ICP-MS methods for metals-PAR1-5 complete.ppt [modalità ...old.iss.it/binary/itti/cont/Palonta_ICP-MS methods for metals_en... · Twinning Contract BG 06 IB EN 01 Ministry of Environment

Twinning Contract BG 06 IB EN 01

Ministry of Environment & Water

ICPICP--MS methods for metals:MS methods for metals:inin house validation and extensionhouse validation and extensioninin--house validation and extension house validation and extension of field of application of methods of field of application of methods from inland waters to transitional from inland waters to transitional

and seaand sea waterwaterand seaand sea--water.water.

Maria T. PalontaMaria T. Palonta

Regional Environmental Protection Agency- Veneto Region LABORATORY REGIONAL DEPARTMENT

VENICE LABORATORY SERVICEVENICE LABORATORY SERVICEVENICE LABORATORY SERVICEVENICE LABORATORY SERVICE

Simitli (BG)- 02/17-19, 2009

SUMMARYSUMMARYSUMMARYSUMMARY11 BACKGROUNDBACKGROUND1.1. BACKGROUNDBACKGROUND2.2. CHARACTERS OF THE METHODS RECOMMENDED BY CHARACTERS OF THE METHODS RECOMMENDED BY

THE EC DIRECTIVETHE EC DIRECTIVE33 AVAILABLE TECHNIQUES FOR METALSAVAILABLE TECHNIQUES FOR METALS3.3. AVAILABLE TECHNIQUES FOR METALSAVAILABLE TECHNIQUES FOR METALS4.4. ICPICP--MSMS

a. Definitiona. Definitionb P & Cb P & Cb. Pros & Consb. Pros & Cons

5.5. THE ISO 17294THE ISO 17294--2 METHOD FOR THE ANALYSIS OF 2 METHOD FOR THE ANALYSIS OF METALSMETALS

66 THE ADOPTED METHOD AND ITS INTHE ADOPTED METHOD AND ITS IN HOUSE HOUSE 6.6. THE ADOPTED METHOD AND ITS INTHE ADOPTED METHOD AND ITS IN--HOUSE HOUSE VALIDATIONVALIDATION

7.7. UNCERTAINTY OF MEASUREUNCERTAINTY OF MEASURE88 EXTENTION FROM INLAND WATERS TO EXTENTION FROM INLAND WATERS TO 8.8. EXTENTION FROM INLAND WATERS TO EXTENTION FROM INLAND WATERS TO

TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERSWATERS9.9. MERCURY AS AN EXAMPLE OF PARTICULARLY MERCURY AS AN EXAMPLE OF PARTICULARLY

COMPLEX INCOMPLEX IN HOUSE VALIDATIONHOUSE VALIDATIONCOMPLEX INCOMPLEX IN--HOUSE VALIDATIONHOUSE VALIDATION







TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERSWATERS9.9. MERCURY AS AN EXAMPLE OF PARTICULARLY MERCURY AS AN EXAMPLE OF PARTICULARLY


11-- BACKGROUNDBACKGROUND11 BACKGROUNDBACKGROUNDDIRECTIVE 2000/60/EC OF THE EUROPEAN PARLIAMENT AND OF DIRECTIVE 2000/60/EC OF THE EUROPEAN PARLIAMENT AND OF

THE COUNCILTHE COUNCILTHE COUNCIL THE COUNCIL of 23 October 2000 of 23 October 2000

establishing a framework for Community action in the field of establishing a framework for Community action in the field of g yg ywater policywater policy

DIRECTIVE 2008/105/EC OF THE EUROPEAN PARLIAMENT AND OF THE COUNCILof 16 December 2008

on environmental quality standards in the field of water policy, amending and subsequently

repealing Council Directives 82/176/EEC, 83/513/EEC, 84/156/EEC, 84/491/EEC, 86/280/EEC and

amending Directive 2000/60/EC of the European Parliament d f th C iland of the Council

11-- BACKGROUNDBACKGROUNDDirective 2000/60/ECDirective 2000/60/EC

(1) Water is not a commercial product… (it must be)… (1) Water is not a commercial product… (it must be)… protected, defended and treated as such.protected, defended and treated as such.

(22) Thi Di ti i t t ib t t th i (22) Thi Di ti i t t ib t t th i (22) This Directive is to contribute to the progressive (22) This Directive is to contribute to the progressive reduction of emissions of hazardous substances to reduction of emissions of hazardous substances to water.water.

(27) The ultimate aim of this Directive is … the (27) The ultimate aim of this Directive is … the elimination of priority hazardous substances and … elimination of priority hazardous substances and …

t ti i th i i t t ti i th i i t concentrations in the marine environment near concentrations in the marine environment near background values for naturally occurring background values for naturally occurring substances.substances.

(45) Member States should adopt measures to (45) Member States should adopt measures to eliminate pollution of surface water by the priority eliminate pollution of surface water by the priority

b t d i l t d ll ti b b t d i l t d ll ti b substances and progressively to reduce pollution by substances and progressively to reduce pollution by other substances…other substances…

DIRECTIVE 2008/105/ECDIRECTIVE 2008/105/EC







TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs9.9. MERCURY AS AN EXAMPLE OF PARTICULARLY MERCURY AS AN EXAMPLE OF PARTICULARLY


CHARACTERS OF THE METHODS CHARACTERS OF THE METHODS RECOMMENDED BY THE EC DIRECTIVERECOMMENDED BY THE EC DIRECTIVERECOMMENDED BY THE EC DIRECTIVERECOMMENDED BY THE EC DIRECTIVE

WFDWFD requirements for analytical methodsrequirements for analytical methodsAnnex V, paragraph 1.3.6Annex V, paragraph 1.3.6

the provision of chemical data by Member the provision of chemical data by Member St t h ll b d b l ti l St t h ll b d b l ti l States shall be ensured by analytical States shall be ensured by analytical methodsmethodsthat conform to relevant international or that conform to relevant international or that conform to relevant international or that conform to relevant international or national standards or to other national or national standards or to other national or international standardsinternational standardsinternational standardsinternational standardsor alternatively by analytical methods that or alternatively by analytical methods that are not standardized but provide data of are not standardized but provide data of ppequivalent or better scientific quality and equivalent or better scientific quality and comparability than standard analytical comparability than standard analytical

th dth dmethodsmethods

Requirements from QA/QC COM Requirements from QA/QC COM

Li it f tifi ti (Li it f tifi ti (LOQLOQ) l b l ) l b l

decisiondecisionLimit of quantification (Limit of quantification (LOQLOQ) equal or below ) equal or below 30%30% of the relevant Environmental Quality of the relevant Environmental Quality Standards (Standards (EQSEQS))Sta da ds (Sta da ds ( QSQS))LOQ versus Lower Limit of LOQ versus Lower Limit of Application(Application(LLOALLOA) ) –– LOQLOQ = lab specific performance value = lab specific performance value –– LLOALLOA = method specific performance value= method specific performance value

Relative Target Uncertainty of 50%Relative Target Uncertainty of 50%Relative Target Uncertainty of 50%Relative Target Uncertainty of 50%measured at the level of the relevant measured at the level of the relevant EQSEQSValidationValidation according to according to EN ISO/IEC 17025EN ISO/IEC 17025gg //

METALS: AVAILABLE METALS: AVAILABLE TECHNIQUESTECHNIQUES

GFAASGFAASFAASFAAS

HGAASHGAASICPICP OESOESICPICP--OESOES

CC SS

COMPARISON OF ICPCOMPARISON OF ICP--MS TO MS TO OTHER TECHNIQUESOTHER TECHNIQUES

Shares applications with ICPShares applications with ICP--OES and AASOES and AASShares multielement characteristic with Shares multielement characteristic with ICPICP--OESOESShares analytical speed with ICPShares analytical speed with ICP--OESOESShares analytical speed with ICPShares analytical speed with ICP OESOESShares detection limits with GFAASShares detection limits with GFAASUnique in isotope measurement capabilityUnique in isotope measurement capabilityUnique in isotope measurement capabilityUnique in isotope measurement capabilityUnique in rapid semiquantitative analysisUnique in rapid semiquantitative analysis









ICPICP--MS (Inductively Coupled MS (Inductively Coupled Plasma Mass Spectrometry)Plasma Mass Spectrometry)

-- An analytical technique to An analytical technique to determine determine ElementsElements using using Mass Mass determine determine ElementsElements using using Mass Mass Spectrometry Spectrometry from from IonsIonsgenerated by an generated by an Inductively Inductively Coupled PlasmaCoupled Plasma

-- Mass spectroscopyMass spectroscopy-- SeparationSeparationand and measurementmeasurement of the mass of of the mass of individual atoms making up a individual atoms making up a given materialgiven materialgiven materialgiven material

ICP-TorchMass SpectrometerQuadrupole NebulizerQ p

Interface

Ionization Process in PlasmaIonization Process in PlasmaIonization Process in PlasmaIonization Process in Plasma

M t l t i i d (90%)M t l t i i d (90%)Most elements are ionized (90%)Most elements are ionized (90%)Most elements form a MMost elements form a M+ + (single ionization)(single ionization)

ICPICP--MS (Inductively Coupled MS (Inductively Coupled Plasma Mass Spectrometry)Plasma Mass Spectrometry)

PROPROPROsPROsRapid multiRapid multi--element element quantitative analysisquantitative analysis

CONsCONsIsobaric Spectral OverlapsIsobaric Spectral OverlapsMole la O e lapsMole la O e lapsq yq y

Very low detection limitVery low detection limitWide dynamic rangeWide dynamic range

Molecular OverlapsMolecular OverlapsNot suitable for samples Not suitable for samples with salt content > 0.3%with salt content > 0.3%

Isotopes analysis Isotopes analysis allowedallowed

with salt content > 0.3%with salt content > 0.3%

40

50

60

60

70

80

90

Pb Cr

20

30

40

20

30

40

50

0

10

204 206 207 208

0

10

20

50 52 53 54

PROsPROs-- Detection LimitsDetection LimitsPROsPROs Detection LimitsDetection LimitsMost below 10 pptMost below 10 pptMost elements 10 X better than GFMost elements 10 X better than GF--AASAASMost elements 10 X better than GFMost elements 10 X better than GF AASAASMost elements less than 0.01 ug/L:Most elements less than 0.01 ug/L:–– < 10 ng/L Al, As, Hg, Mg, Ti< 10 ng/L Al, As, Hg, Mg, Ti–– < 5 ng/L Ag, Au, Ba, Cd, Cu, Co, Mn, Mo, Sn, Sb, Pb, < 5 ng/L Ag, Au, Ba, Cd, Cu, Co, Mn, Mo, Sn, Sb, Pb,

PtPt–– < 1 ng/L all rare earth elements, Uranium and Thorium< 1 ng/L all rare earth elements, Uranium and Thorium

Even halogens have useful detection limits:Even halogens have useful detection limits:–– II 0.01 ug/L0.01 ug/L–– BrBr 0 2 ug/L0 2 ug/L–– BrBr 0.2 ug/L0.2 ug/L–– ClCl 10 ug/L10 ug/L

CONsCONs-- Molecular OverlapsMolecular OverlapsCONsCONs Molecular OverlapsMolecular OverlapsThe chemical and physical conditions existing in the The chemical and physical conditions existing in the plasma and interface region may allow the formation of plasma and interface region may allow the formation of

l i l l i i O COl i l l i i O COpolyatomic, or molecular ions. i.e. OH, CO, ArHpolyatomic, or molecular ions. i.e. OH, CO, ArHThe mass spectrum produced by introducing aqueous The mass spectrum produced by introducing aqueous solutions into the plasma include masses originating from solutions into the plasma include masses originating from p g gp g gthe solvent and any associated impurities i.e. SO, ArCl, the solvent and any associated impurities i.e. SO, ArCl, ClOClOBackground spectral features have been well Background spectral features have been well g pg pcharacterized characterized (Tan & Horlick (Tan & Horlick --Appl. Spectroscopy, 40, 445Appl. Spectroscopy, 40, 445--1986)1986)

Cl35O16 vs. V51

andand

Cl37O16 vs. Cr53

Isobaric InterferencesIsobaric InterferencesDue to isotopes shared among different elements

Nichel IronIsotope Abundance

58 68 %Isotope Abundance

54 6 %60 26 %61 1 %

56 92 %57 2 %

62 4 %64 1 %

58 0,3 %

Th il d th h ti ti18

They are easily removed through correction equationNi58(correct)= Ni58- 0.1429 * Fe57

Molecular Interferences in ICP-MS

Most difficult elements:

Interferent Element Isotope Ion

Calcium 40Ca 40Ar+

Vanadium 51V 16O35Cl+

Chromium 52Cr 40Ar12C+

Iron 56Fe 40Ar16O+ 40Ca16O+Iron 56Fe 40Ar16O+, 40Ca16O+

Arsenic 75As 40Ar35Cl+

Selenium 78Se 40Ar38Ar+Selenium Se Ar Ar

Typical Polyatomic InterferenceTypical Polyatomic InterferenceTypical Polyatomic InterferenceTypical Polyatomic Interference









ENEN ISO 17294ISO 17294 2 METHOD2 METHODENEN-- ISO 17294ISO 17294--2 METHOD 2 METHOD EN ISO 17294EN ISO 17294 2:20052:2005EN ISO 17294EN ISO 17294--2:20052:2005Metals on waterMetals on waterDetermination of 62 elements in water by ICPDetermination of 62 elements in water by ICP--MSMS

Thi th d h b li d t th d t i ti f Al A B CdThi th d h b li d t th d t i ti f Al A B CdThis method has been applied to the determination of: Al, As, B, Cd, This method has been applied to the determination of: Al, As, B, Cd, Cr, Cu, , Hg, Mn, Ni, Pb, Sb, Se and Zn.Cr, Cu, , Hg, Mn, Ni, Pb, Sb, Se and Zn.

The sample is filtered thruogh a 0.45µm filter and the liquid phase is The sample is filtered thruogh a 0.45µm filter and the liquid phase is acidified with nitric acidacidified with nitric acidacidified with nitric acidacidified with nitric acid

All these metals are determined with the ICPAll these metals are determined with the ICP--MS technique MS technique The content of the indicated metals in water samples is determined with The content of the indicated metals in water samples is determined with

ICPICP MSMSICPICP--MS. MS. The sample, in case diluted, is sucked up with a peristaltic pump, The sample, in case diluted, is sucked up with a peristaltic pump,

nebulized and ionized with the plasma (the most of elements is nebulized and ionized with the plasma (the most of elements is ionized at the 90% level)ionized at the 90% level)ionized at the 90% level). ionized at the 90% level).

The formed ionic stream is filtered with a quadrupole, which selects the The formed ionic stream is filtered with a quadrupole, which selects the mass to be analyzed, and measured by the detector. The use of the mass to be analyzed, and measured by the detector. The use of the internal standard is necessary to compensate drift effects of the tool internal standard is necessary to compensate drift effects of the tool y py pand effects of suppression of the signal related to the matrix. and effects of suppression of the signal related to the matrix.

For waters is used as internal standard the Rh.For waters is used as internal standard the Rh.

MW080.1CVE InMW080.1CVE In--house methodhouse method(determination of 30 metals in drinking,ground, and surface fresh (determination of 30 metals in drinking,ground, and surface fresh

waters and medium salt waters)waters and medium salt waters)

InIn--House Application of ISO 17294House Application of ISO 17294--2:20052:2005Characteristics:Characteristics:A.A. Selection of 30 out of 62 elements Selection of 30 out of 62 elements BB Selection of a restricted spectrum of Selection of a restricted spectrum of B.B. Selection of a restricted spectrum of Selection of a restricted spectrum of

isotopes to grant lower detection limitsisotopes to grant lower detection limitsDiff t d t i ti f LOQ (l Diff t d t i ti f LOQ (l C.C. Different determination of LOQ (lower Different determination of LOQ (lower quantification limit) in order to meet the quantification limit) in order to meet the

t i l t t ti f i l d t i l t t ti f i l d matrix element concentration of inland matrix element concentration of inland waters in the areawaters in the area

(A) and (B): Monitored Isotopes (A) and (B): Monitored Isotopes d C ti E tid C ti E tiand Correction Equationsand Correction Equations

(C): Solutions for Interference (C): Solutions for Interference ControlControl

The presence and rate of molecular interference is determined by The presence and rate of molecular interference is determined by The presence and rate of molecular interference is determined by The presence and rate of molecular interference is determined by the composition of the matrix, and, in turn, affects LOQthe composition of the matrix, and, in turn, affects LOQFor this reason, the solutions for LOQ determination have been For this reason, the solutions for LOQ determination have been prepared in order to mirror the matrix element concentration of prepared in order to mirror the matrix element concentration of p pp pdrinking water drinking water (ICS_POT(ICS_POT) and of inland water () and of inland water (ICSICS--SUPSUP) in the ) in the areaarea

Interferents

VALIDATION ACCORDING TO VALIDATION ACCORDING TO EN ISO/IEC EN ISO/IEC 1702517025SelectivitySelectivity Power to Power to distinguishdistinguish the analyte from interfering the analyte from interfering

speciesspecies

TruenessTrueness Closeness of agreementCloseness of agreement between the average value between the average value TruenessTrueness Closeness of agreementCloseness of agreement between the average value between the average value and an accepted reference valueand an accepted reference value

RecoveryRecovery Power to Power to detect a known quantitydetect a known quantity of the analyte of the analyte dd d t th t idd d t th t iadded to the matrixadded to the matrix

RepeatabilityRepeatability PrecisionPrecision underunder repeatabilityrepeatability conditionsconditions (same (same method, equipment, operator, short interval of time)method, equipment, operator, short interval of time)

ReproducibilityReproducibility Precision Precision under under reproducibility conditionsreproducibility conditions (same (same method, different equipment, operator)method, different equipment, operator)

Reproducibility Reproducibility 95% Absolute difference between two single test 95% Absolute difference between two single test Reproducibility Reproducibility limitlimit

95% Absolute difference between two single test 95% Absolute difference between two single test results obtained under reproducibility conditions results obtained under reproducibility conditions ≤≤R.L.R.L.

LODLOD Smallest quantitySmallest quantity of analyte that can be of analyte that can be detecteddetectedLODLOD Smallest quantitySmallest quantity of analyte that can be of analyte that can be detecteddetected

LOQLOQ Smallest quantitySmallest quantity of analited that can be of analited that can be measuredmeasured

i ii i RR i hi hi h h h d i i hi hi h h h d i liliLinearity rangeLinearity range RangeRange within which the method is within which the method is linearlinear

Application rangeApplication range RangeRange within which the method is within which the method is applicableapplicable

In house validationIn-house validationParameter Acceptability criteriona a p ab y oSelectivity Interferences < LOQ

Trueness t ≤ 2

Recovery 80 ÷ 120 %

Repeatability CV < 10 %

Reproducibility In the range 1- 10 µg/l:Al, B, Zn: CV < 30%Others: CV < 20%Others: CV < 20%

Repeatability limit ∆% max following readings < r%

LOD <1/5 limit fixed by National RegulationsLOD <1/5 limit fixed by National Regulations

LOQ < limit fixed by National Regulations

Linearity range Within application rangey g Within application range

Application range Suitable to concentration typical of drinking and inland water

InIn--house validation: selectivity & house validation: selectivity & LOQLOQ

The selectivity of the method was evaluated studying The selectivity of the method was evaluated studying the effect which main possible inteferents can exert the effect which main possible inteferents can exert the effect which main possible inteferents can exert the effect which main possible inteferents can exert on the analytes we are looking for (on the analytes we are looking for (false positivefalse positive).).

LOQs are determined experimentally according to LOQs are determined experimentally according to l il iregulationsregulations

Interferents

In–house validation: Trueness, recovery, repeatability, reproducibility

All thi t h b 1. All this parameters have been determined with test realized upon certified materials:certified materials:

TM-15 fortified water – NWRITM 27 2 f tifi d t NWRITM-27.2 fortified water – NWRI

These materials have two different levels f l t t ti t i th of analyte concentration to mirror the

levels most commonly found in our samplessamples

2. Trueness has furthermore been validated with partecipation to interlaboratory with partecipation to interlaboratory Proficiency Tests

PROFICIENCY TEST

PROFICIENCY TEST 2PROFICIENCY TEST-2 In-house validation: LOD, LOQ, linearity range

LOD h been dete mined n l ing ol tion LOD has been determined analyzing a solution fortified with concentration similar to predicted LODLODLOQ has been determined as three times the standard deviation of 10 measures obtained analyzing two solutions of interferents ICS-POT (drinking water) and ICS-SUP (inland water)water)The verification of linearity range has been carried out by means of a linear regression carried out by means of a linear regression using different standards at known concentrations

EXPERIMENTAL LOQs AS DETERMINED AFTER VALIDATION (FRESH WATERSAFTER VALIDATION (FRESH WATERS

AND MEDIUM SALT WATERS)

Analyte LOQ (µg/l) Analyte LOQ (µg/l)

Al 1.0

As 1.0

Hg 0.05 (CV-ICPMS)Mn 0.5

B 5.0

Be 0.5

Mo 0.5Ni 1.0

Cd 0.2

Co 0.5

Pb 0.5Sb 1.0S 5 0

Cr 1.0

Cu 1 0

Se 5.0Tl 0.5V 1 0Cu 1.0 V 1.0Zn 1.0









UNCERTAINTYUNCERTAINTY(VIM 3.9, UNI ENV 13005, B.2.18)Parameter, associated to the results of a measure, which quantify the dispersion of values reasonably attributable to the analyte being measuredthe analyte being measured.

To calculate the measurement uncertainty the top-down(*) approach has been applied, repeating tests on CRM (TM-15– NWRI; TM-27.2– NWRI), obtaining the standard deviation and comparing them with the method g p gISO-17294 precision data and applying the f-test

(*)

http://www.eurolab.org/docs/technical%20report/Technical_Report_Measurement_Uncertainty_2007.pdf

UNCERTAINTYIsotope CRM

Extended Uncertainty (M=1) Extended Uncertainty (M=2)

µg/l µg/l % µg/l %Al 27 NWRI TM 27 2 14 5 3 92 27 2 79 19UNCERTAINTY Al 27 NWRI TM-27-2 14,5 3,92 27 2,79 19

NWRI TM-15 21,7 6,5 30 4,62 21

As 75 NWRI TM-27-2 2,4 0,27 11 0,20 8

NWRI TM-15 14 6 1 93 13 1 38 9NWRI TM-15 14,6 1,93 13 1,38 9

Cd 114 NWRI TM-27-2 1,2 0,14 12 0,10 9

NWRI TM-15 13,2 0,57 4 0,41 3

Mn 55 NWRI TM-27-2 2,6 0,30 12 0,22 8Mn 55 NWRI TM 27 2 2,6 0,30 12 0,22 8

NWRI TM-15 18,4 2,48 13 1,76 10

Ni 58 NWRI TM-27-2 2,6 0,71 27 0,51 19

NWRI TM-15 18,1 2,33 13 1,65 9

Ni 60 NWRI TM-27-2 2,6 0,72 28 0,52 20

NWRI TM-15 18,1 2,36 13 1,67 9

Pb 206 NWRI TM-27-2 3,2 0,66 21 0,47 15

NWRI TM-15 11,8 2,11 18 1,50 13

Pb 207 NWRI TM-27-2 3,2 0,61 19 0,43 14

NWRI TM-15 11,8 1,64 14 1,17 10

Pb Sum NWRI TM-27-2 3,2 0,65 20 0,46 14

NWRI TM-15 11,8 1,84 16 1,31 11

V 51 NWRI TM-27-2 2,4 0,48 20 0,34 14

NWRI TM-15 12,4 2,33 19 1,65 13

Zn 66 NWRI TM-27-2 14,1 2,63 19 1,89 13

NWRI TM-15 32 4,83 15 3,45 11









EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs

THE DESCRIBED INSTRUMENTS & METHODS THE DESCRIBED INSTRUMENTS & METHODS CANNOT BE USED FOR SEA-WATERSMETHOD ISO-17294 NOT VALIDATED FOR METHOD ISO-17294 NOT VALIDATED FOR SEA-WATERS (ICP-MS NOT SUITABLE FOR SEA-WATER ANALYSIS))THEREFORE OTHER INSTRUMENTS AND/OR METHODS SHOULD BE USED

i i– Matrix separation

– Analyte preconcentration

– High Resolution ICP-MS

– Collision/Reaction Cell ICP-MS (not suitable for Collision/Reaction Cell ICP MS (not suitable for Hg)

EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO TRANSITIONAL AND SEATRANSITIONAL AND SEA WATERWATERTRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERsCollision Reaction Interface

(CRI)

EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs

TO CARRY OUT THE A l t (& it AA EQS Oth TO CARRY OUT THE ANALYSIS, SEA-WATERS SHOULD BE DILUTED 10-

Analyte (& its compounds)

AA-EQS- Other surface waters

FOLDLOQ 10-FOLD LOWERTHEN METHOD

µg/L

THEN, METHOD VALIDATION PROCESS IS TO BE RE-SHAPED (DIFFERENT METHOD

Cd 0.2

Pb 7 2(DIFFERENT METHOD, INSTRUMENT AND LIMITS) PROCESS CURRENTLY

Pb 7.2

Ni 20GOING ON (MeLA4-Project)

Hg 0.05

EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO TRANSITIONAL AND SEATRANSITIONAL AND SEA WATERsWATERsTRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs

EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO TRANSITIONAL AND SEATRANSITIONAL AND SEA WATERWATERTRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs









DIRECTIVE 2008/105/ECDIRECTIVE 2008/105/EC

MERCURY AS AN EXAMPLE OF A MERCURY AS AN EXAMPLE OF A PARTICULAR INPARTICULAR IN--HOUSE VALIDATIONHOUSE VALIDATIONPARTICULAR INPARTICULAR IN--HOUSE VALIDATIONHOUSE VALIDATION

►►SeaSea--water contains water contains 3030 g/Lg/L of dissolved of dissolved g/g/solidssolids-- Hg to be Hg to be measured= 1 x 10 measured= 1 x 10 --99((3030 ng/Lng/L))

Available I t t t

((3030 ng/Lng/L))

Instruments not sensible enough

(FIA-CV)

or not suitable for ot suitable for samples with samples with samples with samples with

salt content > salt content > 0.3%0.3%

(ICP-MS)

COLD VAPOR GENERATOR (CV) COUPLED WITH ICP MSCOUPLED WITH ICP-MS

METHOD VALIDATION ( ARPAV / PROCEDURE # PG01DL)

SELECTIVITY– Implied in Mass Spectrometryp p ySPECIFICITY– Implied in Hydride Generator p yLINEARITY (Tested up to 500 ng/L)

LOD (2 ng/L)LOD (2 ng/L)

LOQ (10 ng/L)

TRUENESS AND RECOVERY (tested with little TRUENESS AND RECOVERY (tested with little spike in matrix) REPEATABILITY (PRECISION)REPEATABILITY (PRECISION)

Hg IN-HOUSE VALIDATION: REPEATABILITY (PRECISION)

RESULTSHg 200 Hg 202

2000250030003500400045005000

Hg 200

Lineare (Hg 200) 3000

40005000

60007000

Hg 202

Lineare (Hg 202)

y = 77,916x + 607,74

0500

100015002000

0 10 20 30 40 50 60

II 608 /608 / 789 /789 /

y = 100,69x + 795,63

01000

2000

0 10 20 30 40 50 60

Intercept = Intercept = 608 c/s608 c/s 789 c/s789 c/sSlope = Slope = 78 c x L/s x ng78 c x L/s x ng 101 c x L/s x ng 101 c x L/s x ng RR22 = = 0,99820,9982 R2 = 0,9982 R2 = 0,9982

FUTHER VALIDATION(COLLABORATIVE TRIAL)

Results obtained with the described method (experimentedResults obtained with the described method (experimented in Lab 3) from certified reference material (Hg in sea water)

C C 9 0 0020 0 0002 /BCR- CRM 579 Hg= 0,0020 ± 0.0002 µg/L

Twinning Contract BG 06 IB EN 01

Ministry of Environment & Water

БлагодарияБлагодария(Grazie) G

MMaria T Palontaaria T PalontaRegional Environmental Protection Agency- Veneto Region

MMaria T. Palontaaria T. Palontag g y g

LABORATORY REGIONAL DEPARTMENT

VENICE LABORATORY SERVICEVENICE LABORATORY SERVICEVENICE LABORATORY SERVICEVENICE LABORATORY SERVICE

Simitli (BG)- 02/17-19, 2009

БлагодарияБлагодария

Grazie

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ICP-MS methods for metals-PAR1-5 complete.ppt [modalità ...old.iss.it/binary/itti/cont/Palonta_ICP-MS methods for metals_en... · Twinning Contract BG 06 IB EN 01 Ministry of Environment