ICP-OES Operation Training Course

ICPS-Operation Training Course
ICPS-Operation Training Course Text
Chapter 1 Inductively Coupled Plasma Emission Spectrometry...................................................5

1. Introduction........................................................................................................................ 5
2. Principle of Emission Spectrometry....................................................................................5
2.1. Emission...................................................................................................................... 5
2.2. Light Dispersion........................................................................................................... 7
2.2.1. Prism Spectrometers............................................................................................. 7
2.2.2. Diffraction-grating Spectrometers..........................................................................8
3. Inductively Coupled Plasma Emission Spectrometers.....................................................12
3.1. Light-source Section.................................................................................................. 12
3.1.1. Generation of Plasma.......................................................................................... 12
3.1.2. Structure and Role of Plasma Torch....................................................................14
3.1.3. Types of Nebulizer and Characteristics...............................................................15
3.2. Spectrometry Section................................................................................................ 16
3.3. Photometry Section................................................................................................... 17
4. Increasing Sensitivity with ICP Emission Spectrometry and Applications.........................18
4.1. Ultrasonic Nebulizer................................................................................................... 18
4.2. Hydride-generation Method.......................................................................................20
4.3. Axial Measurement.................................................................................................... 22
Chapter 2 Qualitative and Quantitative Analysis...........................................................................23

1. Qualitative Analysis.......................................................................................................... 23
1.1. Emission Spectrometry and Qualitative Analysis.......................................................23
1.2. Qualitative Analysis with Sequential ICP Emission Spectrometry..............................24
1.2.1. Spectral Interference and Discrimination of Elements.........................................25
1.2.2. Calculation of Semi-quantitative Values..............................................................26
2. Quantitative Analysis........................................................................................................ 27
2.1. Calibration Curve Method.......................................................................................... 27
2.1.1. Creation of Calibration Curve..............................................................................27
2.2. Standard Addition Method......................................................................................... 28
2.3. Detection Limit and Limit of Quantitative Determination............................................29
Chapter 3 Analysis with the ICPS Series......................................................................................31

1. Qualitative Analysis.......................................................................................................... 31
1.1. Qualitative Analysis 1................................................................................................. 32
1.2. Switching from Qualitative Analysis 1 to Qualitative Analysis 2.................................32
1.3. Qualitative Analysis 2................................................................................................. 33
1.4. Measurement Results (Semi-quantitative Values and Degree of Reliability).............34
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1.4.1. Semi-quantitative Values.....................................................................................34

1.4.2. Degree of Reliability............................................................................................ 35
1.4.3. Database of Semi-quantitative Values.................................................................36
1.5. From Qualitative Analysis 2 to Quantitative Analysis.................................................37
2. Quantitative Analysis........................................................................................................ 38
2.1. Scan Mode................................................................................................................ 38
2.1.1. Peak Search Mode.............................................................................................. 38
2.1.2. Direct Mode: ICPS-7500/8100............................................................................40
2.1.3. Direct Mode: ICPS-7000.....................................................................................40
2.1.4. Fixed-wavelength Mode (ICPS-7500/8100)........................................................42
2.2. Calibration Curve Method and Standard Addition Method.........................................42
Chapter 4 Interference and Correction Methods.........................................................................43

1. Interference...................................................................................................................... 43
1.1. Physical Interference................................................................................................. 44
1.2. Chemical Interference................................................................................................ 44
1.3. Ionization Interference............................................................................................... 45
1.4. Spectral Interference................................................................................................. 46
2. Correction Methods.......................................................................................................... 47
2.1. Matrix Matching Method............................................................................................ 47
2.2. Internal Standard Correction......................................................................................47
2.2.1. Simultaneous Internal Standard Correction.........................................................48
2.2.2. Sequential Internal Standard Correction.............................................................48
2.3. Background Correction.............................................................................................. 49
Chapter 5 Pretreatment Examples and Selecting Equipment (Accessories) for Different Types of
Samples..................................................................................................................... 50
1. Processing Room and Equipment....................................................................................50
1.1. Processing Room...................................................................................................... 50
1.2. Testing Apparatus...................................................................................................... 50
1.3. Equipment for Pretreatment.......................................................................................51
1.4. Equipment and Reagents for Testing.........................................................................51
1.4.1. Deionized Water.................................................................................................. 51
1.4.2. Standard Samples............................................................................................... 51
1.4.3. Acids and Alkalis................................................................................................. 53
2. Decomposition methods................................................................................................... 54
2.1. Dry Ashing................................................................................................................. 54
2.2. Wet Decomposition.................................................................................................... 54
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2.3. High Pressure Decomposition...................................................................................54

2.4. Melting....................................................................................................................... 54
3. Examples of Pretreatment and Equipment (Accessories) Selection for Different Sample
Types...................................................................................................................................... 54
3.1. Analyzing Water Quality............................................................................................. 55
3.1.1. Seawater............................................................................................................. 55
3.1.2. Water from Rivers and Lakes..............................................................................55
3.1.3. Ground Water and Hot Springs...........................................................................55
3.1.4. Rain Water.......................................................................................................... 55
3.1.5. Effluent................................................................................................................ 56
3.1.6. Public Water System and Untreated Drinking Water...........................................56
3.2. Metals and Industrial Materials..................................................................................56
3.2.1. Steel.................................................................................................................... 56
3.2.2. Nonferrous Metals............................................................................................... 56
3.2.3. Ceramics............................................................................................................. 56
3.2.4. Oil........................................................................................................................ 57
3.3. Geochemical Samples............................................................................................... 57
3.4. Biological Samples.................................................................................................... 57
3.4.1. Serums, Blood, and Blood Cells..........................................................................57
3.4.2. Urine.................................................................................................................... 57
3.4.3. Hair...................................................................................................................... 58
3.4.4. Organs................................................................................................................ 58
3.5. Food Products........................................................................................................... 58
3.5.1. Animal Food Products......................................................................................... 58
3.5.2. Vegetable Food Products....................................................................................58
3.5.3. Alcoholic Beverages............................................................................................ 58
3.5.4. Soft Drinks........................................................................................................... 59
Appendix 1 Analysis of Organic Solvents with ICP (ICPS-7500/8100)..........................................61

1. Points to Note Regarding Organic-solvent Samples........................................................61
1.1. Plasma Ignition (Example)......................................................................................... 61
1.2. Standard Samples..................................................................................................... 61
2. Plasma Conditions........................................................................................................... 62
3. Example: Creating Oil Samples.......................................................................................64
3.1. Analyzed Sample....................................................................................................... 64
3.2. Calibration-curve Samples......................................................................................... 64
3.3. Examples of Methods for Creating Analyzed Samples and Calibration-curve Samples64
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Appendix 2 Analysis Using the Hydride-generation Method.........................................................66

1. Plasma Conditions........................................................................................................... 66
2. Points to Note Regarding Analysis Using the Hydride-generation Method.......................68
2.1. Pre-reduction............................................................................................................. 68
2.2. Interference due to Co-existing Substances..............................................................68
2.3. Introduction System................................................................................................... 68
2.4. Rinse Time................................................................................................................. 68
2.5. Chemical Forms of Arsenic........................................................................................ 68
3. Examples of Analysis Using the Hydride-generation Method...........................................69
3.1. Influent....................................................................................................................... 69
3.1.1. Pretreatment for Analysis of Arsenic and Antimony.............................................69
3.1.2. Pretreatment for Analysis of Selenium................................................................69
3.2. River Water................................................................................................................ 69
3.2.1. Pretreatment for Analysis of Arsenic and Antimony.............................................69
3.2.2. Pretreatment for Analysis of Selenium................................................................69
Appendix 3 Standardization of Measured Intensity (Drift Correction)............................................70
Appendix 4 Calculation Sequence for Analytical Values...............................................................71
Appendix 5 Glossary..................................................................................................................... 72
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Chapter 1 Inductively Coupled Plasma Emission Spectrometry
1. Introduction
Emission spectrometry is a method for performing qualitative and quantitative analysis by applying
electrical and thermal energy to a sample so that it emits light, dispersing this light, and detecting
the existence and measuring the intensity of light (spectral lines) corresponding to different
elements in the sample.
2. Principle of Emission Spectrometry

3. Emission
In order to generate spectra, the sample must be vaporized into an atomic state (vaporization
and atomization), and high-speed particles must be created and made to perform inelastic
collisions with the sample (excitation). These processes are usually carried out almost
simultaneously. The mechanisms of excitation and emission are described here.
An atom consists of a nucleus together with the electrons (orbital electrons) that move around it
in their particular orbits (See Fig. 1-1). If energy is imparted to this atom in some way, an orbital
electron absorbs this energy, and moves from its regular orbit to an orbit corresponding to a
higher energy level (E2). This electron, however, does not stay in this orbit and within
approximately 10-7 to 10-8 seconds moves to an orbit corresponding to a lower energy level (E1).
When this happens, the electron emits the difference in energy levels, E, in the form of light
(spectral line).
Ionization
イオン化
Ionized state
励起準位
(free state)
E2
Excited state ２ Excitation
Ionization
イオン化ｈν level
E1 Light of energy
エネルギー
frequency v １ ΔＥ
E
2
Electron E２2
Ｅ E
Ｅ１1
Nucleus
E : High energy level

2
E : Low energy level
1
Fig. 1-1 Model of the Atom v: Frequency of the spectral line
Fig. 1-2 Generation of Atomic Spectra
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If the frequency of the spectral line is v, E can be expressed by the following equation:
E = E2 - E1 = hv h : Planck's constant
Also, the frequency, ν, and the wavelength, , satisfy the following relationship:
10
= C / v C : Speed of light (3×10 cm/sec)
Atoms have their own peculiar orbits and so the energy difference, E, is specific to that atom. In
other words, light that is peculiar to that atom (atomic spectra) is emitted. When this emitted light
is directed into a spectrometer, it is dispersed using prisms or diffraction gratings, and atomic
spectral lines that are peculiar to the elements are measured. The number of spectral lines
usually measured across the ultraviolet, visible, and infrared regions ranges from several
thousands, for rare earth elements and uranium, to several tens, for alkali metals. Also, the
spectral lines can be divided into two types according to the state of the emitting atoms: neutral
atomic lines (arc lines) and ionized lines (spark lines).
In order to generate these spectral lines, the sample must be excited. The energy required for
this excitation process is provided by current (arc or spark) or by combustion (flame), and this
part is referred to as the "light source".
With a light source under atmospheric pressure and in thermal equilibrium (the gas temperature
and electron temperature are the same), the average kinetic energy of the various particles in
the light source can be determined in terms of the temperature, T. If I is the amount of energy
radiated per unit volume of the light source in relation to a spectral line of frequency v, then the
following holds:
I = NAhv N : Number of atoms per unit volume
A : Spontaneous emission probability of going from
excited state to steady state
H : Planck's constant
In one unit volume of plasma in thermal equilibrium, the atoms describe the Boltzmann
distribution with respect to energy, giving the following:
N0 : Number of atoms in steady state

e-- E / kT
N = N0.g / g0 g, g0 : Statistical weights in excited and steady states
E : Excitation energy
K : Boltzmann's constant
The following well-known equations can be derived from the above.

e – E / kT
I = N0.g / g0 .A.hv
and
e- E / kT
I = N .g / Z .A.hv Z : Partition function (temperature function)
As can be seen from the above equations, the spectral-line intensity can be expressed as a
function of the number of atoms of the target element there are in the light source and the
temperature of the light source. It can be seen that, in general, the intensities are larger for
spectral lines with a low excitation energy, E, and a large spontaneous emission probability, A.
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4. Light Dispersion
Out of the products currently available, spectrometers that use diffraction gratings as the
dispersive element are by far the most common. There are some special spectrometers that use
prisms but diffraction gratings are more effective as dispersive elements.
5. Prism Spectrometers
A prism spectrometer disperses light by utilizing the way light is refracted by prisms.
A prism is a transparent body with two optical surfaces. The line where the two surfaces
intersect is referred to as the "apex" and the angle, A, that these surfaces form is called the
"apex angle". When parallel rays are incident on the prism, because the prism's refractive
index varies with the wavelength, the parallel rays are dispersed into monochromatic rays.
Suppose that the prism's refractive index for light of wavelength  is n, that the angle the
incident light makes with the perpendicular to the incident surface (i.e., the incident angle) is i,
and that the angle the light makes with the other surface when it leaves the prism (i.e., the
refraction angle) is r. The diffraction of the light is shown in Fig. 1-3. The angle between the
incident light and the emitted light is referred to as the "deviation angle" ().
A
θ
i r
i : Incident angle, r : Refraction angle,  : Deviation angle

T : Length of prism's bottom surface
Fig. 1-3 Prism
If rays whose wavelengths differ by only  enter the prism at the same angle, and if  is the
difference in the deviation angles, then  /  (d / d) is referred to as the "angular
dispersion". The angular dispersion is determined by the prism's apex angle and material. The
deviation angle, , is a function of the refractive index, n, and the refractive index, n, is a
function of the wavelength, . This gives the following:
d / d=d / dn.dn / d
The relationships between n and  and between  and n can be obtained empirically, making it
possible to obtain d / d.
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6. Diffraction-grating Spectrometers
A diffraction-grating spectrometer disperses light by utilizing the way light is diffracted by
diffraction gratings. If there is an object in the path of a wave, the wave is bent as it passes
through the gaps in the object. This phenomenon is referred to as "diffraction".
Waves
Fig. 1-4 Diffraction of Waves
Fig. 1-4 shows the way waves on the surface of water are bent as they pass through the gap
in a wall. Light also exhibits this wave-like behavior. The way you can see dim light even if you
cannot directly see the light source is another example of diffraction.
Light source
Bright
Wave crest fromS 1
Wave trough
S1 Dark
Wave troughs Bright
S2
Wave crest Dark
Wave crest fromS 2
Bright
Screen
Fig. 1-5 Light Interference
Let us consider the case where diffracted light occurs in two places, in the way shown in Fig.
1-5. Interference occurs at places where these two sets of waves meet. At places where two
wave crests meet, the crests reinforce each other to become twice as high. (Similarly, at
places where two wave troughs meet, the resulting trough is twice as low.) On the other hand,
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at places where a crest meets a trough, they cancel each other out. As a result, an alternating
sequence of light and dark areas is created on the screen. The pitch of the stripes formed by
the dark and light areas on the screen depends on the interval between the waves emitted
from the light source (i.e., the wavelength). The smaller the wave interval, the smaller the pitch
of the stripes; the larger the wave interval, the larger the pitch of the stripes.
dsin 
↑ )
d
↓
)
Focus
Fig. 1-6 Diffraction
When two parallel rays are incident on two slits, separated by a distance d, in a direction
perpendicular to the surface, diffraction occurs at both slits. In the direction corresponding to a
diffraction angle of , a difference of dsin  occurs in the lengths of the respective optical
paths. Interference occurs in a way that depends on this optical-path difference. If the optical-
path difference is equal to a multiple of the wavelength then the light is intensified; if it is not,
then the waves cancel each other out to some extent and the light is weaker. In other words,
light of wavelength , where n= dsin , is intensified in the direction corresponding to
diffraction angle  whereas light of other wavelengths is weaker. n is an integer and is referred
to as the "diffraction order".
A diffraction grating consists of a large number of these slits, lined up in parallel at regular
intervals to form a lattice. The interval, d, between the slits of the diffraction grating is referred
to as its "grating constant".
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The diffraction gratings that are generally used are made by vapor depositing metal onto a
glass surface and making a large number of equally spaced, parallel grooves in the surface.
They can be classified into two types, plane diffraction gratings and concave diffraction
gratings, depending on the profile.
Normal to diffraction grating's surface

Normal to groove's surface
 
Vapor-deposited metal
ｄ
 Synthetic resin
Glass
Fig. 1-7 Diffraction Grating
If light coming from a given direction is incident on the diffraction grating, then, by diffraction,
the components of the light are intensified in directions that depend on the wavelengths. As a
result, spectra are formed. If  is the angle formed by the perpendicular to the diffraction
grating's surface and the incident light,  is the angle formed by the perpendicular and the
diffracted light (i.e., the diffraction angle), d is the grating constant, and  is the wavelength,
then the following holds:
n= d (sin  + sin ) n : Diffraction order
Here, n=0 corresponds to the direct image and n=±1, n=±2, n=±3, … correspond to diffraction
images of the first order, second order, third order, and so on. The wavelength dispersion can
be expressed in terms of the amount by which the diffraction angles changes with respect to
changes in the wavelength. If the incident angle is constant, and β is the difference in
diffraction angle between two rays whose wavelengths differ by only , then the angular
dispersion,  /  (d / d), satisfies the following:
 /  = n / d cos 
The angular dispersion is proportional to the order, n, and increases in inverse relation to the
grating constant. The dispersion at the focal plane can be expressed in terms of the way
distance on the focal plane corresponds to differences in wavelength (i.e., linear dispersion). If
two rays whose diffraction angles differ by only  form an image and l is the distance
between the two lines on the focal plane, then the line distribution l/ (d l/d) satisfies the
following:
d l / d= f . d / d f : Spectrometer's focal length

= n . f / d cos 
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In fact, the reciprocal of this expression, the inverse dispersion, is often used and is expressed
in nm/mm units.
d / d l = d cos  / (n . f)
= cos  / (N . f . n) N : Diffraction grating's groove density
(grooves/mm)
Therefore, the ability to separate small differences in wavelength increases in relation to the
diffraction grating's groove density, the spectrometer's focal length, and the diffraction order, n.
Table 1-1 Spectrometer Comparison

Diffraction
grating's Focal length Wavelength Reciprocal Resolution
Model groove density
(mm) range (nm) (nm/mm) (nm)
(grooves/mm)
ICPS-7000
2,160 750 Up to 380 0.22 0.0066
(2nd order)
ICPS-7000
2,160 750 Up to 850 0.44 0.013
(1st order)
ICPS-7500
3,600 1,000 Up to 458 0.22 0.0066
(main)
ICPS-7500
1,800 1,000 Up to 850 0.44 0.013
(sub)
ICPS-8100
4,960 1,000 Up to 372 0.15 0.0045
(No. 1)
ICPS-8100
4,320 1,000 Up to 426 0.17 0.0051
(No. 2)
ICPS-8100
1,800 1,000 Up to 850 0.44 0.013
(sub)
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7. Inductively Coupled Plasma Emission Spectrometers

A description of emission spectrometers that use inductively coupled plasma (ICP) as the light
source is given over the following pages. The advantages of using ICP as the light source are
listed below.
(1) Solutions can be introduced as samples. This means that compared with using solid
samples, it is easier to produce standard samples and analysis can be performed with a
higher degree of precision.
(2) For many elements, the detection limit is low and the sensitivity is extremely high.
(3) Because the plasma is at a very high temperature, and because the sample enters the
inside of a donut-shaped ring and stays there for a relatively long time, there is hardly any of
the chemical interference that occurs with the flame method.
(4) There is little self-absorption, and the linear range of the calibration curve goes up to 5 or 6
digits, giving an extremely wide "dynamic range".
(5) Many elements can be excited under the same conditions, and it is possible to perform
quantitative analysis simultaneously for elements present in widely differing amounts,
ranging from primary-constituent elements down to trace-constituent elements.
Fig. 1-8 shows a simple block diagram of the configuration of an ICP emission spectrometer.
Sample
introduction
ICP Spectrometer Photometer Data processing
Solution -> Atomization Emission Element spectra Light -> Electric signals Results
Spectrometry
Light-source section section Photometry section
Fig. 1-8 Configuration of ICP Emission Spectrometer
8. Light-source Section
This section is where the sample is made to emit light, thereby becoming the light source. In
general, light emission is achieved using flame or electric discharge. With an ICP emission
spectrometer, inductively coupled plasma is used.
9. Generation of Plasma
A high-frequency current (approx. 27.12 MHz (40.68 MHz), 1.2 kW) is passed through a high-
frequency coil wrapped around a plasma torch. The argon in the plasma torch is ionized by a
spark from a tesla coil, and plasma is generated in the way shown in Fig. 1-9.
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When high-frequency current is passed

through the high-frequency coil, magnetic
field lines are created around the coil, Plasma
Magnetic
and a high-frequency magnetic field is field line High-frequency
created inside the plasma torch. An induction coil
electric field of an intensity proportional to
the rate of change of this high-frequency
magnetic field is created by
electromagnetic induction. A spark is Coolant
discharged from a tesla coil and the water
electrons and ions that are generated are
accelerated by the electric field, receive
Sample
energy, and pass through the electric field
particles
at high speed. These high-speed
electrons repeatedly collide with the
argon gas molecules, ionizing some of
Fig. 1-9 Generation of Plasma
them. If the amount of electrons
generated per unit time is greater than the amount lost, the electron density increases rapidly,
and plasma is instantaneously generated at the open end of the plasma torch. When plasma is
generated, the electrons are attracted by the ions, and recombination reactions proceed. Also,
the argon gas passes through the high-frequency magnetic field at a constant speed, and
electrons and ions are lost. In this way, the plasma is maintained with a state of equilibrium
existing between the generation and loss of electrons and ions due to the ionization of the
argon gas molecules.
The way that the plasma forms a donut-shaped ring is referred to as the high-frequency
current's "skin effect". The skin effect describes the phenomenon where the high-frequency
current density is not uniformly distributed within a cross section of a conducting body; there is
a higher concentration at the surface layer than at the center. As a result, heating of the
plasma by current occurs at the periphery, and the center is heated by the conduction of heat
and radiation from the periphery. If carrier gas is introduced into the center of the plasma, the
temperature at the center drops even further, and a donut-shaped ring of plasma is formed.
Plasma
プラズマ
Sample
試料粒子particles
10 MHz max.
10MHz 以下 10 MHz min.
10MHz 以上
Fig. 1-10 Frequency Characteristics of Plasma
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10. Structure and Role of Plasma Torch

The type of plasma torch widely used today consists of three concentric quartz tubes (See Fig.
1-11). Coolant gas, plasma gas, and carrier gas are fed into torch from outside. Usually argon
gas is used as the coolant gas and is fed at a rate of 10 to 20 L/min. Argon gas is also used as
the plasma gas and is fed at a rate of 0 to 5 L/min. The main role of this gas is to lift the
plasma slightly so as to protect the intermediate quartz tube. The carrier gas introduces the
spray of the nebulized sample solution into the center of the plasma and is fed at
approximately 1 L /min. The flow rate of this gas not only determines the rate at which the
sample is introduced. If the rate is too high, the plasma is cooled excessively, the retention
time for the sample in the plasma becomes shorter, and the sensitivity drops. Therefore,
precise adjustment is necessary.
Plasma torch (quartz)
Coolant gas, 10 to 20 L/min
Plasma gas, 0 to 5 L/min
Carrier gas (sample)
Fig. 1-11 Structure of Plasma Torch
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11. Types of Nebulizer and Characteristics

At present, ICP emission spectrometry is generally used to analyze samples as solutions. The
introduction of liquid samples has been a subject of research for many years (e.g., for flame
photometry and atomic absorption spectrometry) and various nebulizers have been
developed. With ICP, however, because the carrier-gas flow rate is approximately 1 L/min, a
nebulizer that can nebulize the solution at a low gas flow rate is required. Fig. 1-12 shows the
concentric nebulizer, which is widely used today. It is made up of concentric glass cylinders,
formed into a single unit, and requires no adjustment for use. Different types of nebulizers can
be used to suit different applications. For example, there are nebulizers that are resistant to
hydrofluoric acid or high-concentration salt, as well as cross-flow nebulizers, which have a
different structure.
ICP
Coolant water
Torch
Coolant gas
Plasma gas
Nebulizer
Chamber
Carrier gas
Drain Sample solution
Fig. 1-12 Typical Sample Introduction System Used in Emission

Spectrometry
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12. Spectrometry Section

The spectrometers used in emission spectrometry must separate large numbers of atomic
spectral lines and so a high resolution is required. For this reason, the spectrometers used are
generally larger and have a higher level of performance than those used for absorption
photometry or atomic absorption spectrometry.
Diffraction gratings can be classified into two types, plane diffraction gratings and concave
diffraction gratings, depending on the profile. Fig. 1-13 shows typical spectrometer mountings
that use each type of diffraction grating.
The Paschen-Runge mounting is a mounting that uses a concave diffraction grating. Some
advantages offered by this mounting include the simple structure, the large measurement
wavelength range, and the high level of stability afforded by the fixed optical system. Because of
these features, it is used in polychromators.
The standard way of using a plane diffraction grating is to direct parallel light at it. With
sequential monochromators, the Czerny-Turner type is generally used. Wavelength scanning is
performed by changing the angle of the diffraction grating and moving the slit.
出口ｽﾘｯﾄ
Exit slit
Detector
検出器
ICP
Diffraction
回折格子
grating
Entrance
入口ｽﾘｯﾄslit
Example of Spectrometer Using Concave Diffraction Grating (Paschen-Runge)
Spherical
球面鏡 mirror
Exit slit
出口スリット
Detector
検出器
平面回折格子
Plane diffraction grating
Plasma
プラズマ
Spherical
球面鏡 mirror 入口スリット
Entrance slit
Example of平面回折格子を用いた分光器例（ツェルニ・タ－ナ－）
Spectrometer Using Plane Diffraction Grating (Czerny-Turner)
Fig. 図
1-13
1－Spectrometers Using Plane and Concave Diffraction Gratings
13 平面回折格子および凹面回折格子を用いた分光器
例
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13. Photometry Section

This section converts the intensity levels for the spectra obtained into electric signals. In general,
the light intensity is output as electricity by a photomultiplier and this is integrated over a fixed
time period by an integrating capacitor. A computer is used to process data and, in addition to
calibration-curve creation and concentration calculation, all types of correction can be performed
with ease. Fig. 1-14 shows the structure of the photometry section.
AMP
Gain V/F Counting P/C
Current, i
Light
Voltage, E Digitalization Integration Calculation
-HV
Fig. 1-14 Structure of Photometry Section
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14. Increasing Sensitivity with ICP Emission Spectrometry and Applications

Some options used to increase the sensitivity attained with ICP emission spectrometry are
explained below.
15. Ultrasonic Nebulizer

The ultrasonic nebulizer is a sample introduction device designed to increase the sensitivity
attained with ICP emission spectrometry.
With conventional pneumatic nebulizers (e.g., coaxial nebulizers), the sample is nebulized by the
negative pressure of the carrier gas. Ultrasonic nebulizers, however, nebulize samples using
ultrasonic energy.
The spray created with this method has the following characteristics:
1. A large amount of spray is generated.
2. The spray particles are small.
3. The nebulization efficiency is high.
For these reasons, the sample is introduced into the plasma more efficiently, and an increase in
sensitivity can be expected. On the other hand, if the sample is introduced with greater
efficiency, this means that the solvent (i.e., water) is introduced into the plasma at a higher rate.
This can have disadvantages; for example, the temperature of the plasma may drop and it may
become difficult to maintain the plasma.
In order to solve this problem, solvent is removed from the nebulized sample in the way shown in
Fig. 1-15. The nebulized sample is first introduced into a heating section, where the solvent is
evaporated. The sample then continues to a cooling section, where the solvent condenses on
the walls and is recovered. After the solvent is removed in this way, the remaining sample is
introduced into the plasma.
Heating section
Cooling section
Carrier gas
Peristaltic pump
Drain valve Nebulization
Sample solution
Fig. 1-15 Ultrasonic Nebulizer
With this method, it is possible to increase the efficiency of sample introduction while maintaining
the plasma stability. Increases in sensitivity by factors ranging up to several tens have been
observed. In the analysis of river water, wastewater, and mains water, the concentration of the
analyzed elements is low and so, with conventional nebulizers, samples must be concentrated
as part of the pretreatment process. This time-consuming task, however, is not necessary when
using an ultrasonic nebulizer.
Training－18
Fig. 1-16 shows some peak profiles obtained with an ultrasonic nebulizer and Fig. 1-17 shows
some calibration curves also obtained with an ultrasonic nebulizer. Table 1-2 shows the analysis
results obtained for wastewater and river water.
試料名称 : 河川水添加(JAC0032) 試料名称 : 河川水添加(JAC0032)
Ni 231.604nm As
Cd 189.042nm
214.438nm Se
Pb 196.026nm
220.351nm
5.00 8.00 8.00
5 2.00 55
1.50
55
6 66 66
4.00
6.00
1.50 6.00
1.00
3.00
4.00
1.00 4.00
2.00
.500
2.00
.500 2.00
1.00
E-1 E-2
E-1 E-2
E-1
0 00 00
 最適  最適
最適  最適
最適
Fig. 1-16 Peak Profiles Obtained with Ultrasonic Nebulizer
E 0 E 0
1.500 Ni 5.000 Cr
231.604 nm 267.716 nm
4.000
1.000
3.000
2.000
0.500
SD
ＳＤ 0.00011 1.000 SD
ＳＤ 0.00006
Correlation
相関 0.99999 Correlation
相関 0.99999
Unit
単位 ppm Unit
単位 ppm
0.000 0.000
0.000 0.010 0.020 0.030 0.040 0.050 0.000 0.005 0.010 0.015 0.020
Coefficients:
係数： a = 0.0000e+000 Coefficients:
係数： a = 0.0000e+000
b = 0.0000e+000 b = 0.0000e+000
c = 3.5998e-002 c = 5.0076e-003
d = -2.1750e-003 d = -1.5483e-003
E 0 E 0
5.000 1.000
Cd Pb
214.438 nm 220.351 nm
4.000 0.800
3.000 0.600
Correlation
Correlation Unit
2.000 Unit 0.400
1.000 SD 0.00007
ＳＤ 0.200 SD
ＳＤ 0.00013
Correlation
相関 0.99999
Unit
単位 ppm Unit
単位 ppm
0.000 0.000
0.000 0.010 0.020 0.030 0.040 0.050 0.000 0.010 0.020 0.030 0.040 0.050
Coefficients:
係数： a = 0.0000e+000
b = 0.0000e+000 b = 0.0000e+000
c = 1.1209e-002 c = 7.1100e-002
d = -4.5621e-004 d = -7.5632e-003
Fig. 1-17 Calibration Curves Obtained with Ultrasonic Nebulizer
Training－19
Table 1-2 Quantitative-analysis Results for Wastewater and River Water (Unit:
mg/L)
Element Wastewater River water Element Wastewater River water
Cd* 0.002 0.0003 Cu* 0.0083 0.0016
Pb* 0.003 0.001 Zn* 0.019 0.0027
Cr* 0.0013 0.0003 Fe* 0.15 0.019
As** 0.006 0.004 Mn* 0.087 0.0076
Se** 0.007 0.005
*Obtained using ultrasonic nebulizer **Obtained using the hydride-generation method
16. Hydride-generation Method

Arsenic, selenium, antimony, tin, tellurium, germanium, or bismuth in an aqueous solution reacts
with nascent hydrogen to form a gaseous hydride. Introducing this hydride into the plasma
enables high-sensitive analysis. Also, in the presence of a reducing agent, inorganic mercury
(Hg) in an aqueous solution is evaporated as liberated mercury. Introducing this vapor into the
plasma enables the high-sensitivity analysis of mercury.
Fig. 1-18 shows the configuration of the apparatus. Solutions of the sample, hydrochloric acid,
and sodium borohydride are pumped to a manifold and, after mixing, they are pumped to the
reaction coil, where the hydride is generated. This hydride, together with the hydrogen and water
vapor that is generated at the same time, along with the sample residue, are carried to a gas-
liquid separator. The gas phase and liquid phase are separated by the separator, the liquid
phase is discharged by the drain pump, and only the gas phase is introduced into the plasma by
the carrier gas, thus enabling high-sensitivity analysis.
Plasma
Gas-liquid separator
Reaction
Peristaltic pump Manifold coil
Sample
HCl
NaBH4
Peristaltic pump
for waste liquid
Carrier gas
Pressure switch Needle valve
Regulator
Fig. 1-18 Configuration of Hydride-generation Apparatus
Training－20
Fig. 1-19 shows some peak profiles obtained for river-water and wastewater samples using
hydride-generation apparatus. Fig. 1-20 shows the calibration curves.
1ppb 1ppb
1ppb
Influent Effluent
Influent
Influent
Effluent Effluent
Fig. 1-19 Peak Profiles for Arsenic, Selenium, and Antimony
E -1 E -1
0.400 As 0.500
Sb
189.042 nm 206.838 nm
0.400
0.300
0.300
0.200
0.200
0.100
SD 0.04827
ＳＤ 0.100 SD
ＳＤ 0.03382
Correlation
相関 0.99997
Unit
単位 ppb Unit
単位 ppb
0.000 0.000
0.000 10.000 0.000 10.000
Coefficients:
係数： a = 0.0000e+000
b = 0.0000e+000 b = 0.0000e+000
c = 2.7666e+002 c = 2.7570e+002
d = -8.7534e-001 d = -1.4053e+000
E -1
0.300
Se
196.026 nm
0.200
0.100
ＳＤ 0.01480
SD
Correlation
相関 0.99999
Unit
単位 ppb
0.000
0.000 10.000
Coefficients:
係数： a = 0.0000e+000
b = 0.0000e+000
c = 4.9532e+002
d = -1.7852e+000
Fig. 1-20 Calibration Curves Obtained with Hydride-generation Method
Training－21
17. Axial Measurement

Fig. 1-21 shows the configuration of the axial-measurement section and Fig. 1-22 illustrates the
principles behind the plasma-measurement direction. The spectra emitted from the plasma are
reflected by a mirror and directed to a spectrometer. Axial measurement, unlike transverse
measurement performed from the side of the plasma, makes it possible to capture the spectra
without passing through the high-temperature section of the plasma. This means that the
background level corresponding to emission from argon is reduced, enabling high-sensitivity
measurement. The sensitivity level is approximately 2 to 5 times that attained with transverse
measurement. Because the temperature at the tip of the plasma is low, however, ions recombine
and spectra are absorbed. To alleviate this problem, argon gas is blown from above to remove
the tip of the plasma.
図１-19 軸方向観測部の構成図
Fig. 1-21 Configuration of Axial-measurement Section
Transverse Measurement Axial Measurement
Fig. 1-22 Principle behind Plasma-measurement Direction
Training－22
Chapter 2 Qualitative and Quantitative Analysis
1. Qualitative Analysis
The Japanese publishing company Iwanami Shoten's Dictionary of Science defines qualitative
analysis in the following way.
Iwanami Dictionary of Science (Iwanami Shoten)

Qualitative Analysis
Chemical analysis for identifying unknown constituent substances in samples. In general, the
characteristic physical properties and chemical reactions are known for the molecules and atoms
(including atomic groups, ions, and isotopes), and these characteristics are used to detect or
confirm their presence. If a substance that may prevent detection is present, a separation
procedure is performed before analysis. Systematic wet-method analysis, which mainly uses the
chemical reactions of aqueous solutions, can be used to detect many types of metal elements.
There are many instrumental analysis methods that, in addition to qualitative analysis, can also be
used for quantitative or semi-quantitative analysis.
2. Emission Spectrometry and Qualitative Analysis

Emission spectrometry has been widely used for many years as it enables the simultaneous
measurement of many elements. In particular, with photographic photometry, which uses
photographic plates, it is possible to measure all the spectral lines for the required wavelength
range in one operation and so this method came to be regarded as a standard method for
qualitative analysis. Development of images, however, is required with this method making it
rather time-consuming. Furthermore, experience is required to detect spectral lines and so this is
not an analysis method that can be used by anyone.
Even when photoelectric photometry became the standard method used for quantitative
analysis, in the early days, it was inferior to photographic photometry in the field of qualitative
analysis. This was because it took a very long time to measure the entire wavelength range
using photographic photometry. With the development of sequential ICP emission spectrometry
brought about by the advancement of computer technology, however, photographic photometry
has become almost obsolete in the field of qualitative analysis.
Training－23
3. Qualitative Analysis with Sequential ICP Emission Spectrometry

Sequential ICP emission spectrometry differs from photographic photometry in that, instead of
measuring the whole spectrum, a scan is performed in the neighborhood of the target spectral
lines and profiles of those lines are obtained. In other words, the few spectral lines that are
required to perform qualitative analysis are quickly measured and the elements are detected.
Also, improvements in machine accuracy and the development of wavelength calibration
programs have helped improve the accuracy of wavelength calibration, making spectral lines
easy to detect. Fig. 2-1 and Fig. 2-2 show examples of peak profiles obtained in qualitative
analysis.
Sample
試料名称 name:: No.
No.33
Li 670.785 Be 313.042 B 249.773 Na 588.995 Mg 279.553 Al 396.153
Si 251.612 P 178.287 S 180.731 K 766.491 Ca 393.366 Sc 361.384
Ti 334.941 V 311.071 Cr 267.716 Mn 257.610 Fe 259.940 Co 228.616
Fig. 2-1 Qualitative Analysis 1 (1 Element, 1 Wavelength)

Sample
試料名称 name:: No.
No.33
B 182.640 B 208.959 B 249.773 Na 588.995 Na 589.592 Na 330.232
Mg 279.553 Mg 280.270 Mg 383.231 Si 251.612 Si 212.415 Si 288.160
P 178.287 P 213.620 P 177.499 S 180.731 S 182.037 S 182.625
Fig. 2-2 Qualitative Analysis 2 (1 Element, 3 Wavelengths)
Training－24
4. Spectral Interference and Discrimination of Elements

With emission spectrometry, many spectral lines are emitted for each element. The spectral
lines for samples containing several elements may overlap. (This is called "spectral
interference.") For this reason, it is necessary to use a spectrometer with a resolution over a
certain level. Even then, spectral interference may be unavoidable. Fig. 2-3 shows an example
of spectral interference.
試料名称 : Al,Fe 500+Cd,Pb 0.05
Cd 1M 226.502nm
2.00 226.505
K 226.504
Fe 226.505
In 226.506
1.50
1.00
.500
E-1
0
e
f
g 最適
c Optimum
d
Interference of Fe (226.505 nm) with Cd (226.502 nm)
Fig. 2-3 Spectral Interference (ICPS-8100)
Even if a peak is obtained at a certain wavelength, it cannot be asserted that a particular

element with a spectral line at that wavelength is present. This is because it may be the
spectral line of another element (co-existing element). It should be possible to say that if no
peak is obtained, then that element is not present. To be precise, however, it can only be said
that the element is not present in an amount greater than the lower detection limit of the
instrument used for measurement. It cannot be asserted that the element is completely
absent.
If a peak is obtained, another wavelength for the corresponding element is investigated.
Naturally, if the element is present, a peak will be detected for the other wavelength. In order to
increase the reliability of the analysis, it is necessary to check as many wavelengths as
possible. Another method is to investigate the existence of possible co-existing elements. If
there is no co-existing element, then there is no interference peak for that element.
This explanation probably makes qualitative analysis seem like a very laborious process. In
the age of photographic photometry, these procedures were carried out by experienced
analysts. With sequential ICP emission spectrometry, however, the knowledge of experienced
analysts is utilized as a database, simplifying the selection and confirmation of wavelengths.
Training－25
5. Calculation of Semi-quantitative Values

The intensity of a spectral line (peak height) is proportional to the concentration of the element
in the sample solution. With quantitative analysis, the concentrations are calculated by making
comparisons with the spectral-line intensities for known concentrations using methods such as
the calibration curve method or the standard addition method. With qualitative analysis,
because quantitative values are calculated without using standard samples, the results are
referred to as "semi-quantitative values." Usually, a database is prepared in order to perform
this calculation. Because of differences in these databases, however, the semi-quantitative
values obtained can vary greatly. Fig. 2-4 shows the semi-quantitative values for qualitative
analysis.
Fig. 2-4 Semi-quantitative Values for Qualitative Analysis
The primary purpose of qualitative analysis is to detect unknown constituent elements. It is to

determine whether or not a certain element is present or to determine which of two samples
contains more of the element. With ICP emission spectrometry, however, the processing of
measurements as digital values and the ability to use large-scale databases, made possible by
a reduction in the cost of computers, has made the semi-quantitative values themselves the
subject of interest. Pay attention to the spectral lines instead of just focusing on the results of
the calculations.
Training－26
6. Quantitative Analysis
With ICP emission spectrometry, which is mainly used to analyze solutions, the following methods
are used for quantitative analysis:
(1) Calibration curve method
(2) Standard addition method
7. Calibration Curve Method

The calibration curve method is a generally used method of quantification. With this method, a
calibration curve is created using standard samples, the emission intensities for the actual
samples are measured, and the target elements are quantified.
The following points must be noted when using the calibration curve method.
(1) There must be no degeneration or contamination of the standard samples.
(2) The standard samples and actual samples must have similar compositions (matrix
matching).
(3) Measurement must be performed within the linear range of the calibration curve.
(4) The analytical lines used must not be subject to spectral interference.
Emi
ssio Emission
intensity for
n
sample
inte
nsity
,E
Concentration for sample
Concentration, C
Fig. 2-5 Principle of Calibration Curve Method
8. Creation of Calibration Curve

The calibration curves used in ICP emission spectrometry have good linearity and so a
calibration curve can be created from just two points, obtained using a blank sample and a
standard sample with a known concentration. In order to confirm that the standard samples
have been prepared properly and to confirm the linearity of the calibration curve, however, it is
recommended that the calibration curve is created using at least three points. The valid range
of the calibration curve is roughly between one hundredth of and two times the calibration-
curve upper-limit sample concentration for the element. The calibration-curve upper-limit
sample concentration must be no less than the BEC (Refer to 2.3). Also, if the actual samples
are subject to interference, it may be necessary to perform correction using techniques such
as internal standard correction or background correction.
Training－27
9. Standard Addition Method

The standard addition method is used if there is interference due to a sample matrix and this
interference cannot be removed. As shown in Fig. 2-6, the concentration is changed by adding
standard solutions to the actual sample solution to obtain several points (1 to 3 points) at roughly
the same concentration level as the measured element. The intensities are measured for each
solution, including the original sample solution, the line through the corresponding points is
extended, and the concentration for the actual sample is calculated from the point of intersection
with the horizontal axis.
The following points must be noted when using the standard addition method.
(1) The linearity of the calibration curve in the measurement range must be confirmed.
(2) From 1 to 3 points must be obtained by adding samples.
(3) The upper limit for the concentration of added samples is several times the predicted
concentration.
(4) If an added sample is diluted in preparation, all other samples must be diluted with the
same dilution factor. (There are cases where the sample solution is diluted by adding the
analyzed element. Add the same amount of water (ultrapure water) to the original sample
as added to the added samples and ensure that all the samples have the same dilution
factor.)
(5) It must be confirmed that there is no spectral interference for the analytical lines used.
(6) Background correction must be performed.

Emission intensity, E
E3
E2
E1
Es
CS C1 C2 C3
Unknown sample Concentration for added samples
concentration
Fig. 2-6 Principle of Standard Addition Method
Training－28
10. Detection Limit and Limit of Quantitative Determination
B
Intensity S
3B
IB
Concentration
BEC
Fig. 2-7 Calibration Curve
BEC
(1) BEC: Background Equivalent Concentration

Concentration for which S/B = 1 (S: Signal B: Background)
BEC = IB×k
IB: Intensity of blank sample
k: Inclination of calibration curve (concentration/intensity (I − I B))
(2) DL: Detection Limit

The background intensity for the measurement wavelength is repeatedly measured, and the
element concentration that gives an intensity equivalent to 3 times the standard deviation of
that intensity is taken to be the detection limit.
DL = 3×B×k
B: Standard deviation of IB
ｋ: Inclination of calibration curve (concentration/intensity (I − IB))
(3) LQD: Limit of Quantitative Determination

The measurement accuracy at the above detection limit is given by RSD=33% and there are
large errors in analysis values. As for the limit of quantitative determination, the value varies
with the level of accuracy sought. In general, the concentration giving an intensity
corresponding to 10B is used as the limit of quantitative determination.
LQD = 10×B×k
In this case, the accuracy for quantification at the LQD concentration is approximately given by
RSD=10%.
Training－29
Reference: 1) The formula for DL rewritten in terms of BEC is as follows:

DL = 3×B / IB×BEC (IB×k= BEC)
= 3×RSD B×BEC RSD B: Coefficient of variation for IB (B/IB)
The coefficient of variation for the background intensity in ICP emission spectrometry is
approximately 1%. This gives the following:
DL≒3×BEC / 100 (RSD B≒1 / 100)

LQD≒10×BEC / 100
This means that approximations for DL and LQD can be obtained from BEC.
Reference: 2) The concentration and measured intensity for an ICPS-series calibration curve
satisfy the following equation. (Fig. 2-8 Calibration-curve Coefficients)
Concentration ＝a×Ｉ 3+b×Ｉ 2+c×Ｉ+d

(I: Measured intensity; a, b, c, d: Calibration-curve coefficients)
LQD and DL are calculated using the calibration-curve E 0

1.000
Pb
coefficients in the way shown below (linear 220.351 nm
expression). 0.800
DL = 3×B×c (inclination of calibration curve) 0.600
LQD = 10×B×c (inclination of calibration curve) 0.400
Also, BEC is equal to calibration-curve coefficient d 0.200 ＳＤ 0.00013

SD
Correlation
相関 0.99999
without its minus sign. Unit
単位 ppm
0.000
0.000 0.010 0.020 0.030 0.040 0.050
BEC= -d Coefficients:
係数： a
b
=
=
0.0000e+000
0.0000e+000
c = 7.1100e-002
d = -7.5632e-003
Fig. 2-8 Calibration-curve Coefficients
Caution: When performing measurement with background correction, the value for the
intensity is the value after deduction of the background constituent. For this reason, the
calculation method for BEC and the simple calculation method for LQD described above
cannot be used.
Training－30
Chapter 3 Analysis with the ICPS Series
1. Qualitative Analysis
There are two methods for performing qualitative analysis with the ICPS series, "Qualitative
Analysis 1" (hereafter referred to as "Qualitative 1") and "Qualitative Analysis 2" (hereafter referred
to as "Qualitative 2"). With "Qualitative 1," one previously determined spectral line is measured for
each element. With " Qualitative 2," several spectral lines can be selected for each element.
Usually, three spectral lines are measured for each element.
These instruments use sequential monochromators. Therefore, the greater the number of spectral
lines, the longer the measurement time. Naturally, the amount of sample and argon gas that is
consumed increases. Bearing in mind the original purpose of qualitative analysis, it would be
desirable to measure as many spectral lines as possible. Because of time considerations,
however, "Qualitative 1" and "Qualitative 2" used selectively.
"Qualitative 1" and "Qualitative 2" have the following characteristics.
Table 3-1 Qualitative Analysis 1 and Qualitative Analysis 2
Qualitative Analysis 1 Qualitative Analysis 2

Element selection Automatic (1) Semi-automatic (2)
Wavelength selection Fixed (3) Semi-automatic (4)
Number of wavelengths per element 1 Free (5)
Maximum number of elements 72 72 (6)
Maximum number of wavelengths 72 216 (6)
(1) 68 elements are selected as the default setting. This number can be increased or decreased
manually. (Maximum: 72 elements.)
(2) When changing from "Qualitative 1," selection is automatic. Elements can be changed and
selected freely.
(3) Fixed for each element.
(4) Selection of recommended wavelengths (up to 3 wavelengths max.) or selection from a
wavelength table.
(5) Limited to the wavelengths registered in the wavelength table for each element (up to 16
wavelengths max.).
(6) The maximum number of wavelengths takes priority over the maximum number of elements.
If the composition of analyzed sample is completely unknown, in other words, if the measured
elements cannot be identified, "Qualitative 1" is used. Depending on the result, it may then be
possible to switch to "Qualitative 2." If the measured elements can be narrowed down, to no more
than roughly 20 elements, "Qualitative 2" is used.
Training－31
2. Qualitative Analysis 1
With "Qualitative 1," one previously determined spectral line is measured for each element. The
result is used to determine the existence of peaks and, consequently, the existence of elements.
Even if a peak is found, however, one piece of information (i.e., one spectral line) is not sufficient
to determine whether this is a peak for a target element, or a peak for a co-existing element. On
the other hand, if no peaks can be found, it can be concluded that there are no target elements.
Think of "Qualitative 1" as a way of identifying elements that are clearly not present.
Sample name: Mains water

試料名称 : 水道水
Li 670.785 Be 313.042 B 249.773 Na 588.995 Mg 285.213 Al 167.079
Si 251.612 P 177.499 S 180.731 K 766.491 Ca 317.933 Sc 361.384
Ti 334.941 V 311.071 Cr 267.716 Mn 257.610 Fe 259.940 Co 228.616
Fig. 3-1 Spectral-line Profile for "Qualitative 1"
3. Switching from Qualitative Analysis 1 to Qualitative Analysis 2

On completing "Qualitative 1" and switching to "Qualitative 2," judgments on the presence of
elements are made. Only elements with a PK level (explained later) of 2 or more in the spectral-
line profile obtained with "Qualitative 1" are investigated in "Qualitative 2." In other words, only
the elements that the computer judges to be present are carried over.
As mentioned previously, only one wavelength is measured for each element in "Qualitative 1"
and so it is not possible to categorically determine whether the detected spectral lines
correspond to the target elements. In any case, elements with a PK value of 2 or more are
carried over. Whether or not this selection is correct is investigated in "Qualitative 2." Elements
with a PK value of less than 2 are not carried over, even if profiles that could be peaks are
present.
Training－32
・PK (Peak) Value

PK = Is / X
Is: Peak signal intensity Ｉ

X: Average intensity for all points in profile s
(X = ΣXn / N）
N pieces of data
Sample
試料名称 name: Mains water
: 水道
B 249.773nm Fe 259.940nm Zn 213.856nm
1.50 SB 2.19 8.00 SB 20.1 1.50 SB 26.1
BG .042 1 BG .033 1 BG .048 1
CV 48.0 CV 159 CV 157
PK 2.38 PK 6.08 PK 5.67
6.00
1.00 1.00
4.00
.500 .500
2.00
E-1 E-1 E0
0 0 0
 最適  最適  最適
Fig. 3-2 PK Values
4. Qualitative Analysis 2
The elements deemed to be present by the computer in "Qualitative 1" are carried over to
"Qualitative 2." Here, measured wavelengths are added for these elements and judgments on
the existence of the elements are made again. Unlike "Qualitative 1," the number of wavelengths
can be selected freely. Usually, three spectral lines per element is an appropriate number. Also,
the computer's judgment on the elements that could be present is not necessarily correct
(elements with a PK value of less than 2 are not carried over, even if profiles that could be peaks
are present) and so elements are added as deemed appropriate.
When starting with "Qualitative 2," select elements that are estimated to be present and
elements whose presence you would like to confirm. Also, use three wavelengths per element.
If a co-existing element is known to be present, change the wavelength used in the wavelength
table. The number of wavelengths per element can be set freely but note that the maximum total
number of wavelengths for all elements is 216.
Training－33
Sample
試料名称 name:: Mains
No.3 water
B 182.640 B 208.959 B 249.773 Na 588.995 Na 589.592 Na 330.232
Mg 279.553 Mg 280.270 Mg 383.231 Si 251.612 Si 212.415 Si 288.160
P 178.287 P 213.620 P 177.499 S 180.731 S 182.037 S 182.625
Fig. 3-3 Spectral-line Profile for "Qualitative 2"
5. Measurement Results (Semi-quantitative Values and Degree of Reliability)
6. Semi-quantitative Values
The peak intensities in the measured spectrum are compared with the information in the
database and the concentrations are calculated. Usually, the database contains data on
aqueous solutions with no co-existing substances. Standard conditions are used as the
analysis conditions. Furthermore, the LQD also varies with the sensitivity of the spectral lines.
Therefore, think of the results that are displayed or output as semi-quantitative values or as
reference values. Make a point of checking for the existence of peaks in spectral-line profiles
before using the values.
Analysts can create their own database. Creating a database in accordance with frequently
used analysis conditions and co-existing substances makes it possible to increase the
accuracy of the semi-quantitative values. It is also possible to switch between several different
databases by replacing database files.
Fig. 3-3 Screen Display of Semi-quantitative Values for Qualitative Analysis 1
Training－34
7. Degree of Reliability
With "Qualitative 1," one spectral line is measured for each element and so one semi-
quantitative value is obtained for each element. With "Qualitative 2," however, the number of
semi-quantitative values obtained is equal to the number of spectral lines for each element.
Using these values, judgments on the existence of elements and the certainty of the semi-
quantitative values are made.
Fig. 3-4 Screen Display of Semi-quantitative Values for Quantitative Analysis 2
As mentioned earlier, spectral interference is expected with ICP emission spectrometry. If

spectral interference is present, the semi-quantitative values are usually larger than actual
values. Conversely, it can be said that the smallest value is the one closest to the actual value.
It can also be said that the less variation there is in the semi-quantitative values for a set of
spectral lines, then the higher the degree of reliability. With "Qualitative 2," the display of semi-
quantitative values is divided into five levels according to degree of reliability.
If only one wavelength is measured for an element, it is not possible to make judgments based
on comparisons with other wavelengths and so the degree of reliability is classified as 0.
The degree of reliability indicates the reliability of the judgment about the existence of the
element, not the reliability of the semi-quantitative values. Even if the degree of reliability is 0,
this does not necessarily mean that the semi-quantitative value is wrong. It just means that no
judgment can be made about the existence of an interfering element (i.e., spectral
interference).
Also, the semi-quantitative value displayed for an element is the smallest semi-quantitative
value obtained from the calculations for all wavelengths corresponding to that element. This
value can be thought of as a maximum value (i.e., the possibility of the element being present
at a greater concentration is remote).
Training－35
Table 3-2 Classification of Degree of Reliability

Degree of reliability Definition
0 Only 1 wavelength measured
1 QMAX QAV×2 and QMIN QAV / 2
2 QMAX QAV×3 QMIN QAV / 3
5 Other than the above
QAV: Average of the semi-quantitative values
QMAX: Maximum semi-quantitative value
QMIN: Minimum semi-quantitative value
8. Database of Semi-quantitative Values

When measuring quantitative values with emission spectrometry, a calibration curve is created
using standard samples (calibration-curve samples) and the concentrations for unknown
samples are calculated. When performing quantitative analysis for completely unknown
samples, however, it is nearly always the case that the measured elements and the
approximate concentrations cannot be ascertained. This makes it impossible to perform
quantitative analysis using a calibration curve.
With ICP emission spectrometry, the calibration-curve linearity is high and so it is possible to
obtain approximate values by extending the calibration curves. It is inconvenient to have to
repeatedly create calibration curves to obtain approximate values and so a database is
created by storing these calibration curves on a computer. Describing this as a "database" is a
slight overstatement; think of it as a collection of calibration-curve information for spectral
lines.
At the time the system is delivered, the database contains values based on 100-ppm aqueous
solutions of single elements and standard analysis conditions. This database is not, however,
prepared for each system individually and so there may be some discrepancies due to
individual differences. Furthermore, the accuracy of semi-quantitative values can be adversely
affected if the analysis conditions are changed or large quantities of co-existing elements are
present. (The values can differ significantly, for example, if an ultrasonic nebulizer is used.)
With the ICPS series, it is possible to create a database using standard solutions of freely
chosen concentrations. If necessary, the accuracy of semi-quantitative values can be
increased by creating a database. Databases can be backed up to a floppy disk and so it is
possible to switch between several databases in accordance with the analysis conditions and
measured samples.
CAUTION
In the database for semi-quantitative values described above, data is registered for each
wavelength. For this reason, if only some of the wavelength data for an element is updated,
discrepancies will occur among the semi-quantitative values for the updated wavelengths and
the wavelengths that are not updated. (This means that a lower degree of reliability may be
displayed for this element.)
Training－36
In order to prevent this kind of discrepancy, measure all the wavelengths used for Qualitative
Analysis 2 when updating the database.
9. From Qualitative Analysis 2 to Quantitative Analysis

With "Qualitative 2," in addition to ascertaining the measured elements and the approximate
concentrations, the conditions for quantitative analysis are set.
Elements for which quantitative analysis is performed are selected in the same way as when
starting from "Qualitative 2." Again, "3 wavelengths per element" is selected. Standard samples
are measured together with unknown samples. Standard samples are measured in order to
confirm the measurement concentrations and so that the sensitivities used for each element
(wavelength) in quantitative analysis are set automatically.
It is confirmed from the profiles that concentrations of the standard samples are appropriate with
respect to the unknown samples. Next, measurement was performed using three wavelengths
per element and so the optimum wavelength is selected out of the three for quantitative analysis.
A qualitative order is ascribed to the three wavelengths. The order is primarily determined by
consideration of the sensitivities for the wavelengths and the influence of co-existing elements.
The computer determines the optimum wavelength using the measurement results (PK values)
of the three wavelengths and this order. The computer's selection is not necessarily the best one
and so change the selection as appropriate.
These operations carry the information about the measured elements, measured wavelengths,
and sensitivities over to the quantitative-analysis stage.
Training－37
10. Quantitative Analysis

In general, basic information is carried over from "Qualitative 2" and so measurement can be
performed after registering the standard samples and setting the display and printing conditions.
If, however, the wavelengths used for measurement are affected by co-existing elements, or if the
measured concentrations are low and the peaks for the measured elements are lower than the
background peaks, the scan mode must be changed.
11. Scan Mode
12. Peak Search Mode

With scanning ICP emission spectrometry, the spectrometer is set in the target wavelength
position, which is calculated using a wavelength-correction curve. Depending on the accuracy
of the wavelength-correction curve, however, there may be some discrepancy between this
position and the actual wavelength position. In general then, a fixed interval containing the
calculated position is scanned, the peak position (i.e., the target wavelength position) is found,
and the spectrometer is set at this position.
(1) (2) ｱ (3)

T
 Fig. 3-5 Peak Search Mode
Measurement Procedure for Peak Search Mode

(1) In accordance with instructions from the computer, the spectrometer moves to the position
of the calculated (i.e., calculated from the wavelength-correction curve) wavelength, .
(2) Measurement is performed in the range ±  to investigate the presence of peaks.
(3)The spectrometer is set at the position of wavelength T, which corresponds to the
detected peak, and integration is started.
(4)If the height of the peak is less than the prescribed level and consequently the peak cannot
be detected, the spectrometer is set at the position of the calculated wavelength, , and
integration is started.
Points to Note Regarding Peak Search Mode

(1) Peaks cannot be detected if they are too small or if there are no peaks.
(2) A peak may be erroneously detected if there is an interfering spectral line in the scanning
range.
Training－38
Sample name: Leaf extract

試料名称 : 葉抽
P 213.620nm Ni 221.647nm Zn 202.551nm
1.50 2 1.50 2 4.00 2
4 4 4
3.00
1.00 1.00
2.00
.500 .500
1.00
E1 E-1 E0
0 0 0
 最適  最適  最適
Fig. 3-6 Existence of Interfering Spectral Lines
Fig. 3-7 Calibration Curve in Peak Search Mode (Existence of Interfering Spectral Lines)
Training－39
13. Direct Mode: ICPS-7500/8100

With the ICPS-7500/8100, direct mode is used if a peak is erroneously detected in peak
search mode. In direct mode, an interval that is smaller than the one used in peak search
mode is scanned, the peak position (i.e., the target wavelength position) is found, and the
spectrometer is set at that position. The width of this interval is roughly equal to the peak width
at half the peak height and so the positions of the calculated wavelength and the actual
wavelength must be very close.
Therefore, as part of the direct-mode procedure, a peak is detected in peak search mode
using a peak-catch sample, for which there is no risk of erroneous peak detection. This is used
to obtain the difference between the actual and calculated wavelength positions. This
difference is used to correct the calculated value for the wavelength.
Measurement Procedure for Direct Mode
(1) Measurement is performed using the peak-catch sample with the same procedure used
with peak search mode to obtain Z.
(2) The wavelength used for each measurement sample is changed to + Z.
(3) Measurement is performed in the range + Z ± Z to investigate the presence of peaks.
(4) The spectrometer is set at the position of wavelength T, which corresponds to detected
peak, and integration is started. If the height of the peak is less than the prescribed level
and consequently the peak cannot be detected, the spectrometer is set at the position of
wavelength + Z, and integration is started.
14. Direct Mode: ICPS-7000

With the ICPS-7000, direct mode is used if, in peak search mode, a peak is erroneously
detected, or if the concentration of the measured element is close to the LQD and the peak is
small or non-existent. In direct mode, peak scanning is not performed for each sample; the
spectrometer is set directly at the peak position (i.e., the target wavelength position).
Therefore, the positions of the calculated wavelength and the actual wavelength must be very
close.
Therefore, as part of the direct-mode procedure, a peak is detected in peak search mode
using a peak-catch sample, for which there is no risk of erroneous peak detection. This is used
to obtain the difference between the actual and calculated wavelength positions. This
difference is used to correct the calculated value for the wavelength.
Measurement Procedure for Direct Mode
(1) Measurement is performed using the peak-catch sample with the same procedure used
with peak search mode to obtain Z.
(2) The wavelength used for each measurement sample is changed to + Z, the
spectrometer is set, and integration is started.
Points to Note Regarding Direct Mode

(1)Measurement of the peak-catch sample must be performed before actual measurement.
(2) It must be confirmed that a peak was definitely detected with the peak-catch sample.
(3) The peak position may vary slightly due to changes in the installation environment, such
as variations in room temperature. In this case, analyze the peak-catch sample
approximately once every hour and correct the peak position.
Training－40
Measurement Using Peak-catch Sample
(2) ± (3)

(1)
Z
Measurement Using Direct Mode
(5) (6)
(4)
Ｔ
±Z
+Z
Fig. 3-8 Direct Mode
Training－41
15. Fixed-wavelength Mode (ICPS-7500/8100)

With the ICPS-7500/8100, fixed-wavelength mode is used if the concentration of the
measured element is close to the LQD and the peak is small or non-existent.
In fixed-wavelength mode, a peak-catch sample is used and the spectrometer is fixed at the
target wavelength position. The samples are measured in order with the spectrometer at the
same position (i.e., wavelength). When measurement is completed for all samples,
measurement for the next element (wavelength) is carried out. Thus, with fixed-wavelength
mode, all samples are measured for one element (one wavelength) (i.e., measurement is
sequential by sample). This contrasts with peak search mode and direct mode where
measurements of all elements are made for one sample (i.e., measurement is sequential by
wavelength).
Sequential by wavelength: Peak search mode, direct mode
Sequential by sample: Fixed-wavelength mode
Points to Note Regarding Fixed-wavelength Mode
(1) The measurement time is long and large amounts of samples and argon gas are
consumed.
(2) It must be confirmed that a peak was definitely detected with the peak-catch sample.
(3) The peak position may vary slightly due to changes in the installation environment, such
as variations in room temperature. In this case, analyze the peak-catch sample
approximately once every hour and correct the peak position.
16. Calibration Curve Method and Standard Addition Method

There are two methods that can be used for quantitative analysis, the calibration curve method
and the standard addition method. Select the method in accordance with the method used to
prepare the standard samples. It is not possible to select both methods. Select either one or the
other.
Training－42
Chapter 4 Interference and Correction Methods
1. Interference
The purpose of qualitative analysis is to detect unknown constituents (elements). It has primarily
been used to determine whether an element is present or to determine which of two samples
contains more of the element. However, considering how the analytical process flows from
qualitative analysis to quantitative analysis, there is still more information that needs to be obtained
from qualitative analysis. Merely identifying the elements for quantitative analysis and determining
the concentration levels of those elements is not sufficient for conducting accurate quantitative
analysis. Certain sample characteristics can affect analytical values (interference), so these
various effects must be eliminated or corrected.
(Section of instrument) (Process) (Interference type)

(Test solution)
↓
Nebulizer Spray
Physical
↓
interference
Chamber torch Mist delivery
↓
Desolvation
↓
Generation of chlorides and
oxides, etc.
Chemical
↓
interference
Separation and vaporization
Plasma ↓
Atomization
↓
Ionization
Ionization
interference
↓
Excitation and emission
↓
Spectrometer and Spectral emission and detection Spectral
detector interference
Fig. 4-1 ICP Emission Spectrometry Processes and Interference Types
Training－43
2. Physical Interference
Interference that is caused by changes in physical factors is called physical interference. As
shown in Figure 4-1, physical interference occurs during the processes of spraying and
delivering test solutions. This type of interference occurs easily in ICP emission spectrometry.
1.2 1.2 1.2
Relative Strength
1 1 1
相対強度
Fe
Zn
Y
0.8 0.8 0.8
0.6 0.6 0.6

0 0.2 2 20 0 0.2 2 20 0 0.2 2 20
Concentration of
硝酸濃度（%）塩酸濃度（%）硫酸濃度（%） Hydrochloric
Sulfuric
Nitric Acid
Acid
Acid
(%)
(%)(%)
Fig. 4-2 Physical Interference
Figure 4-2 shows how emission intensity changes when the concentration level is varied for
various types of acids. The spray volume and emission intensity decrease in inverse relation to
viscosity. In addition, the same phenomenon also occurs when high concentrations of chlorides
or organic substances are coexistent.
3. Chemical Interference
During the processes ranging from desolvation through atomization, insoluble compounds can
appear between elements. These compounds are not completely decomposed by atomization
and reduce the effectiveness of atomization. Interference occurring for this reason is called
chemical interference. Many coexisting substances are known to cause such chemical
interference in atomic absorption spectrometry using a flame. Some examples include PO 43- with
respect to Ca, Al or Si with respect to Mg, and Al with respect to Ti. On the other hand, there
have been no reported cases of chemical interference with ICP emission spectrometry. This is
due to the high plasma temperatures, which quickly decompose such compounds.
Training－44
4. Ionization Interference
If easily ionized elements are present in the sample, such as Na, K, or Ca, the ionization
equilibrium will shift and the emission intensity will change. This increases the intensity of neutral
atom lines and decreases the intensity of ion lines. Interference occurring for this reason is
called ionization interference.
Relative Intensity
1.2
1.1 (nm)
相対強度
Ca396.847
1 Ca317.933
Ca422.673
0.9
0.8 changes in intensity for Ca analytical lines due to ionization interference. The
Figure 4-3 shows
horizontal axis is 0the level of sodium
500 concentration
2000 and10000
the vertical axis is the relative intensity of
Na Concentration (mg/L)
each analytical line (given anNa濃度（mg／L）
intensity of one at a sodium concentration of zero). Ca 396.847 nm
and Ca 317.933 nm are ion lines and Ca 422.673 nm is a neutral line. When the concentration of
Sodium is increased, the ion lines decrease and the neutral line increases.
図４－３　イオン化干渉
Training－45
5. Spectral Interference
Interference occurring from fluctuations in the emission intensity of target elements due to
spectroscopic causes associated with argon or other constituent substances in the plasma gas
are called spectral interference. There are three types of spectral interference. Spectral lines can
overlap or overlap the edge of an adjacent intense line, or the background can increase due to
continuous emission. These modes are illustrated in Figure 4-4.
(A) (B)
Ip
Ip
Ip
Ip
Intensity
(C) (D)
Ip Ip
Ip Ip
Wavelength
波　長
図 4 － 4 　分光干渉
Dark line: Total signal Thin line: Background signal Ip: Peak intensity of target element
(A) Spectrum without spectral interference (B) With small overlapping interference peak
(C) Overlapping edge of intense interfering peak (D) With increased background emission
The effects of spectral interference always appear as increases in signal intensities that are
independent of the target element concentration. Therefore, the problem is even more important
when analyzing trace quantities, so extra care is required.
Training－46
6. Correction Methods
The previous section described various types of interference and explained their causes and
characteristics. To eliminate or suppress such interference, the substances causing the
interference must be removed using pretreatment. However, pretreating samples is very labor
intensive, so typically measurements are corrected instead.
7. Matrix Matching Method

ICP emission spectrometry is a comparative method of analysis. Quantitation is performed by
preparing a calibration curve from standard samples. As explained earlier, standard samples
must have a composition that is similar to the test sample. This means that if the composition of
the standard sample does not match the test sample, the affects of any interference will cause
an error in quantitation values. On the other hand, if the composition is similar to the test sample
then standard samples will be affected by interference in the same way as the test sample, so
there is no problem. In other words, if the concentrations of acids and key constituents that can
cause physical or ionization interference can be determined, then the composition of the
standard and test samples can be matched. This makes it possible to perform quantitation
without interference effects. However, care must be taken to avoid introducing impurities from
the reagents added to prepare the matrix.
8. Internal Standard Correction

Physical interference varies depending on variations in the amount of sample introduced.
Therefore, the quantities introduced are measured and corrections are made for the variance.
However, normally these quantities are not measured by measuring volume or weight. The
internal standard correction method involves measuring the emission intensity of a reference
element (an internal standard) that functions as an indicator of variations in sample quantities
introduced and then corrects the intensity values to compensate for those variations. In some
cases, JIS has specified an internal standard method, such as the yttrium standard sample
method used for steel analysis.
A fixed quantity of the internal standard element is added to the standard sample and the ratio of
the measured element intensity (IS) and the internal standard intensity (I R) is obtained. A
calibration curve is generated by plotting this intensity ratio with respect to the measured
element concentration level. Similarly, a fixed quantity of the internal standard is also added to
the test sample, the intensity ratio is measured, and the concentration level of the measured
element is obtained (See Figure 4-5).
発光強度比 I S／I RIntensity Ratio (IS/IR)
Correction Formula
Corrected Uncorrected Intensity (Is)

Intensity = Internal Standard Intensity x100
(IR)
実試料の
Intensity ratio
for test sample
発光強度比
Sample
Concentration
試料濃度
濃度Ｃ (C)
Concentration
Training－47
Fig. 4-5 Internal Standard Correction
Internal standard correction makes it possible to eliminate physical interference. In addition,

simultaneous internal correction can correct for emission intensity fluctuations from plasma
flicker and other causes, allowing significant improvements in measurement accuracy
(repeatability).
Conditions for internal standards:
(1) It should not be contained in the sample or contained only in trace quantities relative to the
added quantity.
(2) It should exhibit the same behavior as the measured element.
(3) It should not be affected by spectral interference from the measured element or coexistent
elements.
(4) It should not cause spectral interference for the measured element.
(5) Adding reasonable amounts should produce sufficient emission intensity.
(6) High purity reagents should be used.
As condition (2) also implies, correction is possible because the fluctuation in emission intensity
for the measured element and the internal standard are the same. However, if the concentration
of the measured element is reduced below BEC, background fluctuations become greater than
fluctuations in the measured element. The behavior of background fluctuations is generally
different than the fluctuations of the measured element and internal standard. Therefore, if
measured element concentrations are below BEC, then corrections could have the opposite
effect and decrease measurement precision (accuracy and repeatability).
Two types of correction methods are available depending on how the internal standard element
is measured.
9. Simultaneous Internal Standard Correction

The term “internal standard analysis” normally refers to simultaneous internal standard
correction. Analyzed elements and internal standard elements are measured simultaneously,
allowing not only correction for variability between samples, but also correction for variability
between repeated analyses. An internal standard spectrometer is required to perform
simultaneous internal standard correction. (Model ICPS-7500 is compatible using optional
equipment.)
10. Sequential Internal Standard Correction

The internal standard is measured sequentially as part of a sequential measurement of
analyzed elements. The analytical elements and the internal sample are not measured
simultaneously, but it is effective in correcting for intensity variations resulting from differences
in sample liquids. In addition, it has the benefit of allowing the internal standard to be freely
selected.
Training－48
11. Background Correction

Calibration curve methods measure the total emission intensity (I P), which is a combination of
the spectral line intensities for target elements (I’ P) and the background intensities (I B). Therefore,
if spectral interference causes the background intensity to vary, the total emission intensity also
varies, resulting in an error in quantitation values. Background correction involves correcting for
these background variations. However, rather than correcting for the magnitude of variation,
background correction corrects by subtracting out the varying background.
Correction Formula
強度
Intensity
IP = I’P - IB I’P
DS
= I’P - IS+ x (IL - IS)
DS+ DL
DS×IL＋DL×IS IL
= I’P - IS IB
DS＋DL
Wavelength
波長
DS DL
IP: Intensity after correction
Figure図４－６　バックグラウンド強度の算出
4-6 Calculating Background Intensity
I’P: Intensity before correction
IB: Background intensity
IS: Intensity at background point on short wavelength side
IL: Intensity at background point on long wavelength side
DS: Wavelength differential on short wavelength side up to background point
DL: Wavelength differential on long wavelength side up to background point
The background point and peak point is measured for each sample.
1Normally, background correction involves measuring background points on each side of the
peak and calculating the background intensity (I B) from these two intensity values, but if the
background is level then the background point from either side can be used as the I B value for
correction (single sided background correction). Whereas normally three emission values (peak
point, background on the short wavelength side, and background on the long wavelength side)
are measured to obtain one measurement value, two points will suffice in this case, allowing the
measurement time to be reduced. To perform this single-sided background correction, set the
background point to zero under “BG correction information” corresponding to the side that is not
measured (-BG or +BG).
Training－49
Chapter 5 Pretreatment Examples and Selecting Equipment

(Accessories) for Different Types of Samples
ICP is generally used for liquid samples. Therefore, samples not already in solution must be
dissolved before they can be analyzed. Furthermore, even samples that are already in solution
may require pretreatment to accommodate coexisting substances (matrix).
1. Processing Room and Equipment

This section describes the facilities, equipment and peripheral devices necessary for pretreating
samples, so they can be measured using ICP. Only the minimum essential equipment is described.
Minor non-essential equipment has been ignored.
2. Processing Room
The environmental requirements for the room where samples are pretreated, such as where
they are decomposed and diluted, depends on the type of elements analyzed and the precision
and concentration levels of the analytical values. Elements abundant in nature, such as Ca, Mg,
Na, Al and Fe are generally contaminants and can cause contamination from nearby industrial
products or testing apparatus, whether to a greater or lesser extent. It is necessary to select the
work room cleanliness level and testing apparatus in accordance with analytical objectives. Also
be careful of cross contamination.
3. Testing Apparatus
ICP systems are analytical instruments designed to measure liquids. Therefore, various
glassware and plasticware is essential. Each of the items listed below are available in multiple
sizes. The type and quantity required depends on the scale of the analysis.
(1) Beakers (glass, quartz and Teflon)
(2) Test tubes (glass, Teflon and PP, etc.)
(3) Volumetric pipettes (glass and Teflon, etc.)
(4) Graduated pipettes (glass and Teflon, etc.)
(5) Micropipettors
(6) Funnels
(7) Filter paper
(8) Other
Always wash any containers or pipettes used to store or measure solutions before using them.
Wash them using detergent, acid and then ultra pure water (in that sequence). Also, even if the
containers are new be sure to wash them using the same process. For trace quantity analysis,
metals contained in the glass can leach out and contaminate samples or trace elements in the
samples can adhere to glass surfaces. Therefore, we recommend using items made from the
following materials for such applications.
Quartz, PMP (Polymethylpentene), PP (Polypropylene), PE (Polyethylene), PFA, PTFE,
TFE, TFE, or FEP (Fluorinated Ethylene Propylene)
Training－50
4. Equipment for Pretreatment

Samples that cannot be analyzed using only dilution or filter techniques, such as solid samples
or liquids that must be analyzed precisely, are measured after acid decomposition. Hotplates,
etc., are used to decompose samples thermally. Other decomposition methods, such as
microwave decomposition (closed systems) are used to reduce the time required for acid
decomposition or to prevent volatilization.
(1) Microwave decomposition system
(2) Hotplate
(3) Electric furnace
(4) Centrifuge
(5) Other
5. Equipment and Reagents for Testing

Hazardous acid vapors are generated when the above decomposition processes are used. A
draft chamber is required to vent these vapors. Ultra pure water and standard reagents for
various elements, which are the most important items for analysis, are also required.
(1) Draft chamber
(2) Ultra pure water generator
(3) Standard solutions (for atomic absorption, etc.), acids and fluxes
(4) Laboratory bench
(5) Storage cabinet (glassware and reagents)
6. Deionized Water
The deionized water used for cleaning, pretreatment, and dilution of standard samples should
be as pure as possible. At a minimum, it should be distilled and deionized water. Various water
purifying systems are available on the market. Regarding water (ultra pure water) purifier
specifications, the larger the purity rating (relative resistance value) the better. The theoretical
maximum value is 18.3 Mohm-cm. The water supply for the purification system must also be
pure. If the public water supply is used as the water source, a filter such as an ion-exchange
resin filter is required before the water enters the water purification system. Ultra pure water is
required not only for preparing samples, but a large quantity is also required for cleaning
containers and other items, so specifications must provide not only purity, but sufficient
capacity. Please consult manufacturers for details.
7. Standard Samples
Standard solutions are prepared by dissolving the target metal elements (99.9% or more) to a
concentration of about 1000 ppm to 1 percent. Use polyethylene or Teflon containers for
storage. Standard solutions of metals (single element solutions for atomic absorption, multiple
element ICP mixtures, etc.) are available commercially from reagent manufacturers. These are
mixed and diluted appropriately to prepare standard analytical solutions (calibration curve
sample solutions) as required. Acids or internal standard elements can be added at that point,
as necessary.
Training－51
ICP emission spectroscopy analyzes multiple elements simultaneously, so normally standard

mixture solutions containing multiple elements are used. Therefore, when mixing the solutions,
make sure the solution is mixed correctly and has the proper pH level. Also, when mixing
solutions of differing elements, constituents could form precipitates or adsorb to the container.
As a reference, Table 5-1 lists examples of commercially available single element standard
solution. The shelf life of standard solutions prepared in this way will vary depending on the
storage container used, the concentrations of the elements contained in the standard solution,
the concentration of acids, and the storage method. Careful consideration of these factors is
necessary. Periodically use standard solutions from a different source to verify the samples for
maintenance and control purposes.
Table 5-1 Acids, chlorides, etc., that could be coexistent in

commercial 1000 ppm standard solutions (reference)
Coexisting Coexistent Coexisting Coexistent
Element elements Element elements
acids / alkalis acids / alkalis
Ag Nitric acid Na
Al Nitric acid Nb Fluoric acid
As Hydrochloric acid Na Nd Hydrochloric acid
Au Hydrochloric acid or Nitric acid Ni Nitric acid
B P KHPO4 K
Ba Hydrochloric acid or Nitric acid Pb Nitric acid
Be Nitric acid Pd Hydrochloric acid or Nitric acid
Bi Nitric acid Pr Hydrochloric acid or Nitric acid
Ca Nitric acid Pt Hydrochloric acid or Nitric acid
Cd Nitric acid Rh Nitric acid
Ce Nitric acid Ru Hydrochloric acid
Co Nitric acid S Nitric acid
Cr Nitric acid K Sb Hydrochloric acid
Cu Nitric acid Sc Hydrochloric acid or Nitric acid
Dy Hydrochloric acid or Nitric acid Se Nitric acid
Er Hydrochloric acid or Nitric acid Si NaCO3 acid or KOH Na, K
Eu Hydrochloric acid or Nitric acid Sm Hydrochloric acid or Nitric acid
Fe Nitric acid Sn Hydrochloric acid
Ga Nitric acid Sr Nitric acid
Gd Hydrochloric acid or Nitric acid Ta Fluoric acid
Ge KOH K Tb Hydrochloric acid or Nitric acid
Hg Nitric acid Te Hydrochloric acid
Ho Hydrochloric acid Ti Sulfuric acid S
In Nitric acid Tl Nitric acid
Ir Nitric acid Tm Hydrochloric acid or Nitric acid
K Nitric acid V Sulfuric acid or Ammonia S
La Nitric acid W Na
Li Hydrochloric acid Y Hydrochloric acid or Nitric acid
Lu Nitric acid Yb Hydrochloric acid or Nitric acid
Mg Nitric acid Zn Nitric acid
Mn Nitric acid Zr Nitric acid
Mo Ammonia
Training－52
8. Acids and Alkalis

Samples are generally decomposed or dissolved using a single acid or alkali or sometimes a
combination. These are commercially available in grades, such as special grade, for precision
analysis, and for measurement of hazardous metals. When measurement concentrations are
trace amounts or when using large quantities of acid for decomposition, use the purest acid
possible. Some examples include the hazardous metal analysis grade from Wako Pure
Chemical Industries, the Suprapur and Ultrapur brand high purity grades from Kanto Kagaku,
or Tamapure-AA-100 from Tama Chemicals.
• Hydrochloric acid
Used alone or in combination with other acids to dissolve metals such as Zn, Cd, Fe, Mn or
Sn or their oxides. This is a reducing agent so it is not suited for decomposition of organic
substances. Also, it becomes a volatile chloride with As, Sb, S, Sn, Se, Ge or Hg, so
volatilization will occur easily if heated.
• Nitric acid
A strong oxidizer, nitric acid is used to dissolve various metals and decompose various
organic substances. It is not very effective for decomposing oxides or carbides of Fe, Al or
Mn, or lipids. For these types of applications, it is used in combination with other acids,
such as sulfuric acid, perchloric acid, or aqueous hydrogen peroxide.
• Perchloric acid
An extremely strong oxidizer when heated, perchloric acid is used to decompose samples
containing organic substances. However, when used alone perchloric acid reacts
explosively with organic substances, so for samples containing large amounts of organic
substances, always initially digest samples with nitric acid alone or in combination with
perchloric acid before using perchloric acid by itself.
• Hydrogen peroxide
A strong oxidizer, it is used in place of perchloric acid to decompose organic and other
substances in combination with acids such as nitric acid.
• Sulfuric acid
Sulfuric acid is used as an oxidizing agent in combination with nitric acid or other acids to
decompose samples containing organic substances or geological matter. Dilute sulfuric
acid is capable of dissolving many metals, but they dissolve poorly with concentrated
sulfuric acid. Heated concentrated sulfuric acid is a strong oxidizer and will dissolve even
metals like Cu and Ag. In addition, concentrated sulfuric acid is hygroscopic and is a
desiccant, so it is often added to prevent drying during wet ashing or to prevent
volatilization of metals. However, the sulfides of Ag, As, Ge, Hg, Re and Se are easily
volatilized when heated and produce insoluble sulfates in the presence of Pb, Ca, Ba or Sr.
• Hydrofluoric acid
Hydrofluoric acid does not affect Pt or Au and attacks only the surface of Pb, but dissolves
all other elements. In particular, it dissolves silicon dioxide and silicates, so it is used to
completely decompose samples containing large amounts of silicates, such as minerals,
soils, sediments, dust or ceramics. Fluorides are produced with B, Si, As or Sb and are
easily volatilized when heated. In the presence of large amounts of Ca or K it produces
insoluble fluorites.
• Aqua regia
Aqua regia is used to decompose metals such as Au, Pt or Pd, or metal alloys such as
solder.
Training－53
9. Decomposition methods
Solid or liquid samples that cannot be analyzed using dilution and filtering processes must be
decomposed using a suitable method and converted to solution. The following decomposition
methods are available.
10. Dry Ashing

This method involves heating samples in an electric furnace at approximately 400 to 550 C in
the presence of air to remove organic substances. Characteristics include allowing
decomposition in a short time (several hours), processing multiple samples simultaneously,
using the minimum quantity of reagent required for dissolving the sample, and being easy to
operate. However, samples are decomposed using high temperatures, so there is a possibility
that elements with low boiling points, such as Hg, As, Se, Cr, B, Pb, Zn, Cd, In, Te and Sb, will
volatilize.
11. Wet Decomposition

This method involves placing samples in a beaker or flask with acid and heating them on a
hotplate (up to 300C). It is effective for both organic and inorganic substances. Decomposition
is accomplished at a low temperature, so it can be used to pretreat elements that are volatilized
easily, but it requires a long time to decompose organic substances (from a few hours to several
days). Therefore, care must be taken to prevent contamination from acids or the operating
environment, such as from the container or atmosphere. Furthermore, care must also be taken
to prevent element losses to adsorption on container surfaces or volatilization.
12. High Pressure Decomposition

This method involves placing the sample and acid in a sealed Teflon container, heating it to
roughly 150C, and decomposing the sample under high pressure. Lately it has been gaining
attention as a method for decomposing environmental samples, such as sediments, soils or
dust, and biological or food samples. Several companies are marketing digestion systems that
combine microwave with high pressure containers. Decomposition occurs in a sealed container,
which allows avoiding volatilization of elements with low boiling points. Other benefits include
minimal contamination from the operating environment, rapid decomposition times, and also low
contamination from acids because less acid is used. The method is especially useful when
analytical elements are present in trace quantities or only a small amount of sample is available.
13. Melting
This method is used to decompose samples that don’t decompose easily using only thermal
decomposition and acids, such as silicates, several oxides of chlorine, or metal alloys. Samples
are mixed with several times their quantity of basic melting agents and melted at high
temperatures (400 to 1000C). Adding large quantities of melting agents makes this method
vulnerable to contamination, so it is generally not suited to trace quantity analysis. In addition,
when the chlorine content in samples becomes too high, it can cause the torch and delivery
systems to become clogged easily.
All the decomposition methods require verifying contamination using a laboratory reagent blank
and performing a spike check to confirm the pretreatment process was effective.
14. Examples of Pretreatment and Equipment (Accessories) Selection for Different Sample
Types
Training－54
15. Analyzing Water Quality

ICP spectrometry seems most suited to the analysis of water quality samples. Certainly, it would
appear that hardly any pretreatment is required and analysis can be performed without any
additional preparation. However, in actuality, analytical elements are often present only in trace
or ultra trace concentrations, making water one of the most difficult things to analyze.
・Test methods
JIS K0101 Test method for industrial water
JIS K0102 Testing methods for industrial wastewater
JIS M0201 Testing method for effluents from coal preparation plant
Testing method for public waterworks
Testing method for environmental water
Testing method for wastewater
・Standards and regulations

Water Pollution Control Law
Water Supply Law
16. Seawater
Even when analyzing unaltered seawater, a water bubbler and high-salinity torch must be used
due to high salt concentrations. Considering the large quantities of salt contained in samples,
matrix matching or standard addition methods must be used. When measuring trace elements,
solvent extraction and sample concentration techniques are required. The extraction solvent
used in JIS K0102 “Testing methods for industrial wastewater” is xylene. This solvent allows
measurements using a standard torch. Depending on the type of solvent, a torch for organic
solvents may be necessary. A hydride generator can be used to measure elements like As, Se
or Sb with high sensitivity. However, depending on the matrix, interference must be
considered. An AX-1 axial observation system allows highly sensitive measurements. An
ultrasonic nebulizer may cause salt precipitation.
17. Water from Rivers and Lakes

Analysis often involves trace quantities, so sample concentration and solvent extraction
techniques are necessary. A hydride generator can be used to measure elements like As, Se
or Sb with high sensitivity. However, depending on the matrix, interference must be
considered. An AX-1 axial observation system or ultrasonic nebulizer allows highly sensitive
measurements. In addition, seawater may enter samples in locations near the ocean, so the
same precautions are required as for seawater.
18. Ground Water and Hot Springs

Typical ground water presents no problems. Select accessories (ultrasonic nebulizer, hydride
generator, axial observation system, etc.) appropriate for the concentration levels of the
elements being analyzed. On the other hand, hot springs often have high salt concentrations.
Precautions for seawater need to be taken.
19. Rain Water

Select pretreatment techniques and accessories appropriate for the concentration levels of the
analyzed elements.
Training－55
20. Effluent
The matrix for effluent water can vary greatly depending on the factory and where the effluent
is discharged. Samples can contain large amounts of specific elements or sometimes they
even contain oils. Pretreatment and accessory requirements are the same as for other water
quality samples described above, but special attention needs to be given to preparing the
standard samples.
21. Public Water System and Untreated Drinking Water

The Japanese Water Supply Law specifies the elements that may be analyzed using ICP.
Except for Na, these water samples often contain only trace quantities of elements, so an
ultrasonic nebulizer is required for directly analyzing the water. Higher sensitivity
measurements are possible using an axial observation system.
22. Metals and Industrial Materials

Most of the samples covered in this section can be thought of as solids. Even oil, which is
mentioned last, contains wear metal after it has been used. When using ICP then, the samples
must first be dissolved. Recently, materials have become more resistant to chemicals and the
analyzed amounts have become extremely small. For this reason, there have been cases where
analysis with ICP is not possible using simple procedures. As with the water-quality samples
mentioned previously, selection of the pretreatment method and selection of the standard
samples are important considerations.
23. Steel
Usually, a sample of 0.5 to 1 g is thermally decomposed using mixed acid, an appropriate
internal standard element is added, and this mixture is diluted to a volume of 100 to 200 ml.
Depending on the type of acid, there may be elements that sublime or precipitate. Alkali fusion
is necessary if an insoluble residue is created. If alkali fusion is used, the concentration of the
alkali metal elements in the solution increases and so a water bubbler and a high-salinity torch
are required. Also, be careful about the matrix matching of standard samples.
With the quantitative analysis of trace elements, there are cases where spectral interference of
the main constituent, iron, can be a problem. Sensitivity may also be insufficient. In this case,
the iron is separated using the solvent extraction method (in particular, MIBK extraction). This
method makes it possible to remove the iron interference and increase the concentration at
the same time. If MIBK is used as the solvent, there is no particular problem but in other
cases, depending on the type of solvent, a torch for organic solvents may be used.
Alkali fusion is used to create solutions of iron ore and slag. As with the processing of the
insoluble residue mentioned previously, steps for dealing with alkaline salt in the solution are
required.
24. Nonferrous Metals

The pretreatment method for nonferrous metals is basically the same as that used for steel.
Hydrofluoric acid is used with some elements, such as titanium, niobium, tungsten, and their
alloys. In processing, the hydrofluoric acid can be masked with boric acid or removed by
evaporation; sometimes an HF-resistant sample-introduction system is used.
25. Ceramics
The oxides and nitrides referred to as "ceramics" have, for some time, been used as
refractories and china. Recently, many different types of ceramics, such as fine ceramics and
new ceramics, have been developed for use in special applications.
Training－56
There are many samples in this category that are difficult to render as solutions, and are
consequently difficult to analyze. In open systems, there are many samples that are difficult to
dissolve, even using hydrofluoric acid, and pressure decomposition using a high-pressure
vessel or alkali fusion are employed.
26. Oil
Samples with a high viscosity, such as lubricating oil or heavy oil, cannot be introduced directly
into the ICP as they are. Therefore, they are diluted using an organic solvent, such as xylene,
MIBK, or kerosene, to reduce the viscosity before being analyzed. In standard systems,
xylene, MIBK, and kerosene can be introduced into the ICP. There are samples, such as some
types of grease, that can only be dissolved in solvents such as cyclohexane and THF. In this
case, after dilution with kerosene, a torch for organic solvents is used.
Also, in order to facilitate speedier engine management, demand for the analysis of used
lubricating oil has increased. A typical sample contains wear metals of various sizes and so,
unlike unused oil, simply diluting the samples, is insufficient for comprehensive analysis. This
is because it is difficult to introduce metal powders of varying particle sizes evenly into ICP. If,
hypothetically, the particle size were uniform, it would be possible to perform trend analysis. In
order to perform a comprehensive analysis, it is necessary to perform acid decomposition and
create an even solution.
27. Geochemical Samples

Some examples of geochemical samples are rock, bottom sediment, soil, coal, and fly ash. They
can basically be thought of as oxides and so, as with ceramics, methods such as hydrofluoric-
acid decomposition, pressure decomposition, and alkali fusion are used for pretreatment. A wide
variety of elements are analyzed for a wide range of purposes. The pretreatment method
suitable for the purpose must be used along with an HF-resistant sample-introduction system, a
water bubbler, or a high-salinity torch, whichever is appropriate.
28. Biological Samples

Biological samples can be classified as solid samples, such as organs and hair, or liquid
samples, such as blood and urine.
Nitric acid and perchloric acid are used for solid samples. Liquid samples are usually too viscous
to be used as they are and so they are diluted, for example, with distilled water.
Samples that have been rendered as solutions can be analyzed as they are but there are many
cases where the matrix is complex and care is required with the creation of standard samples.
29. Serums, Blood, and Blood Cells

These types of sample all have high viscosity and, although they are solutions, they cannot be
introduced into the ICP as they are. Serums need to be diluted by a factor of approximately 5
to 10 and blood needs to be diluted by a factor of approximately 10. Dilution is performed with
dilute nitric acid (1% nitric acid). If concentrated nitric acid is added, the protein in the sample
coagulates and precipitates. Elements for which the sensitivity is insufficient with the dilution
method are decomposed with nitric or perchloric acid before measurement.
There are usually large amounts of alkali metals in blood and there are also alkali metals in the
anticoagulant added when taking blood samples and so care must be taken regarding
interference.
30. Urine
Urine can basically be analyzed as it is. Depending on the conditions under which the urine
Training－57
sample is obtained, however, there are many cases where the constituents are not at constant
levels. In particular, fluctuations in the alkali-metal concentration can influence the nature of
the interference and so care is required. In order to eliminate this influence, urine is collected
over a 24-hour period. In this case, however, preservative is sometimes used and so the
influence of this preservative must be considered.
31. Hair
Hair is often used to check for contamination with heavy metals and to investigate the physical
condition. Naturally, to perform measurement with ICP, the hair must be rendered as a
solution. Decomposition using, for example, nitric or perchloric acid is also possible. The
content of the hair can also be affected by hair gel, shampoo, and perms. Also, elements may
be lost by rinsing after sampling and so processing must always be performed with an
established method.
32. Organs
There is a high fat content and performing wet ashing with acid in an open system can result in
the consumption of a large amount of acid over a long period. This can cause contamination of
the sample. Therefore, after carrying out dry ashing at a low temperature, the amount of acid
and the decomposition time is reduced by performing acid decomposition using a microwave
and a high-pressure vessel.
33. Food Products

As with biological samples, solid samples of food products must be rendered as solutions.
Interference due to coexisting substances must also be considered when dealing with liquid
samples, such as alcoholic beverages or juice.
34. Animal Food Products

As with biological samples, the fat content can hamper the decomposition of meat, seafood,
and food products containing them. Using dry ashing or high-frequency waves can be
effective. It is also important to consider the possibility of contamination from the tool used to
obtain the sample. For example, the constituent elements may be contaminated if a stainless-
steel knife is used. The effectiveness of using other tools, such as ceramic knives, is being
considered.
35. Vegetable Food Products

Cereals, pulse products, and mushrooms are dissolved with nitric acid. These food products
contain large amounts of silicon and germanium and so decomposition with hydrofluoric acid
or alkalis can also be used as well.
Vegetable oils are, in the way described for oil in 3.2.4, diluted with organic solvent in order to
reduce the sample viscosity before being analyzed.
36. Alcoholic Beverages

Whiskey, for example, contains hardly any elements to be analyzed. Sake, beer, and wine,
however, are analyzed for the presence of a wide range of elements. All of these beverages
contain alcohol and so care is required with the creation of standard samples. The standard
addition method is often used. Although these beverages contain ethanol, which acts as an
organic solvent, a torch for organic solvents is not required.
The samples can be analyzed as they are but effervescent beverages, such as beer, must be
degassed. Alkali decomposition can also be used to eliminate the influence of alcohol and
coexisting substances.
Training－58
37. Soft Drinks

High viscosity due to the sugar content can be a problem. This can be alleviated by diluting
with water or using a high-salinity torch.
Training－59
Table 5-5 Official Methods Using ICP Emission Spectrometry (Reference)

Official Methods
K0101-98 Testing methods for industrial water
K0102-98 Testing methods for industrial wastewater
K0116-95 General rules for atomic emission spectrometry
K0553-95 Testing methods for determination of metallic elements in highly purified water
K9901-94 Highly purified nitric acid
K9902-94 Highly purified hydrochloric acid
K9903-94 Highly purified ammonia solution
K9904-94 Highly purified perchloric acid
H1055-96 Methods for determination of manganese in copper and copper alloys
H1062-89 Methods for determination of zinc in copper and copper alloys
H1063-89 Methods for determination of beryllium in copper alloys
H1101-90 Methods for chemical analysis of electrolytic cathode copper
H1108-89 Methods for determination of lead in zinc metal
H1109-89 Methods for determination of iron in zinc metal
H1110-89 Methods for determination of cadmium in zinc metal
H1111-89 Methods for determination of tin in zinc metal
H1181-96 Methods for chemical analysis of silver bullion
H1161-91 Methods for chemical analysis of cadmium metal
H1191-91 Methods for chemical analysis of gallium arsenide
H1282-88 Methods for determination of tungsten in nickel alloys
Methods for inductively coupled plasma emission spectrometric analysis of aluminium
H1307-93
and aluminium alloys
H1621-92 Methods for determination of palladium in titanium alloys
H1650-88 General rules for chemical analysis of zirconium and zirconium alloys
H1667 Method for determination of hafnium in zirconium and zirconium alloys
H1661 Methods for determination of aluminium in zirconium and zirconium alloys
H1654-89 Methods for determination of iron in zirconium and zirconium alloys
H1655-89 Methods for determination of nickel in zirconium and zirconium alloys
H1656-89 Methods for determination of chromium in zirconium and zirconium alloys
H1659-89 Methods for determination of tin in zirconium alloys
M0202-87 Testing methods for mine water and/or waste water
M8126-94 Ores – Methods for determination of nickel
M8134-94 Ores – Methods for determination of selenium
B8224-93 Boiler feed water and boiler water – Testing methods
Iron and steel – Methods for inductively coupled plasma atomic emission
G1258-89
spectrometry
Environment Agency Notice No. 59 (environmental quality standards for water quality)
Environment Agency Notice No. 64 (testing methods for wastewater standards specified by the
Direction-General of the Environment Agency)
Methods for testing the water supply in accordance with the Water Works Law (2001)
Hygiene testing methods (2000)
Training－60
Appendix 1 Analysis of Organic Solvents with ICP (ICPS-7500/8100)
1. Points to Note Regarding Organic-solvent Samples

2. Plasma Ignition (Example)
The target solvent (e.g., xylene) is
Bright part at
プラズマの中心の
introduced and the plasma is ignited
Plasma center
明るい部分 of plasma
in organic-solvent ignition mode. プラズマ
After plasma ignition, the carrier-
gas flow rate is set at the meter 高周波コイル Top side of
プラズマト－チの
High-frequency coil plasma torch
display screen. This carrier-gas flow 上端
rate varies with the type of solvent
introduced and the sample viscosity.
The carrier-gas flow rate is set so
that the bright part in the center of
the plasma is roughly the same
height as the plasma torch, or is
slightly higher (See Fig. 1).
The carrier-gas flow rate for xylene
is 0.7 to 0.8 L/min.
To perform accurate quantitative Appendix Fig. 1 Plasma
analysis, the plasma must be stable
for at least 30 minutes. After stabilization, the carrier-gas flow rate is checked. Also, the initial
analysis conditions for the analysis group are set for aqueous solutions and so the conditions are
changed to those for organic solvents (Refer to "2. Plasma Conditions").
3. Standard Samples
CONOSTAN is often used as a standard sample. (Sold by Seishin Trading Co., Ltd.; TEL: +81-3-
3459-7491; FAX: +81-3-3459-7499.) This is a standard sample for lubricating oil and is diluted
with xylene, MIBK, or kerosene before use. Because this standard sample is for lubricating oil, it
has a high viscosity. For this reason, it may be necessary to either make the viscosities for the
analyzed sample and the standard sample the same or to use internal standard correction. If the
analyzed element is present at a high concentration, the influence of viscosity can be reduced by
using a large dilution factor (100 or higher).
Other standard samples include oil-soluble organic-metal standard samples, which are sold by
Wako Pure Chemical Industries and Kanto Kagaku. The concentration must be carefully
controlled, however, after dissolution.
Also, solvents such as NMP (N-methyl-2-pyrrolidone) and DMA (N-N dimethylacetamide) are
hydrated and aqueous-solution standard samples can be added. Wako Pure Chemical
Industries, Kanto Kagaku, and other companies sell 1,000-ppm solutions of single elements as
standard reagents for atomic absorption and multiple-element mixtures as standard reagents for
ICP. With organic metals (analyzed samples) and inorganic samples (standard samples),
however, there are differences in the introduction efficiencies and excitation efficiencies, and
errors may occur in measurements. Give consideration to the measurement method (e.g.,
ashing) beforehand.
Training－61
4. Plasma Conditions
Table 1 shows typical conditions used for ICP. As mentioned previously, the ideal conditions (e.g.,
the carrier-gas flow rate) for introducing an organic solvent may vary with the type of solvent.
Appendix Table 1-1 Example of Plasma Conditions for Organic-solvent Analysis
Solvent Water Ethanol Xylene MIBK NMP

Condition
High-frequency
1.2 1.4 1.4 1.4 1.4
output (kW)
Coolant-gas flow
14 16 16 16 16
rate (L/min)
Plasma-gas flow rate
1.2 1.4 1.4 1.4 1.4
(L/min)
Carrier-gas flow rate
0.7 0.9 0.7 0.7 0.8
(L/min)
Chamber Cyclone Double tube Double tube Double tube Double tube
Torch Standard Standard Standard Standard Standard
Nebulizer 07,10 ＊
10 ＊
10 ＊
10 ＊
10
Transverse/
Observation method Transverse Transverse Transverse Transverse
axial
Notes:
＊
10: A 23 nebulizer is sometimes used.
The tube used to connect the sample tube and the nebulizer must be changed when analyzing
NMP or DMA.
The values given in the table are reference values. These may vary slightly depending on the
equipment used, the analyzed elements, the introduction system, and the type of solvent.
Identifying the Optimum Conditions

Usually, the carrier-gas flow rate, the high-frequency output, and the torch observation height
are set so as to optimize the plasma stability (e.g., ignition, matching, and brightness) and the
sensitivity (BEC) for the target elements. With organic-solvent samples, the carrier-gas flow rate
has a large influence on the sensitivity. If the rate at which the sample is introduced is
increased, the sensitivity increases and so the carrier-gas flow rate is increased. If it is
increased too much, however, the top of the bright part at the center of the plasma (the horn)
mentioned previously becomes too high. The background light for this part is very intense and
so the sensitivity is very poor here. Therefore, the carrier-gas flow rate is adjusted so that this
part is not measured.
If the analyzed sample has a high viscosity, the state of the plasma differs from the state when
only the solvent is used for cleaning. For this reason, use the analyzed sample or a sample very
similar to it when considering the analysis conditions.
Training－62
Appendix Table 1-2 ICP-compatibility of Various Organic Solvents

Vapor
Boiling point Introduction into
Compound pressure
(ºC) ICP
(mmHg)
Methanol 64.7 99 O
Ethanol 78.3 120 
n-propyl alcohol 97.5 15 
Isopropyl alcohol (IPA) 82.4 33 
n-butyl alcohol 117.5 4 
n-hexyl alcohol 157 3 
Ethyl acetate 77.1 74 O
n-butyl acetate 126.3 10 
Isobutyl acetate 118 13 
Amyl acetate 148.8 
Isoamyl acetate 142 4 
Acetone 56.3 175 
Dichloromethane 40 349 O
1,2-dichloroethane 83 64 O
Methyl isobutyl ketone (MIBK) 117 5 
Diisopropyl ketone 125 3 
Diisobutyl ketone (DIBK) 168 2 
Acetylacetone 140.5 
Acetic acid 117.8 12 
Proprionic acid 141 2.8 
n-butyl cellosolve 171.2 
Chloroform 61.2 160 
Carbon tetrachloride 76.7 90 
o-dichlorobenzene 180 1 
Toluene 110.6 21 O
Xylene 138 to 144 4 
Nitrobenzene 210.9 <1 
Aniline 184.6 <1 
Pyridine 115.5 15 
Acetonitrile 81.6 70 
Benzyl alcohol 205.4 <1 
Tributyl phosphate 289 
Dimethyl sulfoxide (DMSO) 189 0.4 
n-methyl-2-pyridone (NMP) 202 
N,N-dimethylacetamide (DMA) 165.5 
Gasoline 35 to 200 
Kerosene 150 to 300 
Light oil 220 to 350 
Naphtha 
 Introduction possible with standard torch and double-tube chamber.

O Introduction possible with torch for organic solvents and double-tube chamber.
 Introduction possible with torch for organic solvents and double-tube chamber
(cooled to 10ºC max.)
Training－63
5. Example: Creating Oil Samples

6. Analyzed Sample
In order to reduce the viscosity of the analyzed sample, it is diluted with xylene by a factor of 10
to 20. Dilution can be performed with either a volumetric method or a gravimetric method. Here,
dilution by a factor of 20 with a gravimetric method is used as an example.
7. Calibration-curve Samples
Either standard solutions of CONOSTAN S-21 are prepared at each concentration (500 ppm and
200 ppm) or high-concentration (e.g., 500-ppm or 900-ppm) standard solutions are diluted with
blank oil. As for sulfur, a Japan Petroleum Institute standard sample of heavy oil with a 4.26%
sulfur content is adjusted by diluting with blank oil. If the viscosities of the standard samples are
considerably higher than that of the analyzed sample, dilution is performed using xylene instead
of blank oil. After adjustment of the concentration, the standard samples are diluted with xylene
in the same way as the analyzed sample, and used to create a calibration curve.
Appendix Table 1-3 Calibration-curve Samples
Sample STD-0 STD-1 STD-2 STD-3 STD-4

Element
B, Na, Mg, Al
Si, P, Ca, Cr
0 250 500
Fe, Ni, Cu, Zn - -
(0) (12.5) (25)
Mo, Ag, Sn, Ba,
Pb
2,000 4,000
S - - -
(100) (200)
Unit: ppm
Figures in parentheses indicate the concentration in the diluted solution (ppm)
8. Examples of Methods for Creating Analyzed Samples and Calibration-curve Samples

(1) Reagents and Equipment
• CONOSTAN S-21 (500-ppm oil standard sample containing a mixture of 21 elements)
Elements contained: Ag, Al, B, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Mo, Na, Ni, P, Pb, Si, Sn,
Ti, V, Zn
• CONOSTAN Base Oil
• Heavy oil standard sample with 4.26% sulfur content (certified by Japan Petroleum
Institute; produced by Tokyo Kasei)
• High-grade xylene
• Electronic balance (capable of measurement at the mg level)
• Flasks (50 ml, 100 ml, etc.)
• Komagome pipettes (2 ml, 5 ml, 10 ml, 20 ml, etc.)
(2) Cleaning
After oil is removed from the flasks and pipettes with detergent, they are cleaned with acid
and pure water. After cleaning, they are dried thoroughly in a dryer.
(3) Creation of Analyzed Samples
Training－64
The analyzed sample is stirred well and then 2 g (accurate to the nearest mg) of the sample
is measured out in a 50-ml flask. Xylene is carefully added to the flask so that the total
weight is 20 times that of the original sample. (2.000 g -> 40.000 g)
(4) Creation of Calibration-curve Samples
If standard solutions can be prepared at each concentration, the samples are carefully
diluted by a factor of 20, as with the analyzed sample, to create calibration-curve samples. If
high-concentration solutions are to be diluted for use, after the concentration is adjusted with
blank oil, the samples are carefully diluted by a factor of 20, as with the analyzed sample, to
create calibration-curve samples.
In practice, however, because dilution of the standard samples and dilution with xylene is
carried out at the same time, using the following kind of procedure can result in greater work
efficiency and dilution accuracy.
Example) Calibration-curve samples are created for elements other than sulfur by diluting
CONOSTAN S-21 (500 ppm) sample oil with CONOSTAN Base Oil and xylene. Calibration-
curve samples are created for sulfur by diluting a heavy oil standard sample with 4.26%
sulfur content in the same way.
 Creation of STD-2
The CONOSTAN S-21 (500 ppm) is stirred well and then 2 g (accurate to the nearest mg) of
the standard sample is measured out in a 50-ml flask. Xylene is carefully added to the flask
so that the total weight is 20 times that of the original sample. (2.000 g -> 40.000 g)
The CONOSTAN S-21 (500 ppm) is stirred well and then 1 g (accurate to the nearest mg) of
the standard sample is measured out in a 50-ml flask. The same amount (1.0 g) of
CONOSTAN Base Oil is then added. Xylene is carefully added to the flask so that the total
weight is 40 times that of the original sample (1.000 g). (1.000 g -> 40.000 g)
2.0 g of CONOSTAN Base Oil is measured out into a 50-ml flask. Xylene is added so that
the weight is 40 g.
 Creation of 2,000-ppm Sulfur Solution

The heavy oil standard sample with sulfur content (sulfur concentration: 4.26%) is stirred
well and 1 g (accurate to the nearest mg) is measured out into a 50-ml flask. Xylene is
carefully added to the flask so that the total weight is 21.3 times that of the original sample.
(1.000 g -> 21.30 g)
The 2,000-ppm sulfur solution is stirred well and 4 g (accurate to the nearest mg) is
measured out into a 50-ml flask. 1.812 g (=2g − 4g / 21.3) of CONOSTAN Base Oil is
added. Xylene is carefully added to the flask so that the total weight is 10 times that of the
original sample (4.000 g). (4.000 g -> 40.000 g)
The 2,000-ppm sulfur solution is stirred well and 2 g (accurate to the nearest mg) is
measured out into a 50-ml flask. 1.91 g (=2g − 2g / 21.3) of CONOSTAN Base Oil is added.
Xylene is carefully added to the flask so that the total weight is 20 times that of the original
sample (2.000 g). (2.000 g -> 40.000 g)
Training－65
Appendix 2 Analysis Using the Hydride-generation Method
1. Plasma Conditions
Examples of the conditions used with the hydride-generation method are given below. The
conditions vary somewhat with the model and observation method.
Appendix Table 2-1 Measurement Conditions for ICPS-7500

System: ICPS-7500
Plasma light source:Inductively coupled plasma
Frequency : 27.120 MHz
Output : 1.2 kW
Reflected waves : 0 W
Coolant-gas flow rate : 14.0 L/min
Plasma-gas flow rate : 1.2 L/min
Carrier-gas flow rate : 0.9 L/min
Purge-gas flow rate : 0.2 L/min
Light-source
: Axial direction
measurement direction
Sample introduction system
Sample take-up volume : 2 to 5 mL/min

: (Dial: 2 to 3)
Maximum suction with
Drainage :
peristaltic pump
Solvent rinse time : 30 s

Sample rinse time : 80 s
Torch : Standard torch
Measurement
Integration time : 10 s × 2
Peak mode : Direct mode
Typical Sensitivities
Element Wavelength (nm) BEC 3
As 189.0 1.5 0.15

Se 196.0 2.0 0.2
Sb 206.8 2.0 0.2
Unit: µg/l
Training－66
Appendix Table 2-2 Measurement Conditions for ICPS-7000

System:ICPS-7000
Plasma light source:Inductively coupled plasma
Frequency ： 40.68 MHz
Output ： 0.8 kW
Reflected waves ： 0 W
Coolant-gas flow rate ： 14.0 L/min
Plasma-gas flow rate ： 0.65 L/min
Carrier-gas flow rate ： 0.45 L/min
Purge-gas flow rate ： 1.5 L/min
Light-source
： Axial direction
measurement direction
Sample introduction system
Sample take-up volume ： 2 to 5 mL/min

： (Dial: 2 to 3)
Maximum suction with

Drainage ：
peristaltic pump
Solvent rinse time ： 30 s

Sample rinse time ： 80 s
Torch ： Minitorch
Measurement
Integration time ： 10 s × 2
Peak mode ： Direct mode
Typical Sensitivities
Element Wavelength (nm) BEC 3
As 189.0 3.0 0.2

Se 196.0 5.0 0.3
Sb 206.8 5.0 0.3
Unit: µg/l
Training－67
2. Points to Note Regarding Analysis Using the Hydride-generation Method

3. Pre-reduction
The elements in environmental samples coexist in chemical forms (ions) with different states of
oxidation. In the hydride-generation reaction, however, arsenic and antimony are used in the
trivalent form and selenium is used in the tetravalent form. This means that pre-reduction, where
the form of pentavalent arsenic and antimony is changed to trivalent and the form of hexavalent
selenium is changed to tetravalent, must be performed beforehand. The reaction also depends
on the type of acid and so matching of the concentrations and types of acid (basically
hydrochloric acid) in the sample is required.
4. Interference due to Co-existing Substances

If organic substances co-exist within the sample, they can hamper the hydride-generation
reaction and so they must be thoroughly decomposed in the pretreatment process. Also, if large
amounts of transition metals co-exist within the sample, they too can hamper the reaction, and
solid matter may be precipitated in the introduction system. Care is therefore required.
5. Introduction System
The liquid level in the gas-liquid separator is always kept constant. Care is also required
regarding the balance of the peristaltic pump for supplying samples and reagents and the
peristaltic pump for draining the system.
6. Rinse Time
Mercury is prone to contamination and so an upper limit of a few ppb is used for standard
samples. A long rinse time is also set. (Solvent rinse time: 30 s min.; Sample rinse time: 80 s
min.)
7. Chemical Forms of Arsenic

Inorganic arsenic can exist in trivalent and pentavalent forms. These are the two most common
forms present in environmental water; organic arsenic is also present in some cases. In order to
decompose this organic arsenic and the co-existing organic substances, nitric acid is added to
the sample (hydrogen peroxide is not required when analyzing mains water or river water) and
thermal decomposition is performed. In this decomposition process, arsenic is converted to its
pentavalent form. As the trivalent form of arsenic is used in the hydride-generation reaction,
however, reduction is performed by adding potassium iodide, thereby unifying to the trivalent
form. This reduction process cannot be carried out successfully if there is still some nitric acid
present and so the sample must be heated until it is almost dry in order to evaporate the nitric
acid. This process of unifying the form of the arsenic to trivalent is referred to as "pre-reduction".
This technique is usually employed in the analysis of environmental water in order to measure
the total amount of arsenic.
On the other hand, commercial standard solutions of arsenic intended for use in atomic
absorption are all in the trivalent form. For this reason, they can be used as calibration samples
without performing pre-reduction. Measurement using a coaxial nebulizer does not depend on
the form of the arsenic and so no particular pretreatment is necessary. Measurement may be
difficult, however, in terms of sensitivity and so care is required.
In cases where separate measurement of each form of arsenic is required, analysis can be
performed by connecting a liquid chromatography system before the ICP stage.
Training－68
8. Examples of Analysis Using the Hydride-generation Method

9. Influent
10. Pretreatment for Analysis of Arsenic and Antimony

(1) 100 ml of the sample is put into a 300-ml glass beaker, 5 ml of nitric acid is added, and this
is concentrated by heating it on a hot plate (approx. 190ºC) until the volume of the solution
is between 10 and 15 ml.
(2) After cooling, 10 ml of nitric acid and 5 ml of hydrogen peroxide water is added, the beaker
is covered with a watch glass and heated (190ºC max.), and the solution is allowed to
evaporate until it is nearly dry.
(3) Step (2) is repeated until all of the organic substances in the sample have been
decomposed.
(4) After cooling, 25 ml of nitric acid (1+1) is added, the beaker is covered with a watch glass,
and heated for approximately one hour (190ºC max.)
(5) After cooling, the total volume is filtered with type-5B filter paper. The residue in the filter
paper is rinsed with warm nitric acid (1+10).
(6) The filtrate is once again heated (190ºC max.) in a 300-ml glass beaker covered with a watch
glass until it is almost dry (until the volume of the liquid is reduced to a few ml).
(7) After cooling, 10 ml of pure water is added, and the solution is heated (approx. 190ºC) until
it is almost dry (until the volume of the liquid is reduced to a few ml).
(8) After cooling, 20 ml of hydrochloric acid (1+1) and 5 ml of potassium iodide (20wt%/V) is
added, the temperature in the beaker is gradually increased to 70ºC, and heating is
continued for approximately 4 minutes.
(9) After cooling, the volume is standardized in a 100-ml measuring flask, and the solution is
used as a sample to be analyzed for arsenic and antimony.
11. Pretreatment for Analysis of Selenium

Steps (1) to (7) of the previous procedure are performed on the sample. After cooling, 20 ml of
hydrochloric acid (1+1) is added and the solution is boiled (approx. 100ºC) for approximately
10 minutes. After cooling, the volume is standardized in a 100-ml measuring flask, and the
solution is used as a sample to be analyzed for selenium.
12. River Water
13. Pretreatment for Analysis of Arsenic and Antimony

(1) 100 ml of the sample is put into a 300-ml glass beaker, 2 ml of nitric acid is added, and this
is heated on a hot plate (approx. 190ºC) until it is almost dry.
(2) After cooling, 20 ml of hydrochloric acid (1+1) and 5 ml of potassium iodide (20wt%/V) is
added, the temperature in the beaker is gradually increased to 70ºC, and heating is
continued for approximately 4 minutes.
(3) After cooling, the volume is standardized in a 100-ml measuring flask, and the solution is
used as a sample to be analyzed for arsenic and antimony.
14. Pretreatment for Analysis of Selenium

Step (1) of the previous procedure is performed on the sample. After cooling, 20 ml of
hydrochloric acid (1+1) is added and the solution is heated (not boiled) for approximately
10 minutes. After cooling, the volume is standardized in a 100-ml measuring flask, and the
solution is used as a sample to be analyzed for selenium.
Training－69
Appendix 3 Standardization of Measured Intensity (Drift Correction)
The measured intensity is subject to a slight variation with passage of time. It also changes when
the plasma is extinguished and then re-ignited. Calibration of the measured intensity so that the
same calibration curve can be used even when it fluctuates is referred to as "standardization".
The sample used for standardization is referred to as the "calibration sample"; it is measured when
creating a calibration curve and when performing standardization, and the measured intensity is
calibration so as to compensate for this change. The intensity measured for the calibration sample
when creating a calibration curve is referred to as the "reference value". There are two methods
that can be used for standardization: 1-point correction and 2-point correction.
Correction Formula
Intensity after correction, I

I= k x (I’ + )
I : Intensity after correction
I’ : Intensity before correction
,: Correction coefficients for 2-point correction
K : Correction coefficient for 1-point correction
I= k x (I�(
Appendix Fig. 3-1 Standardization of Measured Intensities
K=1.0 is used with 2-point correction and =1.0 and =0.0 are used with 1-point correction.
The calculation methods for the correction coefficients are as follows:
Intensity before correction, I'

2-point Correction
IHT - ILT
= = ILT - αIL
IH - IL
IHT : Reference value for high-concentration calibration sample

ILT : Reference value for low-concentration calibration sample
IH : Measured value for high-concentration calibration sample
IL : Measured value for low-concentration calibration sample
1-point Correction
IKT
K=
IK
IKT : Reference value for calibration sample

IK : Measured value for calibration sample
Training－70
Appendix 4 Calculation Sequence for Analytical Values

Calculations required for quantitative analysis are performed in the following order.
Measured intensity I
BG correction
Internal standard correction

I= I’ / IR (internal standard element)
Blank elimination correction
Standardization correction I= K x (I’ + )
Intensity I (This value is output as the intensity result.)
Concentration conversion C= aI3+bI2+cI+d
Co-existing element correction
Weight correction C= C’ X Weight reference value / Weight value
Special virtual-element calculation
Average (R, S, CV) calculation
Deviation judgment (R check)
Standard judgment
Concentration C (This value is output as the concentration result.)

Display/printing of average values (R, S, CV), files,
transmission
Appendix Fig. 4-8 Calculation of Analytical Values
I’ ,C’ : Intensity/concentration before correction

I ,C : Intensity/concentration after correction
Training－71
Appendix 5 Glossary
1. ICP (Inductively Coupled Plasma)
Plasma generated by inductively coupling high-frequency electrical power.
2. Torch
Body of concentric tubes used to supply the gas flow required for igniting and sustaining the
ICP.
3. Nebulizer
Device for turning test solutions into fine droplets.
4. Spray Chamber
Device for separating out large droplets and introducing only extremely fine droplets into the
emission section.
5. Plasma Gas (or Coolant Gas)
Forms the main part of the ICP. Supplied through the outermost tube of the torch, it also cools
the torch. Also referred to as "coolant gas".
6. Auxiliary Gas (or Plasma Gas)
Gas used with ICP at an auxiliary level to lift the plasma upwards. Supplied through the
intermediate tube of the torch. Also referred to as "plasma gas" (corresponding to "coolant gas"
above.)
7. Carrier Gas
Gas used with ICP to introduce the sample into the plasma. Supplied through the central tube of
the torch.
8. Purge Gas
Gas delivered between the light source and the spectrometer and into the spectrometer in order
to eliminate absorption due to oxygen when performing measurement using wavelengths in the
vacuum-ultraviolet region. Nitrogen or argon is usually used.
9. Sequential Spectrometer
Device that disperses incident light and measures the intensity of single spectral lines or
sequentially measures the intensities of series of spectral lines.
10. Simultaneous Spectrometer
Device that disperses incident light and simultaneously measures the intensity of multiple
spectral lines.
11. Resolution
The ability of a spectrometer to separate two spectral lines that are approximately convergent.
12. Integration Time
The fixed period of time over which the emission intensity is measured and integrated.
13. Test Solution, Analytical Sample
The solution obtained by performing pretreatment on a liquid or solid sample and preparing it for
measurement.
14. Sample/Solution for Calibration (Working) Curve
Sample/solution containing the target element at a known concentration and used to create a
calibration (working) curve.
15. Sample/Solution for Correction of Calibration (Working) Curve
Sample/solution used to calibrate the calibration (working) curve after a certain time has elapsed
or after a certain number of samples have been measured.
Training－72
16. Laboratory Reagent Blank

Water or matrix that does not contain the target element and that has been subjected to exactly
the same treatment as the sample, including exposure to equipment and apparatus used for
analysis, such as glass, and addition of solvents, reagents, and internal standard elements.
Used to investigate the existence of contamination of the target element or interference
elements originating in the laboratory environment, the reagents, or the apparatus.
17. Calibration Blank
Solution for which the concentration of the target element is zero and that has the same
composition as the calibration-curve standard solutions.
18. Background Equivalent Concentration (BEC)
Element concentration that produces a signal intensity equal to the background intensity.
19. Detection Limit (DL)
Concentration that produces a signal intensity 3 times the standard deviation of the emission
intensity for a blank-test solution.
20. Limit of Quantitative Determination (LQD)
Concentration that produces a signal intensity 10 times the standard deviation of the emission
intensity for a blank-test solution.
21. Instrument Limit of Detection (ILOD)
Concentration that produces a signal intensity 3 times the standard deviation obtained when a
blank solution is measured 10 times in succession.
22. Method Limit of Quantification (MLOQ)
Concentration that produces a signal intensity 14.1 (=2×10) times the standard deviation
obtained when a laboratory reagent blank is measured 10 times in succession.
23. Short-term Precision
The standard deviation in the emission intensity or the intensity ratio when the same sample is
measured repeatedly over a short time period.
24. Long-term Precision
The standard deviation in the emission intensity or the intensity ratio when the same sample is
measured repeatedly over a long time period.
25. Quality Control
Procedure for certifying that analysis is performed correctly within the prescribed limits.
26. Quality-control Solution
Solution that contains the target element at a known concentration and is used to investigate the
accuracy of calibration-curve standard solutions prepared by dilution or mixing, and to perform
initial and periodic inspections of system performance. It is obtained from an external source,
separately from the calibration-curve standard solutions, and the acid concentration is adjusted
to equal that of the calibration-curve standard solutions. It is readjusted 4 times a year or more
frequently if deemed necessary.
27. Memory Effect
A phenomenon where some of the target element from a sample used in an earlier analysis
remains in the system and shows up in measurements together with the target element in the
sample for the current analysis.
28. Internal Standard
Element(s) added to calibration-curve standard solutions, calibration blanks, and test solutions
in equal amounts in order to correct for the non-spectral interference and changes in sensitivity
that occur over time in ICP emission spectrometers. Correction is performed by comparing the
Training－73
signals obtained for the target element and the internal standard. It is desirable that the internal
standard is not contained in the test solution, that it does not cause spectral interference with
respect to the target element, that it is not subject to spectral interference due to constituents of
the sample, and that it exhibits the same behavior as the target element.
29. Hydride Generator
Device used to reduce the target constituents (e.g., compounds of arsenic, selenium, and
antimony) in a solution, converting them into hydrides, and introducing them into the emission
section.
Training－74

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Chapter 1 Inductively Coupled Plasma Emission Spectrometry...................................................5

Chapter 2 Qualitative and Quantitative Analysis...........................................................................23

Chapter 3 Analysis with the ICPS Series......................................................................................31

1.4.1. Semi-quantitative Values.....................................................................................34

Chapter 4 Interference and Correction Methods.........................................................................43

2.3. High Pressure Decomposition...................................................................................54

Appendix 1 Analysis of Organic Solvents with ICP (ICPS-7500/8100)..........................................61

Appendix 2 Analysis Using the Hydride-generation Method.........................................................66

Appendix 3 Standardization of Measured Intensity (Drift Correction)............................................70

Appendix 4 Calculation Sequence for Analytical Values...............................................................71

Chapter 1 Inductively Coupled Plasma Emission Spectrometry

2. Principle of Emission Spectrometry

E : High energy level

Fig. 1-1 Model of the Atom v: Frequency of the spectral line

Fig. 1-2 Generation of Atomic Spectra

N0 : Number of atoms in steady state

The following well-known equations can be derived from the above.

i : Incident angle, r : Refraction angle,  : Deviation angle

Fig. 1-4 Diffraction of Waves

Wave troughs Bright

Fig. 1-6 Diffraction

Normal to diffraction grating's surface

Fig. 1-7 Diffraction Grating

n= d (sin  + sin ) n : Diffraction order

d l / d= f . d / d f : Spectrometer's focal length

Table 1-1 Spectrometer Comparison

7. Inductively Coupled Plasma Emission Spectrometers

Fig. 1-8 Configuration of ICP Emission Spectrometer

When high-frequency current is passed

Fig. 1-10 Frequency Characteristics of Plasma

10. Structure and Role of Plasma Torch

Plasma torch (quartz)

Coolant gas, 10 to 20 L/min

Plasma gas, 0 to 5 L/min

Carrier gas (sample)

Fig. 1-11 Structure of Plasma Torch

11. Types of Nebulizer and Characteristics

Drain Sample solution

Fig. 1-12 Typical Sample Introduction System Used in Emission

12. Spectrometry Section

Example of Spectrometer Using Concave Diffraction Grating (Paschen-Runge)

13. Photometry Section

Fig. 1-14 Structure of Photometry Section

14. Increasing Sensitivity with ICP Emission Spectrometry and Applications

15. Ultrasonic Nebulizer

Drain valve Nebulization

Fig. 1-15 Ultrasonic Nebulizer

Fig. 1-16 Peak Profiles Obtained with Ultrasonic Nebulizer

Fig. 1-17 Calibration Curves Obtained with Ultrasonic Nebulizer

16. Hydride-generation Method

Fig. 1-18 Configuration of Hydride-generation Apparatus

Fig. 1-19 Peak Profiles for Arsenic, Selenium, and Antimony

Fig. 1-20 Calibration Curves Obtained with Hydride-generation Method

17. Axial Measurement

Fig. 1-21 Configuration of Axial-measurement Section

Transverse Measurement Axial Measurement

Fig. 1-22 Principle behind Plasma-measurement Direction

Chapter 2 Qualitative and Quantitative Analysis

Iwanami Dictionary of Science (Iwanami Shoten)

2. Emission Spectrometry and Qualitative Analysis

3. Qualitative Analysis with Sequential ICP Emission Spectrometry

Si 251.612 P 178.287 S 180.731 K 766.491 Ca 393.366 Sc 361.384