Unit 5 of the Soil Chemical Analysis

The Analysis of Cation Exchange Phenomena

in Soils
Part 1. Determination of Cation Exchange Capacity and
Exchangeable Cations
土壤陽離子交換現象之分析
(⼀) 陽離子交換容量及交換性陽離子之測定

Sheng-Bin Ho
Department of Agricultural Chemistry
National Taiwan University

2019/11/01 1
 Sources of Negative Charge in Soils
 Constant Charge (Permanent Charge, Structural Charge)
The surface charge for constant charge minerals is not
influenced by pH, electrolyte concentration, solvent
characteristics, ionic makeup of the embedding solution or
temperature, however the surface potential for these minerals
is affected by all of the above parameters.
 Variable Charge (pH-dependent Charge)
The surface potential for variable charge minerals does not
vary with electrolyte concentration, solvent characteristics,
temperature, or ionic makeup of the embedding solution
provided the ions are not PDIs or CDIs, however the surface
charge does.
The surface potential on variable charge minerals does change
with adsorption of PDIs or CDIs, or a pH change.
PDI: Potential determining ion; CDI: Charge determining ion 2
 Characteristics of Constant Charge
Isomorphic substitution is the principle source of negative charge for
2:1 and 2:1:1 layer silicates, but is of minor importance for the 1:1
minerals and accessory minerals.
Isomorphic substitution in minerals almost universally creates
negatively charged surfaces.
2 σ cc = surface charge density (cmol c kg -1 )
- 10 X
σcc = - - - - - -(5 - 1) X = layer charge of mineral (mol c mol -1
)
M FW -1
M FW = formula weight of mineral (kg mol )

Often effective surface charge or CEC is more important than total

structural charge.
Less importance is given to surface area since constant charge is not
derived from surface reactions.
The ions balancing charge on constant charge surfaces are usually
considered as a homogeneous layer. Site numbers are not important
and adsorption is “mobile” being parallel to the surface.
3
 Characteristics of Variable Charge
The primary source of variable charge is considered to be the loss of
adsorbed H+ and OH- on inorganic solids( Inorganic surface hydroxyl
groups ) and H+ from organic acids, phenols and other functional
groups in soil organic matter( Organic surface functional groups ).
Variable charge results from the sum of proton transfer reactions( σ H)
and other surface coordination reactions ( σ CDI ).
ΓH = adsorption density of protons (cmol c kg -1 )
σ vc = σ H + σCDI − − − −(5 − 2)
ΓOH = adsorption density of hydroxyls (cmol c kg -1 )
σ H = [ ΓH - ΓOH ] - - - (5 - 3)
Z CDI = Valence of adsorbed CDIs other than H + or OH -
σCDI = Σ ( Z CDI ΓCDI ) - - - (5 - 4) ΓCDI = adsorption density of CDIs other than H + or OH - (cmol c kg -1 )

The charge on variable charge surfaces is usually considered to be

“discrete” or to occur at a specific site. Site numbers on the particle
surface are quite important with adsorption localized at recognizable
sites.
4
 CEC and Exchange Phase Composition
 Definition of Exchangeable Ion:
Operational definition: an ion that is removed from the soil
by a solution containing a neutral salt.
Mechanistic definition: an ion in the fully hydrated state
that is bound at the soil surface solely by outer-sphere and
diffuse-ion swarm mechanisms.
 Cation Exchange Capacity of Soils (a pH dependent
property):
“The sum total of the exchangeable cations that a soil can
adsorb.” or ”The capacity of a soil to hold cations.”
The sum of exchangeable bases plus total soil acidity at a
specific pH value, usually 7.0 or 8.0.
x+ x-
CEC = M Excess + ADeficit - - - - - - - (5 - 5)
5
Figure 5-1 Schematic representation
of the solid-solution interface
illustrating the adsorption planes (s,
is, os, and d) and the associated
charge densities (σH, σis σos,and σd).
6
 Major exchangeable cations in field soils:
Ca2+, Mg2+, K+, Na+, (H+, Al3+)

5-1.

7
 Cation Exchange Capacity of Soils

The CEC of a soil depends rather critically on the manner and

conditions in which it is determined.

The charge of the variable charge component is very

definitely altered by both the concentration and valence of
the ions in the equilibrium solution.
Specific adsorption of both cations and anions can have
marked effects on CEC.
CEC always must be operationally defined in terms of
variables such as pH, concentration, nature and valence of
the ions and buffer capacity of the extracting salt solution,
the nature of the washing liquid to remove entrained salt
solution and the temperature.
8
 5-2.
 Cation exchange capacity of soils
range from 1 to 60 cmolc Kg-1
(centimoles of positive charge per
kilogram of soil).

Unit of CEC
meq (100 g)-1
= cmolc kg-1 (or cmol+ kg-1)

9
 Exchange Phase Composition
The dilution of a solution in equilibrium with the
exchanger phase favors the retention of more highly
charged exchangeable ion. (The valence dilution effect)
-----(5-6)

-----(5-7) Rearrange to -----(5-8)

10
5-3.

11
 Lyotropic series: The relative replaceability of
exchangeable cations (ease of removal).

(Hydrated radii in nm)

IZ : the ionization energy

(Misono softness parameter) -----(5-9) of cation of valence Z
and radius r.

12
5-4.

13
 -----(5-10)

----(5-9)

IZ: the ionization energy of cation

of valence Z and radius r.

5-2.

14
 Complementary cation effect: Exchanging one
cation for another in the presence of a third cation
becomes easier as the retention strength of the third
cation increases.
 Preference for a particular ion in some soil
components.

15
 Determination of Cation Exchange Capacity and
Exchangeable Cations

General Procedure: (saturation, washing, replacement)

1. The soil is saturated with a single index ion (e.g., NH4+).
NH4+ + M-Soil → NH4+-Soil + M -----(5-11)
(Index cation) (Exchangeable cations)
(Ca2+, Mg2+, K+, Na+, Al3+ …)
2. The soil is then washed free of soluble salts, including index ion,
often with alcohol to keep soil flocculated and to prevent loss of
the index cation by hydrolysis.
3. The index cation is then extracted with another salt solution (e.g.,
NaCl) and measured to give the CEC.

16
 Commonly used index ions:
NH4+ (0.2 M or 1 M NH4Cl, 1 M NH4OAc, 1 M NH4NO3)
Ba2+ (0.1 M or 0.2 M BaCl2, 0.25 M BaCl2-TEA)
Na+ (0.4 M NaOAc-0.1 M NaCl, 1 M NaOAc).
Solution buffered at pH 7.0 or 8.2
Unbuffered solution
 Commonly used washing solution: 95% ethanol,
99% methanol, 99% isopropyl alcohol.
 Extracting or Replacing solution: depends on index ion used.
(KCl, NaCl, NH4Cl …)

17
 Problems in measurement of Cation Exchange Capacity
(To be continued)
 Presence of Soluble Salts and Carbonates
Underestimation of CEC
CEC cannot be estimated by summing exchangeable cations,
and often not by simple saturation techniques.
 Effect of Cation and Anion Type
Underestimation or overestimation of CEC
• Fixation of K+ and NH4+ by micaceous minerals
• Many polyvalent ions form hydroxy ions
• Considerable hydrolysis may occur when monovalent
cations are used for index cations at reduced electrolyte
concentration
• Effects of specific adsorbed anions. (e.g., SO42-, PO43-)
• Soluble complex or ion-pair formation (e.g., CaCl+) 18
 Problems in measurement of Cation Exchange Capacity
(Continue)

 pH Effects and the Use of Buffered Solutions

Almost all topsoils and many subsoils contain variable
charge surfaces.
Buffered solution cannot be used to estimate exchangeable
Al3+.
 Ionic Strength Effects and Removal of Entrained Electrolyte
It is important to fix or measure the ionic strength of the
solution at the end of the extraction process during CEC
measurement.
Incomplete removal of entrained electrolyte and prolonged
washing result in errors in CEC measurement.

19
 Three-step CEC Determination
Ammonium Acetate (pH 7) Method, Standard Method

Entrained
electrolyte

5-3.

20
Figure 5-4. Complete vacuum-filtration assembly using a Büchner funnel.

21
5-5.
22
5-6. 23
5-7. 5-8.
24
5-9. 25
 Connecting
L-tube
在組合、拆卸、及淋洗操作過程 125-mL Rubber
Separatory tubing
中應盡量避免使土壤管柱受到過 funnel
多的振動，尤應避免以外力(如拆
卸裝置、真空抽氣等)強迫淋洗。 Leaching
solution Rubber
stopper

Stop
cork Leaching
column
Soil
sample
Sintered
Celite glass plate

Connecting
L-tube
Figure 5-10. Modification of 250-mL
the leaching apparatus of Erlenmeyer
flask Leachate
Schollenberger and Simon.
26
Sintered
glass plate
250-mL
Erlenmeyer
flask
Leaching
column

Rubber
125-mL tubing
Separatory
funnel

Rubber Two
stoppers Connecting
L-tubes 27
 Construction
of the
Fixation of assembly
column
Begin to
leaching

Addition
of Celite
and soil
28
 Some features of ammonium acetate (pH 7)
method in the determination of soil CEC

 Ammonium acetate is highly buffered.

 Ammonium is easily determined.
 Simultaneously measurement of exchangeable
cations.
 It will often give somewhat lower values for CEC.
 The solubility of CaCO3 and CaSO4 in the ammonium
acetate solution are relatively high.

29
 現時(或田間狀態)土壤pH下的陽離子交換容量，稱為現時陽
離子交換容量(Effective cation exchange capacity, ECEC)：
通常以總和法測定之；即以1 M NH4OAc，0.2 M NH4Cl，
0.1 M BaCl2或1 M BaCl2-TEA等溶液交換所得之鹽基離子(即
交換性鹽基離子)的總量，加上以1 N KCl、0.2 M NH4Cl或
0.1 M BaCl2溶液萃取出之鋁離子及氫離子(即交換性酸度)的
量。亦可使用強迫置換法(Compulsive exchange method)
測得。

30
Unbuffered Salt Extraction Method for Soil CEC Determination
(1) Weigh 5 g of soil into 50-mL centrifuge tube.

(2) Add 30 mL of 0.2 M NH4Cl and shake for 5 min.

(3) Centrifuge and decant supernatant into a

250-mL volumetric flask.
(4) Add 30 mL of 0.2 M NH4Cl, resuspend the
soil using the Vortex stirrer, shake for 5 min,
centrifuge and decant supernatant into
volumetric flask.
(Repeat the process three more times.)
(5) Combining supernatants prior to making up Determination of
to volume with 0.2 M NH4Cl. Exchangeable Ca,
(6) Add 3 x 30 mL portions of 0.04 M NH4Cl, Mg, K, Na, and Al
resuspend, shake for 5 min, centrifuge, and
discard the supernatant each time. 31
 (7) Weigh tube to determine volume of entrained
solution (VEn).
(8) Add 30 mL of 0.2 M KNO3, resuspend, shake for
5 min, centrifuge and collect supernatant in a
250-mL volumetric flask.

(Repeat the process four more times.)

(9) Combining the supernatants and make up to

volume with 0.2 M KNO3.

(10) Analyze this solution for NH4+ and Cl-.

(11) Calculate the CEC.

CEC (cmolc kg-1) = (NH4+-N x 5)/14 – 0.80 x VEn-----(5-12)

32
 強制交換(Compulsive exchange)法

 本法係先將土壤以Ba2+離子予以飽和，再以MgSO4溶液將吸附之Ba2+離
子強制交換出，並添加足量的MgSO4溶液，使懸浮液維持適當的離子強
度，由MgSO4溶液的添加量以及平衡溶液中之Mg2+離子濃度，即可計
算陽離子交換容量。以100 g土壤而言：

x土壤 - Ba + y BaCl 2 (殘留) + z MgSO 4

→ x土壤 - Mg + y MgCl 2 + ( z - x - y )MgSO 4 + ( x + y )BaSO 4 ↓ - -( 5 - 13)

其中 x, y, z 之單位為 milliequivalents

CEC = 自溶液中消失之 Mg = z - [ y + (z – x - y)] = x meq (100 g)-1 ---(5-14)

33
 Compulsive Exchange Method
Soil W1 = Wb + Ws (g)
 Saturating solution (0.2 M BaCl2/0.2 M NH4Cl )
Exchangeable Ca, Mg, K, Na
 0.05 M BaCl2

 Equilibrating solution (0.002 M BaCl2 , C1 (meq mL-1))

Weighing after centrifugation, W2 (g)
Reactant solution (0.005 M MgSO4 ), 10 mL
Adjust ionic strength Ionic strength reference solution
Weighing, W3 (0.0015 M MgSO4)
• Centrifugation
CR = ECsusp/Ecref
Solution Analyze Mg2+(C2) and If CR < 1.0 add 0.05 M MgSO4(V, mL)
Cl-(C3)
If CR > 1.0 add DI water
100
CEC (meq (100 g) -1 ) = [0.01 × (10 + 10 × V ) - C 2 × (W 3 - W1 )] - - - - - (5 - 15)(If add MgSO 4 )
Ws
100 34
CEC (meq (100 g) -1 ) = [0.1 - C 2 × (W 3 - W1 )] - - - - - (5 - 16)(If add DI water )
Ws
 土壤酸度(soil acidity)也是⼀種操作型的定義，通常包含四種型態；即(1)
交換性鋁離子(Al3+, Al(OH)2+, Al(OH)2+)水解產生的氫離子，(2)部分水解
及非交換性鋁水解產生的氫離子，(3)具弱酸性質之官能基，以及(4)交換
性氫離子；其在土壤中主要存在的pH範圍及其中和反應可表示如下：
pH < 5.5
(1) Al 3+ + 3 OH - → Al(OH) 3 - - - - - - (5 - 17a)
Al(OH) 2+ + 2 OH - → Al(OH) 3 - - - - - - (5 - 17b)
Al(OH) 2+ + OH - → Al(OH) 3 - - - - - - (5 - 17c)
pH > 5.5
(2) Al x (OH) 3 x-y + y OH - → Al x (OH) 3 x - - - - - - (5 - 18)
O O
=
=

(3) R - C - OH + OH - → R - C - O - + H 2O - - - - - - (5 - 19)

pH < 4.0
(4) H + + OH - → H 2O - - - - - - (5 - 20) 35
 傳統操作上，將土壤酸度區分為可滴定性酸度(Titratable acidity)
或總酸度(Total acidity)、交換性酸度(Exchangeable acidity)(型
態(1)及(4))以及可滴定之非交換性酸度(Titratable but
nonexchangeable acidity)(型態(2)及 (3))。此外，下列陰離子交
換反應亦會消耗氫氧基離子而被包含在總酸度及可滴定之非交換性
酸度中。

X - Al(OH)(H 2 PO 4 ) + OH - → X - Al(OH) 2 + H 2 PO -4 - - - - - - (5 - 21)

36
 土壤酸度測定

 總酸度：氯化鋇-三⼄醇胺法 (Barium Chloride-

Triethanolamine Method)

 交換性酸度：氯化鉀法 (Potassium Chloride Method)

37
 總酸度：氯化鋇-三⼄醇胺法
(Barium Chloride-Triethanolamine Method)

Soil
Blank • Extracted by Barium chloride-Triethanolaminen buffer
(Buffer solution, pH 8.2 (Mixing, standing, and filtration)
solution + • Leaching with Barium chloride exchange solution
Exchange
solution) Leachate ( + Bromcresol green and Mixed indicator )
(Green Color) (Green Color)

• • Titrate with 0.2 N HCl ( Vblank , Vleachate )

(Purple Color) (Purple Color)

38
Calculations:

(Vblank - Vleachate ) × N HCl × 100

Total acidity (meq/100 g) = - - - - - - (5 - 22)
Wt

其中 Vblank 與 V leachate 分別為空白溶液與土壤濾液之HCl溶液滴定量，

N HCl 為標準鹽酸溶液之當量濃度， Wt 為土壤重量(g)。

39
交換性酸度：氯化鉀法(Potassium Chloride Method)

Soil

• Extracted by 1N KCl (Mixing, standing, and filtration)

Extarct ( Al 3+ , Al(OH) 2+ , Al(OH) +2 , H + ) (+ Phenolphthalein)

(Colorless)

• Titrate with 0.1 N NaOH ( V NaOH, sample )

(Pink color) ( pH 8.2 )
3- x + 3− -
• Addition of 1 N KF ( Al ( OH) x + 6 KF → K + AlF6 + x OH )

(Pink color)

• Titrate with 0.1 N HCl ( V HCl )

(Colorless)
40
Calculations:
(Vsample - Vblank ) × N NaOH × 100
Exchangeable acidity (meq/100 g) = - - - (5 - 23)
Wt
VHCl × N HCl × 100
Exchangeable Al (meq/100 g) = - - - - - - (5 - 24)
Wt
Exchangeable H (meq/100 g) = Exchangeable acidity - Exchangeable Al - - (5 - 25)

其中 Vsample 與V blank 分別為土壤濾液與空白溶液之氫氧化鈉溶液滴定量，

V HCl 為土壤濾液之鹽酸溶液滴定量，
N NaOH 與 N HCl 分別為標準氫氧化鈉溶液與標準鹽酸溶液之當量濃度，
Wt 為土壤重量(g)。

41
 Atomic Spectrometry, Training Courses Series no.1

Atomic Absorption Spectrometry

原子吸收光譜法

Sheng-Bin Ho
Department of Agricultural Chemistry
National Taiwan University
42
References :

B. Welz and M. Sperling. 1999. Atomic Absorption Spectrometry. 3rd Ed. Wiley-
VCH, Weinheim. L. H. J. Lajunen and P. Perämäki. 2004. Spectrochemical
Analysis by Atomic Absorption and Emission. 2nd Ed. Royal Soc. Chem.,
Cambridge.
José A. C. Broekaert. 2002. Analytical Atomic Spectrometry with Flames and
Plasmas. 2nd Ed. Wiley-VCH, Weinheim.
E. Rosenberg and U. Panne. 2003. Atomic Absorption Spectrometry (AAS) and
Atomic Emission Spectrometry (AES). In Handbook of Spectroscopy. Vol. 1.
G. Gauglitz and T. Vo-Dinh (Eds.). pp. 421-496. Wiley-VCH, Weinheim.
B. Welz, H. Becker-Ross, S. Florek, and U. Heitmann. 2005. High-Resolution
Continuum Source AAS. Wiley-VCH, Weinheim.
D. J. Butcher and J. Sneddon. 1998. A Pratical Guide to Graphite Furnace Atomic
Absorption Spectrometry. John-Wiley & Sons, New York.
J. Nölte. 2003. ICP Emission Spectrometry--- A Pratical Guide. Wiley-VCH,
Weinheim.
Jiří Dědina and D. L. Tsalev. 1995. Hydride Generation Atomic Absorption
Spectrometry. John-Wiley & Sons, New York.
43
 AAS_2014s. (PDF files)
 Holler, E. J., D. A. Skoog, and S. R. Crouch. 2007. An Introduction to optical
atomic spectrometry. In Principles of Instrumental Analysis. 6th Ed. Chap. 8.
pp. 215-229. Thomson Brooks/Cole. Canada. (AAS_Text01_2007, a PDF file)
 Holler, E. J., D. A. Skoog, and S. R. Crouch. 2007. Atomic absorption and
atomic fluorescence spectrometry. In Principles of Instrumental Analysis. 6th
Ed. Chap. 9. pp. 230-253. Thomson Brooks/Cole. Canada. (AAS_Text02_2007,
a PDF file)
 Holler, E. J., D. A. Skoog, and S. R. Crouch. 2007. Atomic emission
spectrometry. In Principles of Instrumental Analysis. 6th Ed. Chap. 10. pp.
254-280. Thomson Brooks/Cole. Canada. (AAS_Text03_2007, a PDF file)
 Holler, E. J., D. A. Skoog, and S. R. Crouch. 2007. Atomic mass spectrometry.
In Principles of Instrumental Analysis. 6th Ed. Chap. 11. pp. 281-302.
Thomson Brooks/Cole. Canada. (AAS_Text04_2007, a PDF file)
 The Perkin-Elmer Inc. 1996. Analytical Methods for Atomic Absorption
Spectroscopy. (Analytical Methods_AAS, a PDF file)
 R. D. Beaty and J. D. Kerber. 1993. Concepts, Instrumentation and
Techniques in Atomic Absorption Spectrophotometry. 2nd Ed. The Perkin-
Elmer Inc., Norwalk, CT. (AAConcpt, a PDF file) 44
LECTURE CONTENTS：

Important Steps in the History of Atomic Absorption

Spectrometry and other related techniques
The Principle of Atomic Absorption Spectrometry
Atomic Absorption Instrumentation
Interferences in Atomic Absorption Spectrometry
Atomic Absorption Analytical Techniques
Applications of Atomic Absorption Spectrometry

45
The History of Atomic Absorption Spectrometry
 Background Companion
Light sources Atomizers correction techniques

Hollow cathode lamps DC plasma source

1960 Flame(air-C2H2)
ICP source
Flame(N2O-C2H2) D2 continuum source AFS
1965
Graphite furnace (GF)
Hydride
1970 Zeeman effect generation AAS
Electrodeless discharge
lamps Plasma AES

1975 DCP-MS
Platform furnace

1980
Smith-Hieftje ICP-MS
Stabilized temperature
1985 platform furnace

1990 Horizontally heated GF

Continuum source
1995 (High pressure xenon Axial ICP-AES
short-arc lamp) TOF ICP-MS
Collision ICP-MS 47
Figure 5-11. Development of the atomic absorption spectrometry
 Flame Emission Spectrometry,
(FES)
(1950s ~ early 1960s)

 Improved nebulizer- Flame Atomic Inductively  Wide dynamic range

burner systems  Lower detection limits
Absorption Coupled
 Using hollow cathode  Truly multielement
lamps as line sources
Spectrometry, Plasma
capability
(FAAS) Atomic
Emission
Spectrometry,
(ICP-AES)
 Better detection limits Electrothermal
 Small sample size Vaporization
(ETV-AAS)
Graphite  Truly multielement
ICP-MS capability
Furnace
 Extraordinarily low
(GFAAS) detection limits 48
原子吸收分光光譜法的基本原理(1)

每⼀元素(原子)都具有特定數目的電子以軌域結構與其原子核結合，其
能量最低與最安定的電子軌域組態稱為“基底狀態”(Ground state)
，是原⼦的常態；當以適當的能量供給⼀原⼦時，原⼦將吸收能量⽽
將外層電子軌域提昇到較高能階且較不安定的軌域組態，稱為”激發
狀態”(Excited state)，由於此狀態不安定，原子將瞬即回復到基底
狀態，而將原先吸收的能量，以熱或光能釋放。

Figure 5-12. Schematic diagram of electron transition and light emission

49
 Resonance lines

Figure 5-13. Energy level diagram for atomic magnesium.

50
原子吸收分光光譜法的基本原理(2)
在原子發射光譜法中，將試樣以高能環境(如火焰或電漿(Plasma))將其原
子化，並產生激發狀態的原子，由於激發狀態的原子不安定，原子將瞬即
回復到基底狀態並發射光，此發射光的強度隨著激發狀態的原子數目之增
加而增強，是為定量的依據。
在原子吸收光譜法中，將試樣以⾼能環境將其原⼦化，再以特定波⻑的光
能供給待測原⼦吸收，當在光路徑中的原⼦數⽬增加時，此特定波⻑的光
被吸收的量就增加，經由測定吸光度，即可將試樣中的元素予以定量。利
⽤特定的光源及謹慎地選擇特定的波⻑，即可將個別元素予以定量。

Figure 5-14. Atomic absorption process. 51

 原子吸收之定量分析

Figure 5-15. The atomic absorption process.

Transmittance (T): T = I/I o

Percent transmission (%T): %T = 100 x I/I o
Percent absorption (%A): %A = 100 - %T
Absorbance (A): A = log (I o/I)

Beer’’s Law: A = abc

Figure 5-16. The relationship between
absorbance and concentration in FAAS.
52
Figure 5-17. Atomic absorption measurements and results. 53
 原子光譜法能測定的元素

Using FAES

Figure 5-18. Elements which can be determined by AAS and plasma AES methods. 54
原子光譜法系統

Figure 5-19. Atomic spectroscopy systems.

55
 原子光譜儀的基本構造
AAS AES
光源
AFS

   
光源 原子化裝置 單光系統 偵測器
AAS Atomizer Monochromator Detector


霧化器 試樣溶液之導入
資料解析與輸出系統
Nebulizer Sample Introduction
Data processor &
Readout

樣本
(固體或液體)

Figure 5-20. The essential components of atomic spectrometers.

56
(a) A single-beam AA spectrometer

Light source Light intensity measurement

(b) A double-beam AA spectrometer

Figure 5-21. Typical flame atomic spectrometers. 57

  原子吸收光譜儀的光源

Line Source  LS-AAS (line width: ~0.002 nm)

Hollow cathode lamps
Electrodeless discharge lamps
Continuum Source  CS-AAS
Deuterium lamp (190~330 nm)
Tungsten-halide lamp (>300 nm)
High pressure xenon short-arc lamp

58
 原子吸收光譜儀的光源
(⼀)、中空陰極燈管（Hollow Cathode Lamp, HCL）
陽極(Anode）中空陰極(Hollow cathode)

石英窗口(Quartz window)
玻璃屏障 Ne or Ar
(Glass shield) at 1~5 torr
(二)、無極放電燈管（Electrodeless Discharge Lamp, EDL）
無線電頻線圈(RF coil)

石英窗口(Quartz window)
石英燈泡 陶瓷管
(Lamp) (Ceramic holder)
59
Figure 5-22. Schematic of line sources used in atomic absorption spectrometry.
Figure 5-23. Hollow cathode lamp with open cathode for non-volatile elements.
60
 中空陰極管的發光過程

1. 濺射 2. 激發 3. 發射
(Sputtering) (Excitation) (Emission)

Ar+ M*
M* hν
ν
(−
−) (−
−) (−
−)
M°° M°°
M°°
Ar+

M°°：基態原子 M*：激發態原子

Figure 5-24. A typical process in the hollow cathode lamp.

61
 Figure 5-25. Electrodeless discharge lamp.
(An accessory power supply is required to operate an EDL.)

62
 (三)、高壓氙氣短電弧燈管（High pressure xenon short-arc lamp）
Electrode distance: < 1 mm
Xenon pressure : 17 bar in cold condition

20VDC, 15A power

supply + 30 kV circuit

Figure 5-26. Photo of the high-pressure xenon short-arc lamp (GLE, Berlin, Germany).
63
Figure 5-27.

64
Figure 5-28.

65
  試樣溶液的導入

 氣流噴霧器 (Pneumatic Nebulizers)

 超音波噴霧器 (Ultrasonic Nebulizers)
氫化物產生器 (Hydride Generators)  HGAAS
(As, Bi, Ge, Pb, Sb, Se, Sn, Te)
−
3BH 4 + 3H + + 3H 3 AsO 3 → 3H 3 BO 3 + 4AsH 3 + 3H 2O
(HCl, KI, Ascorbic acid)
(H3AsO3 + H3AsO4) H3AsO3

冷蒸氣汞技術(Cold Vapor Mercury Technique)

[註] : 高靈敏度取樣系統(High sensitivity sampling systems)

66
 常見之氣流噴霧器

67
Figure 5-29. Types of neumatic nebulizers.
Figure 5-30. Ultrasonic nebulizer. 68
Figure 5-31. A hydride generation and atomization system for AAS.
69
 Batch generation Continuous generation

Flow-
Flow-injection generation

Figure 5-32. Three types of hydride generation systems. 70

冷蒸氣汞技術(Cold Vapor Mercury Technique)
(Cold vapor atomic absorption spectrometry, CVAAS)
CVAAS is a technique used to determine only mercury.
The main absorption wavelength for mercury is at 184.9 nm.
When using flame method, less sensitive lines have to be used
because of the proximity of this wavelength to the maximum
absorption wavelengths of flame gases.
Free mercury atoms can exist at room temperature and,
therefore, mercury can be measured by atomic absorption
without a heated sample cell.
The detection limit for mercury by this cold vapor technique is
approximately 0.02 µg/L.
Hg2+ (aq) + Sn2+ (aq) → Hg(l ) + Sn4+ (aq)
( Reducing agent: NaBH4 or SnCl2 ) 71
  原子化裝置(Atomizers)
Table 5-5. Types of atomizers used for atomic spectroscopy

Type of Atomizer Typical Atomization

Temperature, oC
Flame 1,700 – 3,150
AAS
Electrothermal Vaporization (ETV) 1,200 – 3,000
Inductively Coupled Argon Plasma (ICP) 4,000 – 6,000
Direct Current Argon Plasma (DCP) 4,000 – 6,000
Microwave-Induced Argon Plasma (MIP) 2,000 – 3,000
AES

Glow Discharge Plasma (GDP) Nonthermal

Electric Arc 4,000 – 5,000
Electric Spark 40,000 (?)
72
 火焰(Flame)的組成: (Fuel – Oxidant)
Table 5-6. Properties of common flames
Theoretical Maximum
Fuel-oxidant Combustion reaction stoichiometric burning velocity
temperature, (K) (cm s-1)
C3H8 – air C3H8 + 5O2 + 20N2 → 2,267 39 – 43
3CO2 +4H2O + 20N2
H2 – air 2H2 + O2 + 4N2 → 2,380 300 – 440
2H2O + 4N2
C2H2 – air C2H2 + O2 + 4N2 → 2,540 158 – 266
2CO + H2 + 4 N2
H2 – O2 2H2 + O2 → 2H2O 3,080 900 – 1,400
C3H8 – O2 C3H8 + 5O2 → 3,094 370 – 390
3CO2 +4H2O
C2H2 – N2O C2H2 + 5 N2O → 3,150 285
2CO2 + H2O + 5N2
C2H2 – O2 C2H2 + O2 → 2CO + H2 3,342 1,100 – 2,480 73
Table 5-7. Atomization efficiencies (β
βa value) in acetylene flame
Element C2H2-air flame C2H2-N2O flame
Al < 10-5 0.42 – 0.59
Ba 0.0011 – 0.009 0.15a – 0.30a
Ca 0.066 – 0.014 0.69a – 1.40a
Cu 0.87 – 1.00b 1.00b
Fe 0.38 – 0.66 ----
Li 0.21 – 0.26a 0.44a
Mg 0.59 – 0.84 1.50 – 2.30
Mn 0.45 – 0.93 0.76 – 0.80
Na 0.50 – 1.00a 0.33a – 0.65a
Sn < 10-4 – 0.078 0.71 – 0.76
Zn 0.45 – 1.10 0.91 – 1.00
a Ionization
suppressor added.
b Some methods were relative to Cu for which β = 1.00 was assigned. 74
a
 Table 5-8. Value of N*/N0 for various resonance lines.
N*
Em Excited state

Absorption Emission

N0
En Ground state

N*/N0 = (gm/gn)e-∆∆Eu/kT
Resonance N*/N0
gm/gn ∆E (eV)
line 2000 K 3000 K
Cs 852.1 2 1.45 4.44 × 10-4 7.24 × 10-3
Na 589.0 2 2.10 9.86 × 10-6 5.88 × 10-4
Ca 422.7 3 2.93 1.21 × 10-7 3.69 × 10-5
Fe 372.0 3.33 2.29 × 10-9 1.31 × 10-6
Cu 324.8 2 3.82 4.82 × 10-10 6.65 × 10-7
Mg 285.2 3 4.35 3.35 × 10-11 1.50 × 10-7
Zn 213.9 3 5.80 7.45 × 10-15 5.50 × 10-10 75
 Flow rate
2 to 5 mL min-1

Figure 5-33. Premixed, spray chamber, nebulizer/burner.

76
Figure 5-34. Premix burner system with flow spoiler and/or
impact bead. (Perkin-Elmer)
77
 Table 5-9. Sensitivities and detection limits (mg L-1)
measured in an air-acetylene flame
Element l(nm) Spoiler Impact Bead
Sens DL Sens DL
Ag 328.1 0.06 0.002 0.03 0.0009
As* 193.7 1.0 0.20 0.51 0.14
Ca 422.7 0.09 0.002 0.08 0.001
Cd* 228.8 0.03 0.001 0.02 0.0005
Cr 357.9 0.08 0.003 0.04 0.002
Cu 324.7 0.08 0.002 0.03 0.001
Fe 248.3 0.10 0.004 0.04 0.003
Mg 285.2 0.008 0.0001 0.0003 0.0001
Mn 279.5 0.05 0.002 0.03 0.001
Ni 232.0 0.14 0.009 0.04 0.004
Pb 283.3 0.45 0.03 0.19 0.01
Se* 196.0 0.59 0.13 0.33 0.07
* EDLs used Zn 213.9 0.018 0.002 0.011 0.0008 78
Table 5-10. Sensitivities and detection limits (mg L-1)
measured in a nitrous oxide-acetylene flame
Element l(nm) Spoiler Impact Bead
Sens DL Sens DL
Al 309.3 1.1 0.03 0.6 0.04

B 249.7 13.0 0.7 12.0 1.2

Mo 313.3 0.7 0.03 --- ---

Si 251.6 2.1 0.06 2.0 0.10

Sn 286.3 3.2 0.11 --- ---

Ti 364.3 1.8 0.05 1.9 0.08

V 318.4 1.9 0.04 1.3 0.06

W 255.1 9.7 1.2 --- ---

79
Table 5-11. Precision — air-acetylene flame
Spoiler Impact Bead
Element l (nm)
Av % CV Av % CV
Co 240.7 0.18 0.37
Cr 357.9 0.17 0.20
Cu 324.7 0.19 0.23
Mn 279.5 0.20 0.24
Ni 232.0 0.29 0.23
Pb 283.3 0.24 0.24
Zn 213.8 0.25 0.34

80
Table 5-12. Precision — nitrous oxide-acetylene flame
Spoiler Impact Bead
Element l (nm)
Av % CV Av % CV

Al 309.3 0.24 0.14

B 249.7 0.25 0.81

Si 251.6 0.32 0.71

Ti 365.3 0.25 0.77

V 318.4 0.23 0.69

81
 火焰(Flame)的構造

Outer cone

Flame
height Interconal
(0~5 cm) region

Primary
combustion zone

Air to be
entrained
Premixed C2H2 + O2
Fine droplets of solution

Figure 5-35. Schematic structure of a laminar flow flame.

82
 (Flame Height)

Figure 5-36.
83
Figure 5-37. Distribution of
atoms in a 10-cm air-
acetylene flame.
Fuel-rich and fuel-lean
results are shown. Contours
are drawn at intervals of 0.1
absorbance unit with
maximum absorbance in
center

84
 火焰式原子化過程
MX*(g) M+(g)+ e- M+*(g)
激態分子 基態離子 激態離子
解 結
激發
霧化 溶劑蒸發 揮發 離 合
(Excitation)
(Nebulization) (Desolvation) (Vaporization) (Ionization)
AAS
MX(aq) MX(aq) MX(s) MX(g) M(g) M*(g)
溶液 溶液煙霧 固體煙霧 氣態分子 基態原子 激態原子
放射
凝結 原子化 FES
(Atomization) AFS
MX(aq) 液化 (MX(l))
捨棄 Liquefaction MO(g), MX (g), MO*(g), X*(g),
MOH(g), etc. MOH*(g), etc.

Figure 5-38. Flame atomization process for the salt MX.

85
Limitations of flame AAS
 Burner – nebuliser is a rather inefficient sampling device.
Majority of the sample gets drained and the small fraction
reaching the flame has a short residence in the light path.
 High sample consumption of the order of 3-5ml/min.
 Matrix interferences limit applications particularly in
analysis of biological and geological samples.
 Analysis limited to ppm concentration ranges.
 電熱蒸發器 ( Electrothermal Vaporizers)
The Graphite Furnace Atomizer
(Used only at concentration levels below the optimum range of
direct flame atomic absorption because it is subject to more
interferences than flame procedure and require increased analysis
time.)
A basic graphite furnace atomizer is comprised of
the following components:
Graphite tube
Electrical contacts
Enclosed water cooled housing
Inert purge gas controls
87
 sample
optical optical
window window

optical path optical path

Graphite tube

Inert gas inlets

Figure 5-39. Cross-sectional view of a graphite furnace.

 Cross-sectional view of a graphite furnace

Figure 5-40. Longitudinally-heated graphite furnace atomizer.

89
Figure 5-41. Cross section of a heated graphite atomizer. 90
The typical graphite furnace program includes 6 steps:
1) Drying
2) Pyrolysis or Ashing (to remove matrix components)
3) Cool down (optional)
4) Atomization
5) Clean out
6) Cool down

91
 Atomizing

Ashing or
Pyrolysis

Drying

Figure 5-42. Temperature profile with ramp heating 92

Figure 5-43. Typical output from a spectrophotometer equipped with an
electrothermal atomizer. The sample was 2 µL of canned orange
juice. The times for drying and ashing are 20 and 60s respectively.
93
 Graphite tube with the L’vov

Figure 5-44. Graphite tube with the L’vov platform.

94
Figure 5-45. The L’vov platform.
95
Figure 5-46. Tube wall and platform temperature profiles. 96
Figure 5-47. A graphite tube for a transversely-heated furnace. 97
Benefits of graphite furnace analysis
 Entire sample is atomised and the atoms are retained in
the atomisation graphite tube for extended user
controlled time periods.
 Microlitre quantities of sample are sufficient and the
quantity can be increased to 50 – 100 μl to enhance
sensitivity.
 Temperature programming steps help remove the
solvent and major matrix interferences.
 Detection limits typically 100 – 1000 times better than
flame techniques are achievable thereby giving routinely
analysis in μg/l(ppb levels).
Limitations of graphite furnace analysis
 Longer analysis time in comparison to flame analysis.
 Lesser number of elements analysed by furnace
technique – around 40 as compared to about 70 in
flame technique.
 Higher cost of graphite furnace assembly but it is also
available as a switching option with flame operation in
most commercial instruments.
 Higher and more complex background levels require
expensive background correction options.
Table 5-13. Comparing AAS techniques
Comparison FAAS-air- FAAS-N2O- GFAAS CVAAS HGAAS
acetylene acetylene (Hg only)
flame flame
Cost Low Medium Very Medium Medium
high
Elemental Good Very good Good Poor Fair
scope
Speed Good Good Medium Medium Medium

Sensitivity Medium Medium Very Good Very

(ppm) (ppm) good (ppm or good
(ppt) ppb) (ppb)

100
感應耦合電漿 (Inductively Coupled Plasma)

Figure 5-48. A typical inductively coupled plasma. 101

Figure 5-49. Temperatures in a typical inductively coupled plasma source.
102
 View Configurations in ICP-AES (1)
Radial(or side-on) Viewing

To Spectrometer

The original ICP view configuration and the only view available
until the mid ‘90’s
Wide dynamic range
Excellent tolerant to dissolved solids
Negligible interferences and EIE (easily ionized elements) effects
Typical radial detection limits
Typical applications: Wear metals in engine oils, Industrial
materials such as brines and fertilizers, Biofuels 103
 View Configurations in ICP-AES(2)
Axial (or end-on) Viewing

To Spectrometer

Superior detection limits

Dynamic range shifts to lower concentrations
(The improvements are best seen in clean sample matrices)
Less tolerant to dissolved solids than radial
Torch lifetimes shorter than the dedicated radial
Beware of EIE (easily ionized elements) interferences
Typical applications: Drinking water, boiler water in
nuclear plants
104
 View Configurations in ICP-AES
Dual Viewing

Axial view

Radial view To Spectrometer

Superior detection limits

Very wide dynamic range when using both views
• Dynamic range shifts lower when with axial view
Tolerance to dissolved solids similar to that of dedicated radial
EIE effects of dedicated axial can be eliminated by using
radial view of DV option
Typical applications: Wastewater, soils, fertilizers
105
Figure 5-50. Major components and layout of a typical ICP-AES instrument.
106
 FAAS

ICP-AES (Radial)

ICP-AES (Axial)

HGAAS

GFAAS
ICP-MS

100 10 1 0.1 0.01 0.001

Detection Limit Ranges (µ

µg L-1)

Figure 5-51. Typical detection limit ranges for the major

atomic spectrometry. 107
Table 5-14. Comparison of atomic emission and atomic absorption techniques.
Factor ICP-AES FAAS GFAAS
Detection limits Best for refractory ele- Similar to ICP-AES, but Generally 10 - 100 times
ments, rare earths and better for group I more sensitive than FAAS
elements with reso- metals and selected or ICP-AES when the
nance lines below 190 volatile elements Na, element can be atomized
nm such as P and S K, Pb, Zn, Cd
Linear concentration 104 - 106 103 102
range
Within run precision 0.3-2% RSD 0.1-1% RSD 0.5-5% RSD
Interferences
Chemical Lowest Intermediate Highest
Spectral Highest Lowest Intermediate
Ionization Lowest Highest Intermediate
Speed of standardi- Most rapid for 6 or more Most rapid for less than Slow
zation and analysis elements per sample 6 elements per sample
Cost
Initial Highest Lowest Intermediate
Operating Highest Lowest Intermediate
Other factors Does not use combusti- Uses combustible gases Does not use
ble gases and can be and cannot be left combustible gases and
used for unattended unattended can be used for
overnight operation unattended overnight
operation
108
  單光系統 (Monochromators)

Components of monochromator: dispersive system and

image transfer system
1. an entrance slit that provide a narrow optical image of
the radiation source,
2. a collimator that renders the radiation emanating
from the entrance slit parallel,
3. a grating or prism for dispersing the incident
radiation,
4. a collimator to reform images of the entrance slit on
the exit slit, and
5. an exit slit to isolate the desired spectral band by
blocking all of the dispersed radiation except that
within the desired range. 109
Figure 5-52. Czerney-Turner grating monochromator. (λ
λ1 > λ2)
110
Figure 5-53. Bunsen prism monochromator. (λ
λ1 > λ2)
111
 (c)
Figure 5-54. Dispersion for three types of monochromators. The point s A and
B on the scale in (c) correspond to the points shown in figure 52
and figure 53. 112
Figure 5-55. Mechanisms of diffraction from an Echellete-
type (conventional) grating. 113
 nλ = d (sin i + sin r ) ≈ 2d sin β

Figure 5-56. Echelle grating: i = angle of incidence; r = angle of

reflection; d = groove spacing. In usual practice,
i ≈ r = β = 63o26′.

114
Table 5-15. Comparison of performance characteristics of a
conventional and Echelle monochromator
Feature Conventional Echelle
Focal length 0.5 m 0.5 m

Groove density 1200/mm 79/mm

Diffraction angle 10 o22’ 63 o26’

Order n (at 300 nm) 1 75

Resolution (at 300 nm), λ/∆λ 62,400 763,000

Reciprocal linear dispersion, D-1 1.6 nm/mm 0.15 nm/mm

(at 300 nm)

Light-gathering power, f f/9.8 f/8.8

115
  偵測器 (Detectors)

Photomultiplier Tubes (PMTs)

Linear photodiode arrays (PDAs).
(one-dimensional transducers)
Charge-transfer detectors (CTDs). (CIDs and CCDs)
(two-dimensional transducers)

116
 原子吸收光譜分析之干擾因子

(⼀)、化學干擾（Chemical Interferences）

(二)、基質干擾（Matrix Interferences）

(三)、離子化干擾（Ionization Interferences）

(四)、光譜干擾（Spectral Interferences）

(五)、背景吸收（Background Absorption）

117
 (⼀) 、化學干擾(Chemical Interferences)
(由於火焰溫度不夠高，以致無法將金屬化合分子或附生之金屬氧化物解
離，而造成吸光度偏低)

磷酸根、硫酸根等對鈣離子、鎂離子的干擾。
矽酸根對錳之干擾 ( 可添加鈣離子予以消除 )。
鋁離子對鈣離子、鎂離子的干擾。
通常使用釋出劑(releasing agents)如鍶離子(Sr 2+)、鑭離
子(La 3+)等或保護劑(protective agents)，如 EDTA, 8-
hydroxyquinoline, Ammonium 1-Pyrrolidine
Carbodithioic acid等的添加來消除干擾。
提高原子化的溫度其降低或消除干擾的效果更顯著。

118
Figure 5-57. Interference of phosphate on calcium. 119
 100

80
Relative Absorbance

Mg (285.21 nm)
60

40 Ca (422.67 nm)

20

0
0 10 20 30 40 50 60 70 80
Al/Ca or Al/Mg Molar Ratio

Figure 5-58. The effect of aluminum on the determination of

calcium and magnesium by flame AAS with air-
acetylene flame. 120
 110
100
100

80
Relative Absorbance

Relative Absorbance
90
PerkinElmer AAnalyst 200 AAS
(Mg: 0.25 mg/L; Al: 10 mg/L)
80 60 PerkinElmer AAnalyst 200 AAS
Mg 285.21 nm
(Ca 422.67 nm)
70 (Ca: 2.5 mg/L; Al: 10 mg/L)
40
Air-Acetylene
60 N 2O-Acetylene Air-Acetylene
N 2O-Acetylene
20
50

40 0
0 200 400 600 800 1000 0 200 400 600 800 1000
Lanthanum Concentration (mg/L) Lanthanum Concentration (mg/L)

Figure 5-59. The comparison of the effect of flame temperature and

lanthanum on the alleviation of aluminum interference in
the determination of calcium and magnesium.
121
 Extraction/Air-Acetylene Flame Method
(NIEA W309.22A, NIEA W321.51A)
(Suitable for the determination of low concentrations of
Ag, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, and Zn)

1. Complexation with ammonium pyrrolidine dithiocarbamate

(APDC)
2. Extraction into methyl isobutyl ketone (MIBK)
The maximum volume ratio of sample to MIBK is 40.
3. Aspiration into an air-acetylene flame

APDC

122
Table 5-16. pH ranges for optimum extraction of APDC-
Metal complexes by MIBK.
Element pH Range for Optimum Extraction

Ag 2 - 5 (complex unstable) (2.3 ± 0.2)

Cd 1-6
Co 2 - 10
Cr 3-9
Cu 0.1 - 8
Fe 2-5
Mn 2 - 4 (complex unstable at room temp.)

Ni 2-4
Pb 0.1 - 6
123
Zn 2 - 6 (2.3 ± 0.2)
 Extraction/Nitrous Oxide-Acetylene Flame Method
(Suitable for the determination of Al at concentration less than 900
µg L-1 and Be at concentration less than 30 µg L-1)

1. Complexation with 8-hydroxyquinoline

2. Extraction into methyl isobutyl ketone (MIBK)
Adjustment of the 8-hydroxyquinoline to sample ratio can
improve recoveries of extremely high or low concentration
of aluminum.
3. Aspiration into a nitrous oxide-acetylene flame

8-hydroxyquinoline

124
 (二)、基質干擾（Matrix Interferences）
(因樣本液之黏度、表面張力等與標準溶液不同，或總酸或鹽類濃
度過高，使得溶液之輸送速率與霧化程度(噴霧口阻塞及霧滴大小
分布)有差異，而造成干擾。)

在AAS, ICP-AES, ICP-MS等方法中均會影響。

通常以儘量使樣本液與標準溶液之基質相似，或避免總
酸或鹽類濃度超過0.5%，來降低干擾。

標準添加法亦是常用的方法。

125
126
Figure 5-60.

127
Figure 5-61. 128
Figure 5-62.

129
Figure 5-63. The method of standard additions. 130
 (三) 、離子化干擾（Ionization Interferences）
(部分元素或因或其離子化位能(ionization potential)較低，或
因火焰溫度過高，在原子化過程中易離子化，以致基底狀態的原子
數目降低，而造成吸光度偏低。 )

通常使用離子化抑制劑(ionization suppressor, or
ionization buffer)來降低干擾。例如鋇離子在air-
acetylene火焰中極易離子化，添加大量離子化位能
(ionization potential)與其相當或較低的離子，如
Na +, K +, Li +，即可克服此干擾。

131
Table 5-17. Degree of ionization of metals at flame temperatures
Fraction ionized at the indicated pressure
Ionization and temperature
Element potential
P = 10-4 atm P = 10-6 atm
(eV)
2000 K 3500 K 2000 K 3500 K
Cs 3.893 0.01 0.86 0.11 > 0.99
Rb 4.176 0.004 0.74 0.04 > 0.99
K 4.339 0.003 0.66 0.03 0.99
Na 5.138 0.0003 0.26 0.003 0.90
Li 5.390 0.0001 0.18 0.001 0.82
Ba 5.210 0.0006 0.41 0.006 0.95
Sr 5.692 0.0001 0.21 0.001 0.87
Ca 6.111 3 x 10-5 0.11 0.0003 0.67
Mg 7.644 4 x 10-7 0.01 4 x 10-6 0.09
132
Figure 5-64. Effect of added potassium on ionization. 133
Figure 5-65.

134
 (四)、光譜干擾（Spectral Interferences）
(因所選擇之待測元素的共振線波⻑與其它元素者相近⽽造成)

通常以選擇最小的光狹縫寬度或選擇其它共振線
波⻑來克服⼲擾。
在ICP-AES中常出現。

135
 (五)、背景吸收（Background Absorption）
(因在原子化過程中之未解離的分子對光的吸收或固體粒子
對光的散射而造成的干擾 。)

背景吸收的干擾在石墨爐式原子吸收光譜法 (GFAAS)中甚為嚴
重。(通常在較低波⻑時背景吸收較⼤)

背景吸收通常利用下列方法來克服干擾：
稀釋樣本、降低樣本取量或改變吸光波⻑。
移除干擾性基質成分 (分離、純化或基質修飾 )。
利用光學背景校正技術。

136
 基質修飾 (Matrix modification)的作用

添加基質修飾劑(Matrix modifiers)
移除會造成背景吸收的基質成分。
(增加基質的揮發性或降低分析物(Analyte)的揮發性)
促進分析物在原子化溫度下的解離作用。
修飾石墨管表面結構與反應性，以增進樣本與石墨管表面的
接觸與影響氣相組成。

137
Figure 56. A graphite furnace
temperature
program.
138
 基質修飾劑(Matrix modifiers)的選擇

廣用的化學修飾劑並不存在。
(由於基質修飾劑的效果決定於分析物的化學特性、基質組成、修飾劑的
化學特性、修飾劑的物理狀態、原子化裝置的設計與效率以及原子化溫
度等等因子，基質修飾劑的選擇相當困難)

無機鹽類是最常用的修飾劑，尤以銨鹽或硝酸鹽為佳。

複雜的樣本常使用混合修飾劑，如Pd(NO3)2 + Mg(NO3)2。

選擇GFAAS較少測定的元素作為修飾劑(如Pd, Mg, Ce, Ta, W, Zr)，以

避免記憶效應。

修飾劑亦可能會造成背景吸收，腐蝕性與降低靈敏度的效應。

139
 Matrix modification using NH4NO3 to remove NaCl
(One of the first published matrix modification procedures)

Reaction: NaCl + NH4NO3 → NaNO3 + NH4Cl

Decomposition Temperatures (oC):
NaCl 1400
NH4NO3 210
NaNO3 380
NH4Cl 330

140
Figure 5-67. Ni(NO3)2 matrix modification for Se determination.

141
Table 5-18. Potential matrix modifiers for electrothermal atomic
absorption spectrometry
Analyses for Which
Modifier Modifier
May Be Useful
1500 mg Pd/L + 1000 mg Ag, As, Au, Bi, Cu, Ge, Mn, Hg, In,
Mg(NO3)2/L Sb, Sn, Te, Tl
500-2000 mg Pd/L + reducing Ag, As, Bi, Cd, Co, Cr, Cu, Fe, Hg,
agent Mn, Ni, Pb, Sb
5000 mg Mg(NO3)2/L Be, Co, Cr, Fe, Mn, V
100-500 mg Pd/L As, Ga, Ge, Sn
50 mg Ni/L As, Se, Sb
2% PO3-4 + 1000 mg Mg(NO3)2/L Cd, Pb
142
 光學背景校正技術

雙譜線校正法 (The two-line correction method)

連續光源校正法(The continuum-source correction
method)
光源自迴性校正法(Smith-Hieftje correction method)
Zeeman 效應校正法(Background correction based on
the zeeman effect)

143
 雙譜線校正法(The two-line correction method)

選擇盡量接近分析譜線但不會被分析物種吸收的波⻑當作
參考譜線。

Figure 5-68. Two-line

background
correction. 144
 連續光源校正法
(The continuum-source correction method)

最常使用的連續光源：
Deuterium lamp (190~330 nm)
Tungsten-halide lamp ( > 300 nm)

校正方式：
時間差脈衝點燈
週波數調變

The typical emission line width of HCL is about 0.002 nm.

145
Figure 5-69. Continuum Source Background Corrector.

146
Figure 5-70. Atomic and background absorption with a primary (line)
source and a continuum (broadband) source.
147
 without
background
correction

with
background
correction

Figure 5-71. Automatic continuum source background correction.

(performed at the Pb 283.3 nm wavelength)
148
For steady state BG signals
(Line source)

Figure 5-72. Background corrector timing diagram.

[AA] = [AA+BG] - [BG] 149

For rapidly changing BG signals

(BGint)

Figure 5-73. Interpolated background correction.

[AA] = [AA+BG] - [BGint] 150

Limitations of Continuum Source Background Correction
(especially impact graphite furnace atomic absorption)
1. Requires additional continuum light source(s) and
electronics.
2. Requires the intensities of the primary and continuum
sources to be similar.
3. Two continuum sources are required to cover the full
wavelength range.
4. Requires critical alignment of the continuum and primary
sources for accurate correction.
5. May be inaccurate for structured background absorption.

151
 光源自回性校正法
(Smith-Hieftje correction method)
利用中空陰極管在高電流狀態下光源自我吸收(self-
absorption or self-reversal))的現象作背景校正。

Figure 5-74.
152
 Zeeman 效應校正法
(Background correction based on the zeeman effect)

利用外加強磁場(≈ ≈10 kG)的作用，使試樣原子只吸收入射

光受偏極分離的π部分(平行於外加磁場)，而背景吸收由於
大部分是分子散射和吸收產生的寬帶所造成，能量差距很
小，不受外加磁場的影響，能同時吸收入射光的 π 和σ±，
利用背景吸收 σ± (垂直於外加磁場) 的程度，作為校正的依
據。

153
 1/2∑ Φπ = ∑ Φσ- = ∑ Φσ+
( 1/2 I π = I σ- = I σ+ )
Figure 5-75.
154
Figure 5-76. 155
Figure 5-77.

156
 157
Figure 5-78. Normal Zeeman effect. Pictoral explanation of the rotating polarizer method.
Advantages of Zeeman Effect Background Correction

1. Corrects for high levels of background absorption.

2. Provides accurate correction in the presence of
structured background.
3. Provides true double-beam operation.
4. Requires only a single, standard light source.
5. Does not require intensity matching or coincident
alignment of multiple sources.

158
Figure 5-79. Zeeman vs. Continuum Background Correction. From
Letourneau, Joshi and Butler, At. Spectrosc. 8, 146 (1987).
159
 Table 5-19. Comparison of continuum source, Zeeman and Smith-Hieftje
background correction systems for line-source atomic absorption.
Background Advantages Disadvantages
correction
Continuum •Corrects for broad band background •Cannot correct high background
source absorption absorption
•Highest sensitivity •Cannot correct structured
(1965) •Reasonably low cost background
•Difficult to match line source and
continuum source intensities
•Optical alignment problems
•Baseline drift problems
Zeeman •Corrects for high background absorption •Reduced sensitivity of some elements
•Corrects spectral interferences if lines are 0.02 •Analyte signal may be included in
(1971) nm apart background correction
•Corrects for structured background •Background absorption may be
absorption affected by magnetic field and light
•Does not require matching of two line sources polarization
•Avoids optical alignment problems •Polarizers contribute to light loss Cost

Smith-Hieftje •Corrects for high background absorption
•Corrects for structured background
(1983) absorption
•Allows correction in the visible and UV regions
•Does not require matching of two light
sources
•Avoids optical alignment problems
•Does not require ancillary equipment such as
magnets and polarizers
•Cannot provide background correc-
tion for elements like Mo and Ti
•Reduced sensitivity compared to
continuum source
•Analyte signal may be included in
background correction
•Special hollow cathode lamps are
required
160
Characteristic concentration (sensitivity): the
concentration of an element (expressed in mg/L)
required to produce a signal of 1% absorption (0.0044
absorbance units).
Conc. of Std. × 0.0044
Characteristic concentration =
Measured Abs
Detection limit: the concentration of the element which will
produce a signal/noise ratio of 3.
Conc. of Std. × 3 Std. Dev.
Detection limit =
Mean
Characteristic concentration check value: the
concentration of element (in mg/L) that will produce a
signal of approximately 0.2 absorbance units under
optimum conditions at the wavelength listed. 161
Table 5-20. Basic definitions of sensitivity
Name Symbo Descriptive definition Mathematica
l definition
l
Calibration m Slope of analytical curve
sensitivity
Atomic absorption mA Concentration or mass which
sensitivity yields 1% absorption or T =
99% or A = 0.004365
Analytical γ Slope of analytical curve
sensitivity divided by SD of analytical
signal measurement

162
 製備檢量線
(Preparation of the calibration curve)

Beer’s law
C = kA

Figure 5-80.

163
 Method of least squares
(Polynomial function vs. Rational function)

Linear curves A = K 0 K1 C
A = K 0 + K1 C

Nonlinear curves

Polynomial function A = K 0 + K 1 C + K 2 C 2 + K 3 C3 + ⋅ ⋅ ⋅ ⋅ ⋅ ⋅

Rational function K 3A 2 + K 1A
C = K0
K 2A - 1
164
Figure 5-81. One Calibration Standard (Linear Plot) 165
Figure 5-82. Calibration Curve for 2 Calibration Standards
166
Figure 5-83. Calibration Curve for 3 Calibration Standards
167
Figure 5-84. Three Calibration Points in Linear Range - S-Shaped Curve.
168
Figure 5-85. Cobalt
Calibration Accuracy
169
 高精確度分析應注意的地方

原子吸收光譜法與分子吸收光譜法相同，都是利用Beer’s law
做為定量的依據，由於有原子化過程的不穩定性等因子的存在，
欲求得類似分子吸收光譜法之高精確度並不容易，但如能注意
下列各項操作，則可得到較佳的精確度。

170
 高精確度分析應注意的地方

 注意取樣與稱重。
 樣本液之吸取應使用容積大於 5 mL 的吸管。
 容量瓶應使用 class A 的容量瓶。
 注意試劑之純度；應使用分析試藥等級以上之化學藥品。
 注意干擾因子之控制。
 校準時應使用適當數量之校準標準液，並注意避免吸光定
律之偏離。
 注意"空白"之妥當性，要能代表樣本液基質。
 注意預混燃燒室之清潔。
 標準溶液要確定配製正確無誤。
 霧化器應使用耐蝕性或鉑-銠合金材質之霧化器。
 為達最佳精確度，積分時間最少要 10 秒以上。

171
Figure 5-86.

172
Table 5-21. A comparison of atomic spectrometric techniques. (1)
Parameters Flame atomic Graphite furnace Inductively coupled Inductively coupled
absorption atomic plasma-atomic plasma-atomic mass
spectrometry absorption emission spectrometry
(FAAS) spectrometry spectrometry (ICP-MS)
(GFAAS) (ICP-AES)
Sample Fast Slow Fast Fast
throughput
Number of Usually one, but As for FAAS Many Many
elements within some modern
a sample instruments can do
up to four at once
Linear dynamic Poor Poor Good Very good
range (LDR)
Maximum > 20% ~ 3% 2-25% depending on 0.1 – 0.4%
proportion of the nebulizer
dissolved solids
Costs Low Higher than FAAS High Very high

173
 Table 5-21. A comparison of atomic spectrometric techniques. (2)
Parameters Flame atomic Graphite furnace Inductively coupled Inductively coupled
absorption atomic plasma-atomic plasma-atomic mass
spectrometry absorption emission spectrometry
(FAAS) spectrometry spectrometry (ICP-MS)
(GFAAS) (ICP-AES)
Running Costs Low Medium High Very high
Detection limits Good for some Excellent for some Good for most Excellent for most
elements. elements. Better elements. elements.
than FAAS for
most.
Precision 0.1 – 1% 1 – 5% 0.3 – 2% 1 – 3%
Interference Many chemical Many chemical Almost none Mainly from isotopes
interferences interferences
Chemical fuels Yes (acetylene for None None None
the flame)

174
 原子吸收分光光譜法的應用 (1)

原子吸收分光光度法可定量分析約七十種元素，由於其儀器之
價格合理、操作簡單，且其測定容易標準化，又具有足夠的偵
測極限與精確度，原子吸收分光光度儀的使用幾乎與分析天平
及pH計⼀樣的普遍，其應⽤範圍極為廣泛，舉凡⼟壤、植物、
水質、生態環境、食品安全及與人類健康有關的領域，都應用
得到。略舉數端如下：

175
 原子吸收分光光譜法的應用 (2)

土壤中植物必須養分缺乏與毒害的診斷分析與施肥推薦；
土壤、植物、空氣、河川、湖泊、海洋之污染分析、監測與調
控；
灌溉水、飲用水等各種水體之水質分析；
食品中礦物質的分析、監測與調控；
金屬元素在生物體中之生理、生化反應機制的研究分析；
地球或外星球地殼岩石、礦物的成份分析；
流行病學中之血液成份分析；
工業、軍事用等各種材料之研發與分析；
其他
。


176
 Instrument Operation — General Procedure

1. Install a hollow-cathode lamp for the desired metal in the

instrument and roughly set the wavelength dial according to
the selected resonance line.
2. Set slit width according to manufacturer’s suggested setting
for the element being measured.
3. Turn on instrument, apply to the hollow-cathode lamp the
current suggested by the manufacturer, and let instrument
warm up until energy source stabilizes, generally 10 to 20 min.
4. Readjust current as necessary after warmup.
5. Optimize wavelength by adjusting wavelength dial until
optimum energy gain is obtained.
6. Align lamp in accordance with manufacturer’s instructions.

177
7. Install suitable burner head and adjust burner head position.
8. Turn on air and adjust flow rate to that specified by
manufacturer to give maximum sensitivity for the metal
being measured.
9. Turn on acetylene, adjust flow rate to value specified, and
ignite flame.
10. Let flame stabilize for a few minutes.
11. Aspirate a blank consisting of deionized water containing the
same concentration of acid in standards and samples.
12. Zero the instrument.
13. Aspirate a standard solution and adjust aspiration rate of the
nebulizer to obtain maximum sensitivity.
178
14. Adjust burner both vertically and horizontally to obtain
optimum response.
15. Aspirate blank again and rezero the instrument.
16. Aspirate a standard near the middle of the linear range.
17. Record absorbance of the standard when freshly prepared
and with a new hollow-cathode lamp
(Refer to these data on subsequent determinations of the
same element to check consistency of instrument setup and
aging of hollow-cathode lamp and standard.)
---- The instrument now is ready to operate. ----
18. Standardization : prepare a calibration curve.
19. Analysis of samples: (Rinse nebulizer by aspirating water
containing 1.5 mL conc. HNO3 /L.)
20. When analyses are finished, extinguish flame by turning off
first acetylene and then air. 179
 FAAS最佳測定條件之決定流程
波⻑的選擇與調校
(包括光源之排列對準(alignment) 燈管之垂直與水平位置之調整、燃
燒頭旋轉角度之調整)
(於氣體開啟前為之)

最佳火焰組成與光路位置
 助燃劑(air or N2O)與燃料(C2H2)之選擇(Air -C2H2 or N2O-C2H2)
 助燃劑與燃料之流速或分壓以及燃燒頭高度之決定(通常以助燃劑之流速或分
壓為固定，在各燃料流速下改變燃燒頭高度，測定標準溶液之吸光值)

燈管電流之設定
(在燈管額定最高電流以下為之)

狹縫寬度之選擇 180
 光源之排列對準(alignment)
upward
Radiation
HCL
forward
Burner Head

downward

backward

Radiation Flame

Burner Head

181