.

28. Time of Flight MS Schematic Diagram of Axial TOF ICP-MS Vacuum Stages1 2 3
Acceleration
Extraction
Skimmer
Sampler
Detector
Ion Mirror
ICP Torch
Vacuum Stages
Flight Tube

29. Field-Free Flight Region
Time of Flight MS
Right-angle/Orthogonal Injection
Repeller
Acceleration
Field
Field-Free Flight Region
Ion Lenses

30. Ion Detection
1. Channeltron electron multipliers

31. Ion Detection
The most common ion detector for ICP-MS.
108 electrons at the collector for an ion strike.
A limited lifetime by a total accumulated charge.
The dark current : 1count/sec
The actual background : counts/sec
The actual dynamic range: 106

32. 3. ICP-MS 다양한 시료 주입 방법 I C P Gas Solid Liquid laser ablation flow
injection
liquid
chromatography
electrothermal
vaporization
probe
hydride
generator
nebulizer
I C P

33. : The majority of ICP-MS analysis
Liquid
: The majority of ICP-MS analysis
Nebulizers
- Liquids→Aerosol by a high speed gas or ultrasonic transducer
- A spray chamber after the nebulizer
: To remove some of the large droplets.(>10㎛)
- Three types of pneumatic nebulizer for ICP-MS
: Concentric nebulizer,
Cross flow nebulizer,
Babington type nebulizer

34. Nebulizer Comparison of detection limit(pg/mL) for USN and PN element
isotope
USN
PN without desolvation Mn 55
0.5 5 Ni 58 2 30 Co 59 1 10 Cu 64 3 20 Zn 65
180 Cd
114
170 In
115 8 Cs
133 4

35. Nebulizer Comparison of detection limit(pg/mL) for USN and PN element
isotope
USN
PN without desolvation Ba
137 1 4 Ce
140 10 Nd
144 20 Pb
208 5 35 Bi
209
0.5 Th
232 17 U
238 2

36. Electrothermal vaporization
For samples in micro-volume amounts with very low elemental concentration
A microliter amount(typically 5-100㎕) of sample on electrically conductive vaporization cell.

37. Hydride generator
Em+
 NaBH4 + 3H2O + HCl → H3BO4 + NaCl + 8H → EHn +H2
Comparison of detection limit (ng ml-1) for hydride generation techniques
Element
Hydride
AAS
Nebuliser
ICP-AES
ICP-MS As
1.0
110
0.8
0.005 Se 70
6.0
0.02 Hg
0.01
120
3.0
0.4 Sb 90
0.5
0.004 Bi
0.3 Te
0.1

38. Direct sample insertion
DIN(Direct Injection Nebulizer)

39. Direct sample insertion
DIHEN(Direct Injection High Efficiency Nebulizer)

40. ICP-MS 분석법의 적용 분야 Environmental Industrial Biological Geological
Others

41. Environmental 1. 폐수 속의 다원소 동시 분석. - Cd, Cr, Cu, Fe, Mn, Pb, Zn 등
2. 음료수중의 Hg 정량.
3. 해수중의 메탈수은 정량
4. 대기분진 분석
- Zn, Pb, Ca, Na, Mn, V, Cu 등

42. Industrial 1. 반도체 분야 - 공정상의 용매 불순물 확인. Wafer 표면 분석. 2. 자동차 산업
- 철/비철 합금, 엔진오일 분석.
3. 요업재료 및 전자자료 분석.
4. 석유화학 분야
- 원유의 열분해를 촉진하는 촉매 방해 중금속(Pb, Cd, Hg 등) 분석. 나프타 등의 성분 분석.

43. Geological 1. 암석 - Al, Ca, Fe, K, Mg, Na, Ti : 암석 주성분 정량
- 희토류 분석 : Y 및 란탄족 15원소
- 광석 중 우라늄의 정량.
- 운석의 분석.

44. Biological 1. 혈청 및 혈액 내의 중금속 정량.
- Na, K, Mg, Ca, P, Fe, Zn, Cu, Sr, Ba.
2. 소변
- Na, K, Mg, Ca, P, Zn, Cu.
3. 두발
4. 뼈와 이
- Ca, P, Mg, Na, K, Sr, Fe, Zn, Cd, Ni, Pb, U, Ti .

45. Others 1. 식품 분야 - 식품의 안정성 검사 - 식품 중 영양원소와 유해원소 감시. 2. 농업 분야
- 토양, 비료, 사료, 식물에 포함된 중금속 분석.
3. 원자력 발전소
- 터빈 냉각수 및 UH와 Pu의 조성비 확인을 위한 핵연료 분석.

46. Dynamic Reaction Cell Schematic
Vent
Sampler
Detector
Lens
Mass Analyzer
Reaction Cell
Prefilter
Skimmer

47. What is Dynamic Reaction Cell Technology?
A controlled environment for the promotion of desirable ion-molecule reactions and collisions which eliminate or reduce polyatomic interferences by a process called Chemical Resolution
Chemical Resolution is achieved by introducing a reactive gas into a cell placed in the ion path.
The ion beam containing the analyte and the interfering species is chemically scrubbed of the interference before entering the mass spectrometer for analysis.

48. Reactions and Collisions
Example of a Reaction Inside the DRC Chemical Resolution of 40Ar16O+ from 56Fe+
Gas Inlet
Quadrupole
Mass Filter
Reactive Gas (NH3)
40Ar16O+ + + + + + + + + + +
56Fe + + + + + + + +
56Fe+
Analyzer
Quadrupole + +
Ion-Molecule
Reactions and Collisions

49. 화학종분류 (Chemical Speciation )를 위한 ICP-MS
Definition
Quantitation of the different chemical species
in a sample.
- Cr+3, Cr+6
- Se+4, Se+6
- As+3, As+5, MMAs, DMAs…

50. Chemical Speciation Importance Cr +3 : essential in nutrition Cr
Cr +6 : very toxic to human beings
Se +4
Se  toxicity : Se +6 > Se +4
Se +6
As(III)
As As(V)  toxicity : As +3 > As +5 > MMA > DMA
MMA
DMA

51. Ion Chromatography coupled with Inductively Coupled Plasma Mass Spectrometry
Eluent Reservoir
Pump
Sample Injector
Generator
Detector
Separator Column
● ● ●
Nebulizer
System
Mass Spectrometer
● ● ●
(HG, USN)
ICP

52. Separation of As3+, As5+ and DMA
50 ng/mL As3+, As5+ and DMA in DDW, Sample pH 8

53. Determination of arsenic species in human urine
Measured (ng/mL)
As 3+
3.7
DMA
47.3

54. Speciation of Se4+, Se6+, SeCys and SeMet with IC-ICP-MS
Chromatogram of 10 μg/mL Se4+, Se6+, SeCys and SeMet
Eluent : 10 mM Oxalic acid, 20 mM Potassium sulfate
Sample pH 2