Palonta - ICP-MS Methods For Metals - En.1235479234 PDF

Twinning Contract BG 06 IB EN 01
Ministry of Environment & Water

ICP ICP- -MS methods for metals: MS methods for metals:
in in house validation and extension house validation and extension in in--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 sea and sea water water and sea and sea--water. water.
Maria T. Palonta Maria T. Palonta
Regional Environmental Protection Agency- Veneto Region
LABORATORY REGIONAL DEPARTMENT
VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE
Simitli (BG)- 02/17-19, 2009
SUMMARY SUMMARY SUMMARY SUMMARY
11 BACKGROUND BACKGROUND 1. 1. BACKGROUND BACKGROUND
2. 2. CHARACTERS OF THE METHODS RECOMMENDED BY CHARACTERS OF THE METHODS RECOMMENDED BY
THE EC DI RECTI VE THE EC DI RECTI VE
33 AVAI LABLE TECHNI QUES FOR METALS AVAI LABLE TECHNI QUES FOR METALS 3. 3. AVAI LABLE TECHNI QUES FOR METALS AVAI LABLE TECHNI QUES FOR METALS
4. 4. I CP I CP- - MS MS
a. Definition a. Definition
b P & C b P & C b. Pros & Cons b. Pros & Cons
5. 5. THE I SO 17294 THE I SO 17294-- 2 METHOD FOR THE ANALYSI S OF 2 METHOD FOR THE ANALYSI S OF
METALS METALS
66 THE ADOPTED METHOD AND I TS I N THE ADOPTED METHOD AND I TS I N HOUSE HOUSE 6. 6. THE ADOPTED METHOD AND I TS I N THE ADOPTED METHOD AND I TS I N-- HOUSE HOUSE
VALI DATI ON VALI DATI ON
7. 7. UNCERTAI NTY OF MEASURE UNCERTAI NTY OF MEASURE
88 EXTENTI ON FROM I NLAND WATERS TO EXTENTI ON FROM I NLAND WATERS TO 8. 8. EXTENTI ON FROM I NLAND WATERS TO EXTENTI ON FROM I NLAND WATERS TO
TRANSI TI ONAL AND SEA TRANSI TI ONAL AND SEA-- WATERS WATERS
9. 9. MERCURY AS AN EXAMPLE OF PARTI CULARLY MERCURY AS AN EXAMPLE OF PARTI CULARLY
COMPLEX I N COMPLEX I N HOUSE VALI DATI ON HOUSE VALI DATI ON COMPLEX I N COMPLEX I N-- HOUSE VALI DATI ON HOUSE VALI DATI ON
METALS METALS
TRANSI TI ONAL AND SEA TRANSI TI ONAL AND SEA-- WATERS WATERS
11-- BACKGROUND BACKGROUND 11 BACKGROUND BACKGROUND
DIRECTIVE 2000/60/EC OF THE EUROPEAN PARLIAMENT AND OF DIRECTIVE 2000/60/EC OF THE EUROPEAN PARLIAMENT AND OF
THE COUNCIL THE COUNCIL THE 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 y g y
water policy water policy
DIRECTIVE 2008/105/EC OF THE EUROPEAN PARLIAMENT
AND OF THE COUNCIL
of 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 il and of the Council
11-- BACKGROUND BACKGROUND
Directive 2000/60/EC Directive 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/EC DIRECTIVE 2008/105/EC
METALS METALS
TRANSI TI ONAL AND SEA TRANSI TI ONAL AND SEA-- WATERs WATERs
CHARACTERS OF THE METHODS CHARACTERS OF THE METHODS
RECOMMENDED BY THE EC DIRECTIVE RECOMMENDED BY THE EC DIRECTIVE RECOMMENDED BY THE EC DIRECTIVE RECOMMENDED BY THE EC DIRECTIVE
WFD WFD requirements for analytical methods requirements for analytical methods
Annex V, paragraph 1.3.6 Annex 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
methods methods
that 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 standards international standards international standards international standards
or 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 pp
equivalent or better scientific quality and equivalent or better scientific quality and
comparability than standard analytical comparability than standard analytical
th d th d methods methods
Requirements from QA/QC COM Requirements from QA/QC COM
Li it f tifi ti ( Li it f tifi ti (LOQ LOQ) l b l ) l b l
decision decision
Limit of quantification ( Limit of quantification (LOQ LOQ) equal or below ) equal or below
30% 30%of the relevant Environmental Quality of the relevant Environmental Quality
Standards ( Standards (EQS EQS)) Sta da ds ( Sta da ds ( QS QS))
LOQ versus Lower Limit of LOQ versus Lower Limit of
Application( Application(LLOA LLOA) )
LOQ LOQ = lab specific performance value = lab specific performance value
LLOA LLOA = 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 EQS EQS
Validation Validation according to according to EN ISO/IEC 17025 EN ISO/IEC 17025 gg //
METALS: AVAILABLE METALS: AVAILABLE
TECHNIQUES TECHNIQUES
GFAAS GFAAS
FAAS FAAS
HGAAS HGAAS
ICP ICP OES OES ICP ICP--OES OES
CC SS
COMPARISON OF ICP COMPARISON OF ICP- -MS TO MS TO
OTHER TECHNIQUES OTHER TECHNIQUES
Shares applications with ICP Shares applications with ICP- -OES and AAS OES and AAS
Shares multielement characteristic with Shares multielement characteristic with
ICP ICP--OES OES
Shares analytical speed with ICP Shares analytical speed with ICP--OES OES Shares analytical speed with ICP Shares analytical speed with ICP OES OES
Shares detection limits with GFAAS Shares detection limits with GFAAS
Unique in isotope measurement capability Unique in isotope measurement capability Unique in isotope measurement capability Unique in isotope measurement capability
Unique in rapid semiquantitative analysis Unique in rapid semiquantitative analysis
METALS METALS
ICP ICP- -MS (Inductively Coupled MS (Inductively Coupled
Plasma Mass Spectrometry) Plasma Mass Spectrometry)
-- An analytical technique to An analytical technique to
determine determine Elements Elements using using Mass Mass determine determine Elements Elements using using Mass Mass
Spectrometry Spectrometry from from Ions Ions
generated by an generated by an Inductively Inductively
Coupled Plasma Coupled Plasma
-- Mass spectroscopy Mass spectroscopy- - Separation Separation
and and measurement measurement of the mass of of the mass of
individual atoms making up a individual atoms making up a
given material given material given material given material
ICP-Torch Mass Spectrometer
Quadrupole
Nebulizer
Q p
Interface
Ionization Process in Plasma Ionization Process in Plasma Ionization Process in Plasma Ionization 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 M Most elements form a M
+ +
(single ionization) (single ionization)
ICP ICP- -MS (Inductively Coupled MS (Inductively Coupled
Plasma Mass Spectrometry) Plasma Mass Spectrometry)
PRO PRO PROs PROs
Rapid multi Rapid multi--element element
quantitative analysis quantitative analysis
CONs CONs
Isobaric Spectral Overlaps Isobaric Spectral Overlaps
Mole la O e laps Mole la O e laps
q y q y
Very low detection limit Very low detection limit
Wide dynamic range Wide dynamic range
Molecular Overlaps Molecular Overlaps
Not suitable for samples Not suitable for samples
with salt content > 0.3% with salt content > 0.3%
Isotopes analysis Isotopes analysis
allowed allowed
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
PROs PROs-- Detection Limits Detection Limits PROs PROs Detection Limits Detection Limits
Most below 10 ppt Most below 10 ppt
Most elements 10 X better than GF Most elements 10 X better than GF--AAS AAS Most elements 10 X better than GF Most elements 10 X better than GF AAS AAS
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,
Pt Pt
< 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:
I I 0.01 ug/L 0.01 ug/L
Br Br 0 2 ug/L 0 2 ug/L Br Br 0.2 ug/L 0.2 ug/L
Cl Cl 10 ug/L 10 ug/L
CONs CONs-- Molecular Overlaps Molecular Overlaps CONs CONs Molecular Overlaps Molecular Overlaps
The 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 CO l i l l i i O CO polyatomic, or molecular ions. i.e. OH, CO, ArH polyatomic, or molecular ions. i.e. OH, CO, ArH
The 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 g p g g
the solvent and any associated impurities i.e. SO, ArCl, the solvent and any associated impurities i.e. SO, ArCl,
ClO ClO
Background spectral features have been well Background spectral features have been well g p g p
characterized characterized
(Tan & Horlick (Tan & Horlick --Appl. Spectroscopy, 40, 445 Appl. Spectroscopy, 40, 445- -1986) 1986)
Cl
35
O
16
vs. V
51
and and
Cl
37
O
16
vs. Cr
53
Isobaric Interferences Isobaric Interferences
Due to isotopes shared among different elements
Nichel Iron
Isotope 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 ti
18
They are easily removed through correction equation
Ni58(correct)= Ni58- 0.1429 * Fe57
Molecular Interferences in ICP-
MS
Most difficult elements:
Interferent Element Isotope Ion
Calcium
40
Ca
40
Ar
+
Vanadium
51
V
16
O
35
Cl
+
Chromium
52
Cr
40
Ar
12
C
+
Iron
56
Fe
40
Ar
16
O
+ 40
Ca
16
O
+
Iron
56
Fe
40
Ar
16
O
+
,
40
Ca
16
O
+
Arsenic
75
As
40
Ar
35
Cl
+
Selenium
78
Se
40
Ar
38
Ar
+
Selenium Se Ar Ar
Typical Polyatomic Interference Typical Polyatomic Interference Typical Polyatomic Interference Typical Polyatomic Interference
METALS METALS
EN EN ISO 17294 ISO 17294 2 METHOD 2 METHOD EN EN-- ISO 17294 ISO 17294--2 METHOD 2 METHOD
EN ISO 17294 EN ISO 17294 2:2005 2:2005 EN ISO 17294 EN ISO 17294--2:2005 2:2005
Metals on water Metals on water
Determination of 62 elements in water by ICP Determination of 62 elements in water by ICP--MS MS
Thi th d h b li d t th d t i ti f Al A B Cd Thi th d h b li d t th d t i ti f Al A B Cd This 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 0.45m filter and the liquid phase is The sample is filtered thruogh a 0.45m filter and the liquid phase is
acidified with nitric acid acidified with nitric acid acidified with nitric acid acidified with nitric acid
All these metals are determined with the ICP All 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
ICP ICP MS MS ICP ICP--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 p y p
and 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 In MW080.1CVE In--house method house 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)
In In- -House Application of ISO 17294 House Application of ISO 17294- -2:2005 2:2005
Characteristics: 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 limits isotopes to grant lower detection limits
Diff 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 area waters in the area
(A) and (B): Monitored Isotopes (A) and (B): Monitored Isotopes
d C ti E ti d C ti E ti and Correction Equations and Correction Equations
(C): Solutions for Interference (C): Solutions for Interference
Control Control
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 LOQ the composition of the matrix, and, in turn, affects LOQ
For 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 p p p
drinking water drinking water (ICS_POT (ICS_POT) and of inland water ( ) and of inland water (ICS ICS- -SUP SUP) in the ) in the
area area
Interferents
VALIDATION ACCORDING TO VALIDATION ACCORDING TO EN ISO/IEC EN ISO/IEC
17025 17025 Selectivity Selectivity Power to Power to distinguish distinguish the analyte from interfering the analyte from interfering
species species
Trueness Trueness Closeness of agreement Closeness of agreement between the average value between the average value Trueness Trueness Closeness of agreement Closeness of agreement between the average value between the average value
and an accepted reference value and an accepted reference value
Recovery Recovery Power to Power to detect a known quantity detect a known quantity of the analyte of the analyte
dd d t th t i dd d t th t i added to the matrix added to the matrix
Repeatability Repeatability Precision Precision under under repeatability repeatability conditions conditions (same (same
method, equipment, operator, short interval of time) method, equipment, operator, short interval of time)
Reproducibility Reproducibility Precision Precision under under reproducibility conditions reproducibility 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
limit limit
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.
LOD LOD Smallest quantity Smallest quantity of analyte that can be of analyte that can be detected detected LOD LOD Smallest quantity Smallest quantity of analyte that can be of analyte that can be detected detected
LOQ LOQ Smallest quantity Smallest quantity of analited that can be of analited that can be measured measured
i i i i RR i hi hi h h h d i i hi hi h h h d i li li Linearity range Linearity range Range Range within which the method is within which the method is linear linear
Application range Application range Range Range within which the method is within which the method is applicable applicable
In house validation In-house validation
Parameter Acceptability criterion a a p ab y o
Selectivity Interferences < LOQ
Trueness t 2
Recovery 80 120 %
Repeatability CV < 10 %
Reproducibility In the range 1- 10 g/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 Regulations LOD <1/5 limit fixed by National Regulations
LOQ < limit fixed by National Regulations
Linearity range Within application range y g Within application range
Application range Suitable to concentration typical of drinking and
inland water
In In--house validation: selectivity & house validation: selectivity &
LOQ LOQ
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 positive false positive). ).
LOQs are determined experimentally according to LOQs are determined experimentally according to
l i l i regulations regulations
Interferents
Inhouse 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 NWRI
TM 27 2 f tifi d t NWRI TM-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
samples samples
2.
Trueness has furthermore been validated
with partecipation to interlaboratory with partecipation to interlaboratory
Proficiency Tests
PROFICIENCY TEST
PROFICIENCY TEST 2 PROFICIENCY 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
LOD LOD
LOQ 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 WATERS AFTER VALIDATION (FRESH WATERS
AND MEDIUM SALT WATERS)
Analyte
LOQ (g/l)
Analyte
LOQ (g/l)
Al 1.0
As 1.0
Hg 0.05 (CV-ICPMS)
Mn 0.5
B 5.0
Be 0.5
Mo 0.5
Ni 1.0
Cd 0.2
Co 0.5
Pb 0.5
Sb 1.0
S 5 0
Cr 1.0
Cu 1 0
Se 5.0
Tl 0.5
V 1 0
Cu 1.0
V 1.0
Zn 1.0
METALS METALS
UNCERTAINTY UNCERTAINTY
(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 measured the 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 g
ISO-17294 precision data and applying the f-test
(*)
http://www.eurolab.org/docs/technical%20report/Technical_Report_Measur
ement_Uncertainty_2007.pdf
UNCERTAINTY
Isotope CRM
Extended Uncertainty (M=1) Extended Uncertainty (M=2)
g/l g/l % g/l %
Al 27 NWRI TM 27 2 14 5 3 92 27 2 79 19
UNCERTAINTY
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 9 NWRI 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 8 Mn 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
METALS METALS
EXTENTION FROM INLAND TO EXTENTION FROM INLAND TO
TRANSITIONAL AND SEA TRANSITIONAL AND SEA-- WATERs WATERs
THE DESCRIBED INSTRUMENTS & METHODS THE DESCRIBED INSTRUMENTS & METHODS
CANNOT BE USED FOR SEA-WATERS
METHOD 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)
TRANSITIONAL AND SEA TRANSITIONAL AND SEA WATER WATER TRANSITIONAL AND SEA TRANSITIONAL AND SEA-- WATERs WATERs
Collision Reaction Interface
(CRI)
TRANSITIONAL AND SEA TRANSITIONAL AND SEA-- WATERs WATERs
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
FOLD
LOQ 10-FOLD LOWER
THEN METHOD
g/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 20
GOING ON (MeLA4-Project)
Hg 0.05
TRANSITIONAL AND SEA TRANSITIONAL AND SEA WATERs WATERs TRANSITIONAL AND SEA TRANSITIONAL AND SEA-- WATERs WATERs
TRANSITIONAL AND SEA TRANSITIONAL AND SEA WATER WATER TRANSITIONAL AND SEA TRANSITIONAL AND SEA-- WATERs WATERs
METALS METALS
DIRECTIVE 2008/105/EC DIRECTIVE 2008/105/EC
MERCURY AS AN EXAMPLE OF A MERCURY AS AN EXAMPLE OF A
PARTICULAR IN PARTICULAR IN--HOUSE VALIDATION HOUSE VALIDATION PARTICULAR IN PARTICULAR IN--HOUSE VALIDATION HOUSE VALIDATION
Sea Sea--water contains water contains
30 30 g/L g/L of dissolved of dissolved g/ g/
solids solids- - Hg to be Hg to be
measured= 1 x 10 measured= 1 x 10
--99
((30 30 ng/L ng/L))
Available
I t t t
((30 30 ng/L ng/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 MS COUPLED WITH ICP-MS
METHOD VALIDATION
( ARPAV / PROCEDURE # PG01DL)
SELECTIVITY
Implied in Mass Spectrometry p p y
SPECIFICITY
Implied in Hydride Generator p y
LINEARITY (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)
RESULTS
Hg 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
2000
0 10 20 30 40 50 60
II 608 / 608 / 789 / 789 /
y = 100,69x + 795,63
0
1000
2000
0 10 20 30 40 50 60
Intercept = Intercept = 608 c/ s 608 c/ s 789 c/ s 789 c/ s
Slope = Slope = 78 c x L/ s x ng 78 c x L/ s x ng 101 c x L/ s x ng 101 c x L/ s x ng
RR
22
= = 0,9982 0,9982 R2 = 0,9982 R2 = 0,9982
FUTHER VALIDATION
(COLLABORATIVE TRIAL)
Results obtained with the described method (experimented Results 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 g/L
Twinning Contract BG 06 IB EN 01
Ministry of Environment & Water

(Grazie) G
MMaria T Palonta aria T Palonta
Regional Environmental Protection Agency- Veneto Region
MMaria T. Palonta aria T. Palonta
g g y g
LABORATORY REGIONAL DEPARTMENT
VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE VENICE LABORATORY SERVICE
Simitli (BG)- 02/17-19, 2009

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Twinning Contract BG 06 IB EN 01

Ministry of Environment & Water

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