Heavy Metal Heavy Metal MonitoringMonitoring in in EnvironmentalEnvironmental Samples Samples usingusing ICPICP--OESOES

Uwe Oppermann and Nils GarnebodeUwe Oppermann and Nils GarnebodeShimadzu Europa GmbHShimadzu Europa GmbH

EnvironmetalEnvironmetal ProtectionProtection

WaterWaterSoilSoilAirAir

Wat

er A

naly

sis

Water AnalysisWater Analysis

•• Atomic Absorption Atomic Absorption (AAS)(AAS)

•• Inductively Coupled Inductively Coupled Plasma (IPlasma (ICP)CP)

•• UVUV--VIS SpectrometryVIS Spectrometry

Ove

rvie

w

OverviewOverview

•• LegislationLegislation/ / DefinitionsDefinitions•• SystemconfigurationsSystemconfigurations•• MeasurementsMeasurements/ / ResultsResults

NormsNorms and and DirectivesDirectives

•• European European DrinkingDrinking waterwater regulationregulation•• MedicinesMedicines LawLaw•• FoodstuffsFoodstuffs and and CommoditiesCommodities ActAct•• MineralwaterMineralwater regulationregulation•• Standards of gas and Standards of gas and waterwater supplysupply industryindustry

(DVGW)(DVGW)

DrinkingDrinking Water RegulationWater Regulation

•• PurposePurpose::

Protection of all human beings from the Protection of all human beings from the dangerous influence of contaminated waterdangerous influence of contaminated water

•• Application areaApplication area::

since 01.01.2003since 01.01.2003for Drinking waterfor Drinking waternot for not for MineralwaterMineralwater, and other types of water, and other types of water

WhatWhat isis DrinkingDrinking Water?Water?

•• for drinking, cooking, preparation of foods for drinking, cooking, preparation of foods and drinksand drinks

•• household purpose:household purpose:•• personal hygiene and cleaningpersonal hygiene and cleaning•• cleaning of goods in touch with foods and cleaning of goods in touch with foods and

drinksdrinks•• cleaning of goods in touch with the human body, cleaning of goods in touch with the human body,

such as clothes, bedclothes, towelssuch as clothes, bedclothes, towels……..•• Water for food and drink producing industriesWater for food and drink producing industries

Chemical Chemical RequirementsRequirements

•• No chemical substances in concentrations which No chemical substances in concentrations which will be harmful for the human healthwill be harmful for the human health

•• No chemical substances in concentrations higher No chemical substances in concentrations higher than the max. allowable concentrations listed in than the max. allowable concentrations listed in App. 2App. 2

•• All substances which will be able to participate in All substances which will be able to participate in any water contamination have to be restricted and any water contamination have to be restricted and must be kept as low as possible according to the must be kept as low as possible according to the actual state of technologyactual state of technology

OrganicOrganic CompoundsCompounds

•• AcrylamidAcrylamid•• BenzolBenzol•• 1,21,2--DichlorethanDichlorethan•• PflanzenschutzmittelPflanzenschutzmittel und und BiozidprodukteBiozidprodukte•• TetrachlorethenTetrachlorethen and and TrichlorethenTrichlorethen•• BenzoBenzo--(a)(a)--pyrenpyren•• EpichlorhydrinEpichlorhydrin•• Polycyclic aromatic HydrocarbonsPolycyclic aromatic Hydrocarbons•• TrihalogenmethaneTrihalogenmethane•• VinylchlorideVinylchloride•• Total organic Carbon (TOC)Total organic Carbon (TOC)

InorganicInorganic CompoundsCompounds (App. 2)(App. 2)

Drinking Water Regulation

Europe TVOParameter Limit [mg/l] Limit [mg/l]

Aluminium 0.2 0.2Antimony 0.005 0.01Arsenic 0.01 0.01Barium n. i. 1Boron 0.3 1

Cadmium 0.005 0.005Calcium n. i. 400

Chromium 0.05 0.05Copper 2 3

Iron 0.2 0.2Potassium n. i. 12

Lead 0.01 0.04Magnesium 50 50Manganese 0.05 0.05

Mercury 0.001 0.001Nickel 0.02 0.05

Selenium 0.01 0.01Sodium 200 150Silver n. i. 0.01Zinc n. i. 5

LatestLatest NormsNorms in Water Analysisin Water Analysis

DIN/ ISO Norms:DIN/ ISO Norms:

Water Quality Control using Water Quality Control using

ICPICP--OES Spectrometry &OES Spectrometry &

UVUV--VIS SpectrometryVIS Spectrometry

……. Maximum . Maximum concentrationconcentration levelslevels of of elementselements havehave beenbeen reducedreduced as as followsfollows::

LeadLead 0,05 >>>> 0,01 mg/l0,05 >>>> 0,01 mg/l

CopperCopper 3 >>>> 2 mg/l3 >>>> 2 mg/l

Nickel 0,05 >>>> 0,02 mg/lNickel 0,05 >>>> 0,02 mg/l

TVO 2005: TVO 2005: ChapterChapter 2 Part II2 Part II……

Determination of 32 Elements Determination of 32 Elements ……

……………………using ICPusing ICP--OES Spectrometry: ICPEOES Spectrometry: ICPE--90009000

Determination of 32 Elements Determination of 32 Elements ……

Multielement Multielement CalibrationCalibration……..

Systemsetup ICPESystemsetup ICPE--90009000

•• IgnitionIgnition Mode: Mode: UltrasonicUltrasonicNebulizerNebulizer

•• AttachedAttached Instruments: Instruments: Mini Mini TorchTorch, , UltrasonicUltrasonic NebulizerNebulizer, , PeristalticPeristaltic PumpPump

•• Radio Radio FrequencyFrequency Power: Power: 1.00 kW1.00 kW•• Plasma Gas: Plasma Gas: 8.00 L/min8.00 L/min•• AuxiliaryAuxiliary Gas: Gas: 0.60 L/min0.60 L/min•• Carrier Gas: Carrier Gas: 0.60 L/min0.60 L/min•• ViewView DirectionDirection: : Axial/ RadialAxial/ Radial

Axial & Radial Axial & Radial ViewView

Emission SpectrumEmission Spectrum

Fe1ppmFe1ppm

Fe1000ppmFe1000ppm

Spectral InterferencesSpectral Interferences

Target element +coexisting element profile

Target element profile

Coexistent element profile

+

Measurement profile

Spectral InterferenceElement profile overlap and are observed as a large measurement profile

Cd Analysis in Fe MatrixCd Analysis in Fe Matrix

The optimal wavelength differs with the matrix and The optimal wavelength differs with the matrix and concentrationconcentration

1000

2000

3000

4000

5000

Inte

nsi

tyCd 226.502

�’ è «

1000

1500

2000

2500

Inte

nsi

ty

Cd 228.802 Best �’ è «

Fe

CdCd

Identification Identification

Optimal wavelength Optimal wavelength with no interferencewith no interference

Inte

nsity

Separation is difficult with simultaneous spectrometers

Which values should we use?Which values should we use?

1000

2000

3000

4000

5000

Inte

nsi

ty

Cd 226.502 �’ è «

1000

1500

2000

2500

Inte

nsi

ty

Cd 228.802 Best �’ è «

500

1000

1500

Inte

nsi

ty

Cd 214.438 � �ðŒ 1

Fe

CdCd

AsFe

Cd

Quantitative value100ppb

Quantitative value18ppb

Quantitative value 40ppbIdentification Identification Identification

Inte

nsity

Inte

nsity

Inte

nsity

CdCd Determination in SoilDetermination in Soil

MeasureMeasure IEC Sample As 20ppmIEC Sample As 20ppm

IEC Wavelength 189.042/ Cd Wavelength 228.802

Calculate Interfering element correction factor FI

0

5000

Inte

nsity

Cd 228.802 Best Cond 1

228.804Cd 228.802

0

500

Inte

nsity

As 189.042 Cond 1

189.041As 189.042Pd 189.041

MeasureMeasure Unk Sample incl. AsUnk Sample incl. As

Measure Unk at As 189.042 & Cd 228.802 Wavelength

Multiply the Intensity at As 189.042 with FI to calculate the Intensity of As at 228.802

Cd Result is obtained by subtracting As

Cd 228.802nm As 189.042nm

As

As

IEC sample

Cd228.802nm As 189.042nm

As

As

Cd

Unknown sample

International International ReferenceReference MaterialMaterial

SampleSample River water standardRiver water standard JACJAC--00320032

ElementElement quantitativequantitative guaranteedguaranteed

PbPb 9.79.7 9.9 +/9.9 +/-- 0.20.2

CrCr 10.110.1 10.1 +/10.1 +/-- 0.20.2

CdCd 1.01.0 1.00 +/1.00 +/-- 0.020.02

CuCu 10.310.3 10.5 +/10.5 +/-- 0.20.2

FeFe 56.456.4 57 +/57 +/-- 22

MnMn 5.45.4 5.4 +/5.4 +/-- 0.10.1

ZnZn 10.910.9 11.3 +/11.3 +/-- 0.40.4

BB 60.360.3 59 +/59 +/-- 22

AlAl 61.261.2 61 +/61 +/-- 22

NiNi 9.99.9 10.2 +/10.2 +/-- 0.30.3

MoMo 0.40.4 --

** CaCa 12.312.3 12.5 +/12.5 +/-- 0.20.2

** MgMg 2.82.8 2.86 +/2.86 +/-- 0.040.04

** NaNa 4.44.4 4.5 +/4.5 +/-- 0.10.1

All Data [µg/L], except * [mg/L]

ConclusionConclusion

ICPEICPE--9000 9000 isis a a „„statestate of of thethe artart““ tooltool forforeasyeasy determinationdetermination of of heavyheavy metals in metals in environmentalenvironmental samplessamples such as such as drinkingdrinking waterwater!!

ThankThank YouYou