Heavy Metals and their Detail Analysis Methodology

Yong Ching TungPerkinElmer Singapore Pte Ltd

Singapore

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PerkinElmerOptima 2100DVHPA-S & GC/MS

LG - Environment Report 2003

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Sony Environmental Monitored substancesSS-00259 3rd Edition

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Sampling

Different Colouredportions

Coded PortionsOuter shield cover Inside Shield cover

Shield cover

Representative Parts & Portions

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Sampling

Plug

Buttons of various colours

Casing Rubberised Buttons

Cable Ties

Shield cover

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Sony Environmental Monitored SubstancesSS-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 Cd2. 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 SubstancesSS-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 Cd2. 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 SubstancesSS-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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Simplified Principle of Flow Injection

Carrier ReagentSample

Low-level Mercury Analysis- FIMS

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FIMS: Optical Path

Detector

Hg GasAbsorption 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 RangeSummary

FIMS ICP-OES OnlyWorking range (ppb) 0.020 - 20 2-20,000Detection limit (ppb) 0.005 5.6 ppb

Time/sample (n=3) 2 Min. 1.5 Min.Sample consumption 4 mL 5 mLAutomation Yes Yes

404E

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EN-1122: 2001 Method B – Total Cd Analysis

Total Cd analysis1. 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 HH22SOSO44 to accuratelyto accurately--weighed weighed 00.500.500gm of sample in a beaker;gm of sample in a beaker;

2.2. Heat for about 20 minutes until char;Heat for about 20 minutes until char;3.3. Cool for about 5 minutesCool for about 5 minutes;;4.4. Add 5 Add 5 mLmL of Hof H22OO22 to the residues, heat for a to the residues, heat for a

further 10 minutes for the reaction to complete;further 10 minutes for the reaction to complete;5.5. Repeat steps 3Repeat steps 3--4 until a pale clear yellow solution 4 until a pale clear yellow solution

is obtained.is obtained.6.6. Cool the solution for about 5 minutes; Add 5 Cool the solution for about 5 minutes; Add 5 mLmL

of of HNOHNO3, until reaction is complete., until reaction is complete.7.7. Dilute to volume(100 Dilute to volume(100 mLmL) and filtered.) 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.

2.2. Fusion Process:Fusion Process:1.1. Add to the residue 3 Add to the residue 3 --10 times its weight of Sodium 10 times its weight of Sodium

carbonate, dependent on the residue. Fused at 800 carbonate, dependent on the residue. Fused at 800 –– 900 900 °°C;C;

2.2. May need to add BMay need to add B2OO3 to aid the fusion; CO2 is evolved is evolved during the fusion, so the fusion has to be carried out very during the fusion, so the fusion has to be carried out very gradually. All would melt.gradually. All would melt.

3.3. Precaution:Precaution:1.1. Shape and size of the samples;Shape and size of the samples;2.2. Digestion has to be carried out very gradually, it can not Digestion has to be carried out very gradually, it can not

be rushed;be rushed;3.3. Purity of the chemical agents used is very criticalPurity of the chemical agents used is very critical

Method from Minebea Co. Ltd.

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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 beakerp Add 2.5 mL (65%) HNO3 10 mL(37%) HClpp Heat at 95℃ ± 5℃ for 15 minutesp Collect the clear filtrate in a 100 mL volumetric flaskp Wash the residue and filter paper with 5mL hot HCl & 5

mL hot D.I. waterp Collect the wash in the same volumetric flaskp Digest the residue with 5 mL HClp Combine the above digestate with the filtrate in the same

volumetric flaskp Make up the total filtrates to volume - 100 mL

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EN71 Part 3 - Open Digestion Method

Sample PretreatmentSample Pretreatment:(:(ENEN--71 Part 371 Part 3))Weigh about Weigh about 0.1000.100gm in a beakergm in a beaker

Add 5 5 mLmL (0.07 mole/L) HCL, & control the pH (0.07 mole/L) HCL, & control the pH at 1 at 1 –– 1.5 using 21.5 using 2 N HCLN HCL

Shake the sample in a Shake the sample in a thermostattedthermostatted bath(37bath(37°° C C ±± 22°° C)C) for 1 hourfor 1 hour

Leave and cool for an hour in the bathLeave and cool for an hour in the bath

Filter the extracted materialFilter the extracted material

Analyze the filtrate for heavy metals using Analyze the filtrate for heavy metals using ICPICP--OESOES

500259025502502560Modelling clay & Nail Polish

5006090607510002560Toys excluding modellingclays & nail polish

Max. Soluble Conc., mg/Kg, ppm

SeHgPbCrCdBaAsSbSamples

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EPA 3052 - Microwave Digestion Method

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Various Digestion Techniques

SurroundSurround

CombinationCombination

ChelationChelation

AttachmentAttachment

Solid CrossSolid Cross--linkedlinked

CombinationCombination

SurroundSurround

ChelationChelation

Complete DigestionComplete DigestionEPA 3052EPA 3052（（Microwave digestionMicrowave digestion））

EN 1122EN 1122

Total MetalTotal MetalContentContent

ChelationExtractiblesExtractiblesEPA 3050BEPA 3050BEN 71 part 3EN 71 part 3EPA 3060AEPA 3060A

Attachment

Attachment Soluble Content

Extractible < = Total Content

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Variation Between Open Digestion & Microwave Digestion

PVC 1 PVC 2 PVC 3Sample I.D.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 15.8Cd 21.3 35.4 2.33 7.43 3.71 9.41Cr 1.11 1.940 1.20 1.21 1.26 1.26Hg N.D. 0.018 N.D. 0.223 N.D. N.D.Pb 1.15 2.50 16.4 35.8 1.64 1.77Se 9.93 14.1 40.7 57.1 8.79 13.2Sb 0.113 1.23 N.D. 1.22 N.D. 1.23

MircrowaveMircrowave is is 1.5 ~ 31.5 ~ 3 times more powerful than Open Vessel times more powerful than Open Vessel Digestion as recommended by ENDigestion as recommended by EN--11221122

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Results of Plastics Analysis（BCR-STD）

Sample NO

Element

EPA 3050B

EN 1122

EPA 3052

Certified value of

BCR-STD

RecoveryOf

EPA 3050B

RecoveryOf

EN 1122

RecoveryOf

EPA 3052

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 fromAcceptable Results with Recovery ranges from 85% ~ 115%85% ~ 115%

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Sony Environmental Monitored SubstancesSS-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+

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.

Calibration Curve

R2 = 0.9998

0

0.20.40.6

0.81

1.2

0 0.5 1 1.5 2

Concentration (ppm)

Abs.

Lambda 25

UV/VIS Spectrometer

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Extractible and Soluble Hexavalent Cr in Samples

COCO22

HH22OO

MOMO22MCMCxxOOyyHHzz

Digestion & SeparationDigestion & Separation

6+6+

ExtractionExtraction 3+3+

6+6+

CrCr6+6+& its Compounds in Samples& its Compounds in Samples

3+3+

6+6+

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Analysis of Cr+6 -- EPA 7196A

3+3+

6+6+ Lambda 25 UV/Vis Spectrometer

6+6+

6+6+

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Hexavalent Cr6+ EPA 3060A and EPA 7196A

Sample 2.5g Add 50ml Digesting liquid（0.28MNa2CO3/0.5MNaOH）

400400mg MgClmg MgCl22 and and 0.5ml 1.0M phosphate buffer0.5ml 1.0M phosphate buffer

Heat with Stirring 90~95Heat with Stirring 90~95℃℃60 minutes60 minutes

Filtered through 0.45Filtered through 0.45μμm m filter paperfilter paper

Add 5M HNOAdd 5M HNO33 , Adjust pH 7~8;, Adjust pH 7~8;Make up to 100mlMake up to 100ml

FilterFilter

cool

EPA 7196AEPA 7196A

Add Add 22ml ml DiphenylcarbazideDiphenylcarbazidesolution to 95 solution to 95 mLmL solutionsolution

Add 10Add 10﹪﹪HH22SOSO4 4 ; Adjust pH ; Adjust pH to to 1.5~2.5 1.5~2.5

Make up to Make up to 100ml; Analyze100ml; Analyze

Potassium Dichromate as StandardPotassium Dichromate as Standard

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DIN 53314 - Extraction & Colorimetry

Sample 2± 0.01 g

Plug, Temp. Controlled at 18~28° C,Shake for 3 hours.

Filter through 0.45μm filter paper Measured pH, Measured pH, 7.5 ~ 87.5 ~ 8

Stand for 10 minutesStand for 10 minutes

Add 100 mL Phosphoric acid, pass Argon gas at 50 mL / minute for 5minutes;

Filter, add 10 mL+1 mL Diphenylcarbazide＋ 1 mL phosphoric acid，make up to 50 mL

Measure Absorbance at 540 nm with an UV-VIS Spectrometer（using 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

0.000 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.5000.000

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.400

10xe-6g/ml

A

∇1∇2 ∇

3 ∇4 ∇

5 ∇6

∇7

Equation: y = 6.389643eEquation: y = 6.389643e--01 * x01 * x

Residual error: 0.000722Residual error: 0.000722

Correlation coefficient: 0.999966Correlation coefficient: 0.999966

Standard SolutionStandard Solution

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Analysis of Cr+6 -- UV/VIS Spectrometry

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 AreasSuitable 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.

NIEA R309.12C

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

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 mLof 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

NIEA R201.11C

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Analysis Results

Yellow TapesYellow Tapes Yellow plastic labelsYellow plastic labels

SamplingSampling

EPA 3060A DigestionEPA 3060A Digestion

EPA 7196 A EPA 7196 A

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Comparison of Result and Analysis Time

NDNDNDConc.of Cr6+

~3 hrs~3 hrs>20 hrsAnalysis Time

DIN 53314EPA 3060ATCLP Methods

Result

ND = not detectedND = not detected

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Page 35ChingChing--tung.yong@perkinElmer.comtung.yong@perkinElmer.com Tel.: (65) 67799533 Fax.: (65) 68726595Tel.: (65) 67799533 Fax.: (65) 68726595