list of annex - jica · theoretical training for aas %1 4.1 electro-thermal atomic absorption flame...

Lecture Document for Metal Analysis

(by the JICA Expert Team)

Theoretical Training for AAS

3.

3.1

.

.

.

.

.

) ( 1 .

.

.

3.2 ) (

.

1/1000

) ( 1/100000 1/1000000 .

. 0.1

.

.

3.1

.

1000 ppm 0.1 .

0.5 1.0 1.5 2.0 ppm .

. 0.5 ppm . 2.0 ppm

. 0.5 1.0 .

52




3.1 4. ) (

. )1 ( )2 ( .

.

.

4.1

) (

4.1) 1 (

.

. .

.

.

(1) (2)

4.1

4.2

) (

. .

4.1) 2(.

x .

4.2 . 100

10 Mg 100 ppm . 0 10 20 30

Mg 1.0 ppm.

53




100 .

x x+0.1 x+0.2 x+0.3 .

4.2) 2 ( x ppm.

10 .

4.2

.

. .

4.3

0.5 0.3 .

1 % (0.0044 Abs) . 1%

0.0044

.

1% 0.004 Abs .

1 %

70 80

0.004 0.3 . Cd 0.12

0.96 ppm 1 % 0.012 ppm

4.1 .

1000 1/10 1/20 1 % .

1 %

1 %

.

54




. 4.3 .

90 . 1/20

.

4.3

55




4.1 1 % Electro-thermal atomic absorption

Flame atomic absorption 1% absorption concentration

(ppb) High

1% absorption concentration

(ppb) Low

1% absorption concentration

(ppm)

Gas type

Analysis line

wavelerngth

(nm)

Element

0.14 0.22 0.005 0.07 0.05 0.05 0.12 0.02 0.5 0.004 0.16 0.13

0.5 1.0 0.48 0.55 0.06 0.02 0.28 0.10 0.20 0.19 0.03 0.02 0.15 0.02 0.40 0.29

0.04 0.63 0.4 0.2 12 0.25 0.025 0.25 0.06 0.02 0.012 0.06 0.08 0.03 0.04 1.0 0.8 0.5 0.08 1.3 30 1.7 16 0.14 1.2 1.4 0.012 70 0.03 12 0.0035 0.028 0.5 0.005 30 0.08 1.5 0.1 0.25

Air-C2H2 N2O-C2H2

Ar-H2

Air-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

328.1 309.3 193.7 242.8 249.7 553.5 234.9 223.1 422.7 422.7 228.8 240.7 357.9 852.1 324.7 421.2 400.8 459.4 248.3 287.4 368.4 265.1 307.3 253.7 410.4 208.8 766.5 550.1 670.8 360.0 285.2 279.5 313.3 589.0 334.9 232.0 290.9 217.0 283.3

Ag Al As Au B Ba Be Bi

Ca(1) Ca(2)

Cd Co Cr Cs Cu Dy Er Eu Fe Ga Gd Ge Hf Hg Ho Ir K La Li Lu Mg Mn Mo Na Nb Ni Os

Pb(1) Pb(2)

0.09 30

Air-C2H2 N2O-C2H2

247.6 495.1

Pd Pr

56




Electro-thermal atomic absorptionFlame atomic absorption

0.25 0.28 0.57 2.0

0.35 1.6 0.7 5.5 2.1 2.1 1.3 0.03

1.3 0.06 12 0.6 0.33 0.5 0.5 1.3 15 2.0 5.0 0.8 2.0 0.06 15 12 0.3 1.8 0.3 1.0 8.0 3.0 0.1 0.011 15 0.06 0.12 0.25

Air-C2H2

Air-C2H2

N2O-C2H2 Air-C2H2

Air-C2H2

N2O-C2H2 Ar-H2

N2O-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2 Air-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

N2O-C2H2

Air-C2H2

N2O-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

Air-C2H2

265.9 780.0 346.0 349.9 217.6 391.2 196.0 251.6 429.7 224.6 286.3 224.6 286.3 460.7 271.5 432.6 214.3 364.3 276.8 318.4 255.1 410.2 398.8 213.9 360.1 193.7 223.1 217.6 196.0 286.3 214.3

Pt Rb Re Ru Sb Sc Se Si Sm

Sn(1) Sn(2) Sn(3) Sn(4)

Sr Ta Tb Te Ti Tl V W Y

Yb Zn Zr

As(H) Bi(H) Sb(H) Se(H) Sn(H) Te(H)

5.

:

.

.

.

.

57




.

.

.

5.1

.

.

Eu3247 (530A)

Cu3247 (540A) V2506 (905A) Si2506 (899A).

. Fe2138 (589A)

Zn2138 (56A) .

.

.

.

.

. 250 nm .

.

.

NaCl .

) . 5.1(

5.1

5.1

.

ppm.

58




.

.

.

. 5nm

. .

5nm .

.

.

.

190nm 430nm .

.

. .

100 .

.

) ( .

)

(.

(200-38456-XX)

.

A 5.2 IH 300 600

IL 60 . 100 .

IH ) (

B 5.2.

.

59




10-2

.

B 5.2.

.

. C 5.2.

10-2 .

B 5.2 .

B 5.2.

IH IL .

:

1. 190nm 900nm.

2.

.

3. .

5.2

5.2

.

.

.

4-methyl-2-pentanone acetic acid-n-butyl

.

.

.

.

.

5.3

60




.

) ( .

.

Ca, Sr, Ba, Rb, Li, Na, K, Cs 1.6 eV

- .

Cs, Rb,K

.

. Mg, Ca

- 5.3 .

MgO.Al2O3.

Mg, Ca .

- .

Al, Si, Ti, V .

5.3

.

.

1.

.

2. .

3. .

4. .

Sr, La, EDTA

. –

.

.

1. .

61




2. .

3. .

:

A. .

B. .

C. ppm.

3.1 ) (

Cd Pd(NO3)2 + NH4NO3

(NH4)2HPO4 + HNO3

Mg (NO3)2

(NH4)H2PO4 + HNO3 or Mg (NO3)2

ppb level OK with blood, serum and urine.

Addition of F', SO4, PO4 effective

Pb Mg (NO3)2

La(NO3)3

Pd, Pt ( g level)

Coexistence with NaCl, KCl, MgCl2, etc.

prevents PbCl2 sublimation

Effective by alloying HNO3 addition

effective, high sensitivity attained by

alloying

Hg Sulfide + HNO3

HCl + H2O2

K2Cr2O7 + Na2S

Au, Pt, Pd ( g level)

Se

Organic acid

(Succinic acid, tartaric acid)

Volatization prevention as HgS

For prevention of reduction

vaporization

Volatization prevention by

amalgamation

Used for soil

T2 Pd, Pt, Ir

La(NO3)

Alloying

Alloying

Bi Pb MIBK extract

Sn Mg (NO3)2, (NH4)2HPO4

La (NO3)3

Use with ascorbic acid to prevent

interference

Effective by alloying

62




K2, WO4, K2MO4

NH4NO3, (NH4)2C2O4

Sensitivity improves remarkably but

chloride interference exists

No chloride interference

Target element Matrix modifier Remarks

Se Mg (NO3)2

Pd, Pt, Cu, Al, Ni

Coexistence with Ni is effective (NiSe

produced)

Particularly Pb good, PdSe produced

As Pd best, Mo, Zr, Ba also good

La (NO3)3

Corxistence with Ni is effective

Production of As2O6 seems to be effective

Sb

Cu best, Ni, Pt also effective

La (NO3)3

Alloying

Alloying

Tl Pd+HClO4

La (NO3)3

Coexistence with ascorbic acid is effective,

Pd checks TlCl production

Alloying

In Pd

La (NO3)3

Pd checks production of subliming InO

Alloying

Ga Ni Ni checks GaO production and avoids

inorganic matter interference

Zn Succinic acid, oxalic acid MaCl2 produces ZnCl2 and sublimes.

Organic acid check it

P La (NO3)3 Sensitivity improves by 6 times

Si, Al, Mn, Cu,

Cd, Ba, Be, Cr

La (NO3)3 Effective with alloying

63

Sam

plin

g fo

r m

etal

s an

alys

es

SS

Suspen

ded

metals

(solid)

SS except

metals

Dissolved metals (liquid,

ionized

) usually invisible

Time

cou

rse

SS precipitate and

adhe

re to

the w

all an

d bottom of the

bottle.

( T

his m

akes an

acc

urate

analysis

Collecting sample in bottle

Adding Acid

i.e. 10m

L HNO

3 / 1L

Generally, metals can

be dissolved by acids

Most of suspende

d m

etals can be

dissolve in liquid and

preserved

well.

SS m

ay be dec

ompo

sed by acid

This makes getting suitab

le sample

easier for analyst.

64

Pretreatment (preliminary treatment)

for metals analyses

65

Lecture Document for Metal Analysis (by the JICA Expert Team)

Handling Toxins

Handling Toxins 1. Be Conscious

The easiest way to know the dangerous level of an element is to check its Maximum

Limits of Water Discharge. If the limit is low, the element should have powerful influence

on the environment or us. Toxicity depends on concentration. For example, even Al can

affect if its concentration is high and you can’t call 1/1,000,000ppb Cr(Ⅵ) a toxin. But be

careful that Cd and Hg are extremely dangerous even diluted.

The importance of consciousness is to prevent not only you but also others from toxins.

If you leave apparatus contaminated by Hg, someone else may touch it. He may eat

something by his bare hand and he may die. This is not an exaggerated example because

something like this can happen anytime. You must be conscious that you are risking

others’ life when you are handling toxins. Follow instructions (O/M-3～5). And never

drain them into sewage because people, animals, plants or other creatures are living as we

are in the downstream regions.

2. Methods to handle Let’s consider how to dispose of waste. For example,

1) You get waste below the AAS. Where should you throw this out? This waste is from

rinsing of the tip for the furnace and draining from the chamber for the flame. The tip for

furnace sucks standards with acid but usually standards are already ppb level and it is

rinsed by much amount of water, which means the water is not contaminated in a

considerable level. As for drain from the flame system, Ba, Cu, Fe and Zn are only

elements measured with flame. All of these elements are shown in the top level in the

figure above and can be drained with concentration below 1ppm. Some of these elements

Maximum Limits of Water Discharge(Syrian, selected as smallest values from several kinds)

Al Ba

Cr

Fe

Mn

Ni

Pb

Sb

Ag As Cr(Ⅵ）

ZnCu

Be HgCd0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

(ppm)

:

68

Lecture Document for Metal Analysis (by the JICA Expert Team)

Handling Toxins

are prepared in about 5ppm but they should be diluted more than 5 times with other

solutions or water from the furnace. The water from the flame system is acidified. In

conclusion, The water from the furnace has little problems and the water from the flame is

obviously acidified, accordingly The waste should be into the tank for acidified waste

water. This is the way to decide the kind of waste.

2) Now you have 1ppm of Cu solution, which choice is the best to waste?

a. Dispose of it into the “Heavy Metal” waste

b. Dispose of it into the “Acidified Water” waste after dilution to make it less than 1ppm

(Max. Limit)

c. Dispose of it into the “Acidified Water” waste

d. Dispose of it into the sewage after dilution to make it less than 1ppm

In this case, d. is not acceptable because Cu with less than 1ppm is not a problem but

standard solutions are usually acidified. As for b. and c., if you put it into “Acidified Water”,

it’ll be diluted anyway that means c. is preferred. When you can dispose of it to “Acidified

Water”, you don’t have to increase the amount of “Heavy Metal” because it should be treated

through more steps than “Acidified Water”. Thus, a. is not suitable.

3) Now you have 100ppb of As solution, which choice is the best to waste?

a. Dispose of it into the “Heavy Metal” waste

b. Dispose of it into the “Heavy Metal” waste after dilution to make it less than 100ppb

(Max. Limit)

c. Dispose of it into the “Acidified Water” waste after dilution to make it less than

100ppb

d. Dispose of it into the sewage after dilution to make it less than 100ppm

In this case, d. is definitely not acceptable because elements shown in the bottom part of

the figure for Max. Limits (elements for the furnace method) are too dangerous unless it is

diluted to a certain very low concentration to be safe and the solution is acidified. As for c.,

this idea is not wrong but it is better to distinguish elements for furnace from others that

means it is not adequate in this case. As for b.., if you put it into “Heavy Metal”, you should

keep the amount of waste as little as possible. Accordingly, it is not correct. In conclusion, a.

is the best choice after all. (See O/M manuals for “Handling Toxins”)

69

) (

1.

.

.

1\1000000 ppb

. .

.

.

.

. )3 5 .(

.

2. .

1 (

.

ppb

.

Ba Cu Fe Zn .

1 ppm .

5 ppm .

Maximum Limits of Water Discharge(Syrian, selected as smallest values from several kinds)

Al Ba

Cr

Fe

Mn

Ni

Pb

Sb

Ag As Cr(Ⅵ）

ZnCu

Be HgCd0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

(ppm)

:

70

) (

.

. .

2 ( 1 ppm

1 . " ".

2 . " " 1 ppm ) (.

3 . " ".

4 . 1ppm.

1 ppm

. " "

.

" " " "

.

3 ( 100ppb

1 . " ".

2 . " " 100ppb ) (.

3 . " " 100ppb.

4 . 100 ppb.

) (

.

.

" " . .

) . .(

71

list of annex - jica · theoretical training for aas %1 4.1 electro-thermal atomic absorption flame...

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