Palonta_ICP-MS methods for metals_en.1235479234.pdf

8/10/2019 Palonta_ICP-MS methods for metals_en.1235479234.pdf

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ICPICP--MS (Inductively CoupledMS (Inductively Coupled

Plasma Mass Spectrometry)Plasma Mass Spectrometry)-- An analytical technique toAn analytical technique to

SpectrometrySpectrometry fromfrom IonsIons

generated by angenerated by an InductivelyInductivelyCoupled PlasmaCoupled Plasma-- Mass spectroscopyMass spectroscopy-- SeparationSeparation

andand measurementmeasurement of the mass ofof the mass ofindividual atoms making up aindividual atoms making up a

ICP-T o r c h M a s s S p e ct r o m e t e r Q u a d r u p o l e

Ne b u l i z e r

Interface

os e emen s are on zeos e emen s are on ze

Most elements form a MMost elements form a M++ (single ionization)(single ionization)

ICPICP--MS (Inductively CoupledMS (Inductively Coupled

Plasma Mass Spectrometry)Plasma Mass Spectrometry)ss

Rapid multiRapid multi--elementelementuantitative anal sisuantitative anal sis

CONsCONs

Isobaric Spectral OverlapsIsobaric Spectral Overlaps

Very low detection limitVery low detection limit

Wide dynamic rangeWide dynamic range

o ecu ar ver apso ecu ar ver aps Not suitable for samplesNot suitable for samples

>> Isotopes analysisIsotopes analysis

allowedallowed

. .

40

50

60

60

70

80

90

Pb Cr

20

30

20

30

40

50

0

10

204 206 207 208

0

10

50 52 53 54

PROsPROs-- Detection LimitsDetection Limits Most below 10 pptMost below 10 ppt

--

Most 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

..

ClCl 10 ug/L10 ug/L


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CONsCONs-- Molecular Overla sMolecular Overla s The chemical and physical conditions existing in theThe chemical and physical conditions existing in the

plasma and interface region may allow the formation ofplasma and interface region may allow the formation ofpo yatom c, or mo ecu ar ons. .e. H, , ArHpo yatom c, or mo ecu ar ons. .e. H, , ArH

The mass spectrum produced by introducing aqueousThe mass spectrum produced by introducing aqueoussolutions into the plasma include masses originating fromsolutions into the plasma include masses originating fromthe solvent and any associated impurities i.e. SO, ArCl,the solvent and any associated impurities i.e. SO, ArCl,ClOClO

Background spectral features have been wellBackground spectral features have been wellcharacterizedcharacterized (Tan & Horlick(Tan & Horlick --Appl. Spectroscopy, 40, 445Appl. Spectroscopy, 40, 445--1986)1986)

Cl35O16 vs. V51

Cl37O16 vs. Cr53

Due 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 %

18

ey are eas y remove roug correc on equa on

Ni58(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+

ron e r , a

Arsenic 75As 40Ar35Cl+

78 40 38 +


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Inhouse validation: Trueness,

recovery, repeatability, reproducibility

1. t s parameters ave een

determined with test realized upon

TM-15 fortified water NWRI

- . ort e water

These materials have two different levelso ana yte concentrat on to m rror t elevels most commonly found in our

2. Trueness has furthermore been validated

Proficiency Tests

PROFICIENCY TEST

-In-house validation: LOD, LOQ,

linearity range as een e erm ne ana yz ng a so u on

fortified with concentration similar to predicted

LOQ has been determined as three times thestandard deviation of 10 measures obtainedanalyzing two solutions of interferents ICS-POT (drinking water) and ICS-SUP (inland

The verification of linearity range has beencarried out b means of a linear re ression

using different standards at knownconcentrations


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..

2 .2 . CHARACTERS OF THE METHODS RECOMMEND ED BYCHARACTERS OF THE METHODS RECOMMEND ED BY

THE EC D I RECT I VETHE EC D I RECT I VE..

4 .4 . I CPI CP - - M SM S

a . D e f i n i t i o n a . D e f i n i t i o n

b . P r o s & C o n s b . P r o s & C o n s

5 .5 . T H E I SO 1 7 2 9 4 TH E I SO 1 7 2 9 4 - - 2 METHOD FOR THE ANALYS I S OF2 M ETHOD FOR THE ANALYS I S OFMETALSMETALS

6 .6 . THE ADOPTED METHOD AND I TS I N THE ADOPTED METHOD AND I TS I N - -HOUSEHOUSEV A LI D A TI O N V A LI D A TI O N

7 .7 . UNCERTA I NTY OF M EASUREUNCERTA I NTY OF M EASURE

8 .8 . EX TENT I ON FROM I N L AND W ATERS TOEXTENT I ON FROM I N L AND W ATERS TOTRANSI T I ONAL AND SEATRANSI T I ONAL AND SEA - - W A T ERs W ATER s

9 .9 . MERCURY AS AN EXAM PLE OF PART I CULARLYMERCURY AS AN EXAM PLE OF PART I CULARLY--

EXTENTION FROM INLAND TOEXTENTION FROM INLAND TO

TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs

CANNOT BE USED FOR SEA-WATERS -SEA-WATERS (ICP-MS NOT SUITABLE FORSEA-WATER ANALYSIS)

THEREFORE OTHER INSTRUMENTS AND/ORMETHODS SHOULD BE USED Matrix separation

Analyte preconcentration High Resolution ICP-MS

Collision Reaction Cell ICP-MS not suitable forHg)


-- ss

Collision Reaction Interface(CRI)


TRANSITIONAL AND SEATRANSITIONAL AND SEA-- WATERsWATERs

ANALYSIS, SEA-WATERSSHOULD BE DILUTED 10-

na y e scompounds)

- - ersurface waters

FOLD LOQ 10-FOLD LOWER

g/L

,VALIDATION PROCESS ISTO BE RE-SHAPED

Cd 0.2

,INSTRUMENT AND LIMITS)

PROCESS CURRENTLY

.

Ni 20

GOING ON (MeLA4-Project)Hg 0.05


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MERCURY AS AN EXAMPLE OF AMERCURY AS AN EXAMPLE OF A

--SeaSea--water containswater contains3030 /L/L of dissolvedof dissolvedsolidssolids-- Hg to beHg to be

measured= 1 x 10measured= 1 x 10--99

Availablens rumen s no

sensible enough(FIA-CV)

or not suitable forot suitable for

salt content >salt content >0.3%0.3%

(ICP-MS)

COLD VAPOR GENERATOR (CV)

-

METHOD VALIDATION

( ARPAV / PROCEDURE # PG01DL)

SELECTIVITY Im lied in Mass S ectrometr

SPECIFICITY Im lied in H dride Generator

LINEARITY (Tested up to 500 ng/L)

LOQ (10 ng/L)

spike in matrix)

Hg IN-HOUSE VALIDATION:

REPEATABILITY (PRECISION)


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RESULTSHg 200 Hg 202

2000

2500

3000

3500

4000

4500

5000

Hg 200

Lineare (Hg 200) 3000

4000

5000

6000

7000

Hg 202

Lineare (Hg 202)

y = 77,916x + 607,74

0

500

1000

1500

0 10 20 30 40 50 60

y = 100,69x + 795,63

0

1000

2000

0 10 20 30 40 50 60

Intercept =Intercept = 608 c/s608 c/s 789 c/s789 c/s

Slope =Slope = 78 c x L/s x ng78 c x L/s x ng 101 c x L/s x ng101 c x L/s x ng

RR22 == 0,99820,9982 R2 = 0,9982R2 = 0,9982

FUTHER VALIDATION

(COLLABORATIVE TRIAL)

in Lab 3) from cert ified reference material (Hg in sea water)

B R- RM 57 g= , . g L

Twinning Contract BG 06 IB EN 01

Ministry of Environment & Water

Grazie)

M

aria T Palontaria T Palonta

Regional Environmental Protection Agency- Veneto Region

M

aria T. Palontaria T. Palonta

LABORATORY REGIONAL DEPARTMENT

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

Grazie

Palonta_ICP-MS methods for metals_en.1235479234.pdf

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