Heavy Metals and

their Detail Analysis Methodology

Yong Ching Tung

PerkinElmer Singapore Pte Ltd
Singapore
 LG - Environment Report 2003

PerkinElmer
Optima 2100DV
HPA-S & GC/MS

Page 2
 Sony Environmental Monitored substances
SS-00259 3rd Edition

Page 3
 Sampling

Representative Parts & Portions

Shield cover
Different Coloured
portions

Coded Portions
Outer shield cover Inside Shield cover

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 Sampling

Cable Ties
Plug

Shield cover

Buttons of various
colours

Casing Rubberised Buttons

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 Sony Environmental Monitored Substances
SS-00259 3rd Edition

Analysis of Cadmium & its Compounds

Pretreatment 4 Methods
Ashing using sulphuric acid;
Closed-vessel digestion under pressure such as microwave digestion method EN 13346:2000 or
EPA 3052:1996;
Nitric acid and hydrogen peroxide such as EPA 3050B Rev. 2:1996
Sulphuric acid, Nitric acid, hydrogen peroxide wet decomposition method such as BS EN
1122:2001 etc;
* Residues can be digested by appropriate dissolution techniques

Analysis Method: 3 recommended

By ICP-AES/ICP-OES, such as EN ISO 11885:1998
By AAS such as EN ISO 5961:1995
By ICP-MS

Maximum permissible level for Cd is 5 mg/Kg(ppm)

Lead can also be analyzed together when ICP-OES and ICP-MS is
used

Nb: 1. Sample Dissolution technique as in EN 71-3: 1994 is not suitable for Cd

2. Industrial Effluent Method JIA K0102-55 is an Analysis Method only, appropriate
Sample Pretreatment must be used in conjunction

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 Sony Environmental Monitored Substances
SS-00259 3rd Edition

Analysis of Lead & its Compounds

Pretreatment 4 Methods
Ashing using sulphuric acid;
Closed-vessel digestion under pressure such as microwave digestion method EN 13346:2000
or EPA 3052:1996;
Nitric acid and hydrogen peroxide such as EPA 3050B Rev. 2:1996
Sulphuric acid, Nitric acid, hydrogen peroxide wet decomposition method such as BS EN
1122:2001 etc;
* Residues can be digested by appropriate dissolution techniques

Analysis Method: 3 recommended

By ICP-AES/ICP-OES, such as EN ISO 11885:1998
By AAS such as EN ISO 5961:1995
By ICP-MS

Maximum permissible level for Pb is 100 mg/Kg(ppm)

Cadmium can also be analyzed together when ICP-OES and ICP-
MS is used
NB: 1. Sample Dissolution technique as in EN 71- 3: 1994 is not suitable for Cd
2. Industrial Effluent Method JIA K0102-54 is an Analysis Method only, appropriate
Sample Pretreatment must be used in conjunction

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 Sony Environmental Monitored Substances
SS-00259 3rd Edition

Analysis of Mercury & its Compounds

Pretreatment 3 Methods
(Similar to that for Cd and Pb)
Closed-vessel microwave digestion method such as EPA 3052:1996;
Commercially available Mercury Analyzer (inclusive of sample
pretreatment and analysis);
Cool Condensing Digestion vessel (Kjeldahl), using sulphuric and
nitric acid wet Decomposition Method;
* Residues can be digested by appropriate dissolution techniques

Analysis Method for low Concentrations:

By cold vapour Hydride Generation AAS Method or
Hydride attachment to ICP-OES/ICP-MS

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 Low-level Mercury Analysis- FIMS

Simplified Principle of Flow Injection

Carrier Sample Reagent

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 FIMS: Optical Path

Detector

Hg Gas
Absorption Cell
Cell Heating 50 C

Quartz Window Holder

Hg Lamp

401E

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 PerkinElmer FIMS

397E

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 Hg - Determination in the ng/L Range
Summary

FIMS ICP-OES Only

Working range (ppb) 0.020 - 20 2-20,000
Detection limit (ppb) 0.005 5.6 ppb

Time/sample (n=3) 2 Min. 1.5 Min.

Sample consumption 4 mL 5 mL
Automation Yes Yes

404E

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 EN-1122: 2001 Method B Total Cd Analysis

Total Cd analysis
1. Applicable Area:
1. All plastics, except teflon
2. Concentration ranges of 10 to 3,000
mg/Kg(ppm)
2. Samples Types:
1. At least 2 g of homogeneous samples cut
using sharp blades in small pieces of less
than 0.1 g each piece.
3. Digestion Procedure:
1. Weigh about 0.5 g to the nearest mg, digested
in appropriate digester
2. In duplicates

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 EN-1122: 2001 Method B - Procedure

1. Add 10 mL of H2SO4 to accurately-weighed

0.500gm of sample in a beaker;
2. Heat for about 20 minutes until char;
3. Cool for about 5 minutes;
4. Add 5 mL of H2O2 to the residues, heat for a
further 10 minutes for the reaction to complete;
5. Repeat steps 3-4 until a pale clear yellow solution
is obtained.
6. Cool the solution for about 5 minutes; Add 5 mL
of HNO3, until reaction is complete.
7. Dilute to volume(100 mL) and filtered.

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 Method for Digesting Teflon Samples for Cd & Pb

1. Procedure:
1. Cut the sample into small pieces, weighed accurately 0.25 g
into a platinum crucible;
2. Add 1-2 mL(1:1 H2SO4). Use appropriate larger volume
when the acid does not cover the sample;
3. Heat the acid mixture gradually until dry, then place the
crucible in the electric furnace, raise and maintain the
temperature at 450 C until a residue is formed.

2. Fusion Process:
1. Add to the residue 3 -10 times its weight of Sodium
carbonate, dependent on the residue. Fused at 800 900
C; Method from
2. May need to add B2O3 to aid the fusion; CO2 is evolved Minebea Co. Ltd.
during the fusion, so the fusion has to be carried out very
gradually. All would melt.

3. Precaution:
1. Shape and size of the samples;
2. Digestion has to be carried out very gradually, it can not
be rushed;
3. Purity of the chemical agents used is very critical

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 Open Digestion Method - EPA3050B

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 EPA 3050B-1 Analysis of Pb

p Weighed accurately about 1g of sample in a beaker

p Add 2.5 mL (65%) HNO3 10 mL(37%) HCl
p Heat at 95 5 for 15 minutes
p Collect the clear filtrate in a 100 mL volumetric flask
p Wash the residue and filter paper with 5mL hot HCl & 5
mL hot D.I. water
p Collect the wash in the same volumetric flask
p Digest the residue with 5 mL HCl
p Combine the above digestate with the filtrate in the same
volumetric flask
p Make up the total filtrates to volume - 100 mL

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 EN71 Part 3 - Open Digestion Method

Samples Sb As Ba Cd Cr Pb Hg Se
Max. Soluble Toys excluding 60 25 1000 75 60 90 60 500
Conc., mg/Kg, modelling
ppm clays & nail
polish

Modelling clay 60 25 250 50 25 90 25 500

& Nail Polish

Sample Pretreatment:(EN-71 Part 3)

Weigh about 0.100gm in a beaker
Add 5 mL (0.07 mole/L) HCL, & control the pH
at 1 1.5 using 2 N HCL
Shake the sample in a thermostatted bath(37 C
2 C) for 1 hour
Leave and cool for an hour in the bath
Filter the extracted material
Analyze the filtrate for heavy metals using ICP-
OES

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 EPA 3052 - Microwave Digestion Method

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 Various Digestion Techniques

Combination

Surround Total Metal

Content
Attachment Chelation

Solid Cross-linked Complete Digestion

EPA 3052Microwave digestion
EN 1122
Surround

Attachment
Soluble
Extractibles
EPA 3050B Chelation
Content
Combination
EN 71 part 3
EPA 3060A

Attachment

Chelation

Page 20 Extractible < = Total Content

 Variation Between Open Digestion & Microwave Digestion

Sample I.D. PVC 1 PVC 2 PVC 3

Element EN1122 MW EN1122 MW EN1122 MW

As 0.231 0.326 N.D. 0.494 N.D. N.D.

Ba 51.1 53.3 11.7 12.3 15.6 15.8
Cd 21.3 35.4 2.33 7.43 3.71 9.41
Cr 1.11 1.940 1.20 1.21 1.26 1.26
Hg N.D. 0.018 N.D. 0.223 N.D. N.D.
Pb 1.15 2.50 16.4 35.8 1.64 1.77
Se 9.93 14.1 40.7 57.1 8.79 13.2
Sb 0.113 1.23 N.D. 1.22 N.D. 1.23

Mircrowave is 1.5 ~ 3 times more powerful than Open Vessel

Digestion as recommended by EN-1122

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 Results of Plastics AnalysisBCR-STD

Sample Recovery
Certified Recovery Recovery
NO EPA EN EPA Of
value of Of Of
3050B 1122 3052 EPA
BCR-STD EN 1122 EPA 3052
Element 3050B

As 193.696 26.5 30.9 86 %

Cd 228.802 85.7 121 140.8 61 % 86 %

Cr 267.716 106 114.6 92 %

Pb 220.353 48.9 99.0 107.6 45.4% 92 %

Hg 253.652 23.0 25.3 91%

Acceptable Results with Recovery ranges from 85% ~ 115%

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 Sony Environmental Monitored Substances
SS-00259 3rd Edition

Analysis of hexavalent Chromium, Cr 6+

Pretreatment
Using hot water extraction

Analysis Method:
By UV-VIS Spectrometry;

Maximum permissible level for Total Chromium is 5 mg/Kg(ppm)

NB: 1. Total concentration for Hg < 5 ppm; Cd < 5 ppm; Pb < 100
ppm; and Cr < 5 ppm
2. Besides AAS, other techniques such as ICP-OES and ICP-MS
may also be used.

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 Hexavalent Chromium Analysis - Cr6+

Calibration Curve

1.2
1
0.8
Abs.

0.6
0.4
0.2
0
0 0.5 1 1.5 2 Lambda 25
Concentration (ppm) 2
R = 0.9998
UV/VIS Spectrometer

AA & ICP-OES results in TOTAL Cr;

Cr 6+ is analyzed by chelation of the extract;
Interference Removal;
Colour of the chelate measured by UV/VIS Spectrometry;
Applicable conc. Range: 0.01mg/L - 10mg/L.

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 Extractible and Soluble Hexavalent Cr in Samples

Extraction 3+

3+ 6+

6+ MO2
MCxOyHz

6+

CO
Cr6+& its Compounds in Samples

2
H2O

Digestion & Separation

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 Analysis of Cr+6 -- EPA 7196A

6+

3+

6+

6+ Lambda 25
UV/Vis Spectrometer

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 Hexavalent Cr6+ EPA 3060A and EPA 7196A

Sample 2.5g Add 50ml Digesting liquid 400mg MgCl2 and

0.28MNa2CO3/0.5MNaOH 0.5ml 1.0M phosphate buffer

EPA 7196A
Heat with Stirring 90~95 Add 2ml Diphenylcarbazide
60 minutes solution to 95 mL solution
cool

Filtered through 0.45m Add 10H2SO4 ; Adjust pH

filter paper to 1.5~2.5

Filter
Make up to
Add 5M HNO3 , Adjust pH 7~8; 100ml; Analyze
Make up to 100ml
Potassium Dichromate as Standard

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 DIN 53314 - Extraction & Colorimetry

Add 100 mL Phosphoric acid, pass Argon

Sample 2 0.01 g gas at 50 mL / minute for 5minutes;

Plug, Temp. Controlled at 18~28 C,

Shake for 3 hours.

Filter through 0.45m

filter paper Measured pH, 7.5 ~ 8

Filter, add 10 mL+1 mL Diphenylcarbazide

1 mL phosphoric acidmake up to 50 mL
Stand for 10 minutes

Measure Absorbance at 540 nm with an UV-VIS

Spectrometerusing 2 cm cell Path length)

Reference is 1 mL Diphenylcarbazide 1 mL Phosphoric acid in 50 mL of water, Potassium

Dichromate as Standard .

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 Analysis Results- Calibration Curve

0.400

0.35

0.30 7
0.25
0.20
A
6
0.15 5
0.10 4
3
0.05 12
0.000
0.000 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.500
10xe-6g/ml

Equation: y = 6.389643e-01 * x
Residual error: 0.000722
Correlation coefficient: 0.999966

Standard Solution

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 Analysis of Cr+6 -- UV/VIS Spectrometry

NIEA R309.12C

Analysis of Extracted hexavalent Cr by UV-VIS Spectrometry

1. Method
Hexavalent Cr reacts with Diphenylcarbazide to form a purplish red compound,
measured at its sensitive wavelength of 540 nm by UV-VIS Spectrometer; (1 mole of
hexavalent Cr would give about 40,000 absorbance units)

2. Applicable Areas
Suitable for extracted hexavalent Cr according to TCLP Method for the industrial waste
in the concentration range of 0.5 to 50 mg/L. Higher Conc. needs to be diluted to this
range for analysis.

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 Toxicity Contract Laboratory Procedure(TCLP):
Cr+6 and Cl-

NIEA R201.11C

Setup:
1. Agitation Apparatus, as in Figure
2. At 30 2 shakings per minute for
extraction

1. Extraction Fluid:
1. Fluid A: In a 1 Litre flask add 5.7 mL of
cold acetic acid to 500 mL of the sample
to be extracted, adjust pH using 64.3 mL
of 1 N NaOH until pH is 4.93 0.05; Check
pH before use
2. Fluid B: In a 1 Litre flask add 5.7 mL of
cold acetic acid to the sample, pH should
be at 2.88 0.005

Use Fluid A when pH < 5.0; Use Fluid B when pH > 5.0

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 Analysis Results

Yellow Tapes Yellow plastic labels

Sampling
EPA 7196 A

EPA 3060A Digestion

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 Comparison of Result and Analysis Time

Methods
TCLP EPA 3060A DIN 53314
Result

Conc.of Cr6+ ND ND ND

Analysis Time
>20 hrs ~3 hrs ~3 hrs

ND = not detected

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 Ching-tung.yong@perkinElmer.com Tel.: (65) 67799533 Fax.: (65) 68726595
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