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SAP/CSC/CAM/AAS-007a

Feb 2002

MATRIX MODIFIER (MM) FOR


GRAPHITE FURNACE ANALYSIS (GFA)
This article is a guide regarding the use of MM in GFA. Although it is derived from
several sources, it is not comprehensive and final. As could be seen, more than one type of MM
can be used for each element. End-users are encouraged to try out the various types of MM, the
appropriate MM concentration as well as the furnace temperature program to suit the various
sample matrixes.

ELEMENT/SAMPLE/MM

REMARKS

Aluminium (Al)
La(NO3)3
*City H2O
10 ppm Mg(NO3)2 or 10 ppm NH4Cl;
sample : modifier = 1:1

Serum and blood


Dilute Triton X-100

Effective with alloying.

Antimony (Sb)
Cu best, Ni, Pt also effective
La(NO3)3
*City H2O
10 ppm Pd using Pd(NO3)2 or
10 ppm Ni using Ni(NO3)2;
sample : modifier = 1:1
@
Electrolytic copper ore
200 ppb La from La(NO3)3

50-1000 ppm Ni(NO3)2

Alloying.
Alloying.

Permits a higher ashing temperature,


stabilises and enhances the signal.

100 ppm Pd(NO3)2 with 2.5% ascorbic


acid

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Permits a higher ashing temperature and


enhances the analyte signal.

Use secondary wavelength or Zeeman


background correction if interference is
expected from high Pb concentration which
may cause a measurable spectral interference
at 217.6 nm.

Arsenic (As)
Pd best, Mo, Zr, Ba also good
La(NO3)3

Mg(NO3)2, Ni(NO3)2

Coexistence with Ni is effective.


Production of As2O6 seems to be effective.

Increase ashing temperature.


(PTO)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Arsenic (As) (cont)


*City H2O
10 ppm Pd using Pd(NO3)2 or
10 ppm Ni using Ni(NO3)2;
sample : modifier = 1:1
@
Electrolytic copper ore
200 ppb La from La (NO3)3
$
10 ppm Ni from Ni(NO3)2
100-2000 ppm Pd or 10 l of 500 ppm
Pd or 100-2000 ppm Pt or 50 ppm Ni or
500-2000 ppm Pd solution + reducing
agent such as ascorbic acid

Nickel nitrate

Formation of nickel arsenide which is stable


up to 900oC so that higher ashing temperature
can be used.

Permits higher ashing temperature and


enhances signal.

Samples may be subjected to losses of As


during sample preparation as elemental As and
many of its compounds are volatile. Process
spiked samples and relevant standard
reference materials to determine if the chosen
dissolution method is appropriate.

Employ with caution the selection


temperatures and times of drying and ashing
cycles.

To minimise volatilisation losses during


drying and ashing.

Employ simultaneous background correction


to avoid erroneously high results due to severe
non-specific absorption and light scattering
caused by matrix components during
atomisation.
As analysis is particularly
susceptible to these problems because of its
low analytical wavelength (193.7 nm).

Use Zeeman background correction or any


appropriate background correction technique
to overcome severe positive interference
caused by Al, especially when using D2 arc
background correction.

Clean tube by operating the furnace at full


power at regular intervals to remove memory
effect caused by analyte that is not completely
volatilised and removed from furnace during
atomisation.

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Barium (Ba)
La(NO3)3

Effective with alloying.

Formation of less volatile barium carbide can


cause losses of sensitivity and memory effects.

Optimise furnace parameters to minimise


severe physical and chemical interferences
caused by long residence time and high
concentration of the analyte in optical path of
graphite furnace.

Do not use N2 as purge gas because of


possible chemical interference.

Do not use halide acids.

Beryllium (Be)
La(NO3)3

Effective with alloying.

Optimise furnace parameters to minimise


severe physical and chemical interferences
caused by long residence time and high
concentration of the atomised sample in
optical path of graphite furnace.

Require simultaneous background correction


to avoid erroneously high results due to severe
non-specific absorption and light scattering
caused by matrix components during
atomisation.

Bismuth (Bi)
Pb
Electrolytic copper ore
200 ppb La from La (NO3)3

1000 ppm Ni or 1000 ppm Pd

Boron (B)
$

500 ppm Ca

100 ppm Ba(OH)2 or 100 or


1000 ppm La(NO3)3/LaCl3

MIBK extract.

Permits a higher ashing temperature and


enhances signal.
$

May enhance sensitivity.


Enhances signal.

Cadmium (Cd)
Blood, serum, urine
Pd(NO3)2 + NH4NO3 ;
(NH4)2HPO4 + HNO3
La(NO3)3
Mg(NO3)2 ;
(NH4)H2PO4 + HNO3 or Mg(NO3)2

1% (NH4)2HPO4

ppb level
Effective with alloying.
Addition of F, SO42-, PO43- effective.

Ashing temperature can be increased. (PTO)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Cadmium (Cd) (cont)


*City H2O
10 ppm Pd using Pd(NO3)2 or
10 ppm NH4NO3;
sample : modifier = 1:1
*Environmental H2O; Wastewater
#
Vegetables, fruits, grains, beans,
potatoes, meat, fish, fats, oils, dairy
products, spirits, alcoholic beverages,
processed food
*10 ppm Pd using Pd(NO3)2;
sample : modifier = 1:1
$

1% (w/v) (NH4)2HPO4 or
1% (w/v) (NH4)SO4 or
0.1% (w/v) (NH4)MoO4.4H2O or
1% (v/v) H2SO4 or H3PO4 can be
substituted for ammonium salt solutions.

Excess NaCl
2% NH4NO3 or 2% NH4 oxalate

By the addition of phosphate ions, ashing


temperature can be increased due to the
formation of cadmium phosphate which is
stable up to 650-800oC.

To aid in low temperature removal of NaCl


through formation of NH4Cl and NaNO3
(reduction in non-atomic absorption).

Seawater
2% (NH4)H2PO4 or 2% NH4 oxalate

Soil
3% H3PO4 or 1-2% (NH4)H2PO4 ;
40 l modifier added to 20 l sample.

Plant tissue
2% H3PO4 or 2% (NH4)H2PO4 ;
40 l modifier added to 20 l sample.

Whole Blood
2% (NH4)2H2PO4

Infant formula, skim milk powder;

Streams, Effluents
0.5% (w/v) (NH4)H2PO4

1000 ppm H3PO4 or


1000 or 5000 ppm (NH4)H2PO4

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Conversion to less volatile phosphate so that


higher atomisation temperature can be used
and ensures a smooth peak.

Permits a higher ashing temperature.

Require simultaneous background correction


to avoid erroneously high results due to severe
non-specific absorption and light scattering
caused by matrix components during
atomisation.
(PTO)
_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM
Cadmium (Cd) (cont)

Ammonium
modifiers

phosphate

or

other

REMARKS

To minimise loss due to excess chloride


which may cause premature volatilisation of
Cd.

Use Cd-free pipette tips.

Cesium (Cs)
$

0.2% (v/v) H2SO4

Chromium (Cr)
La(NO3)3
*City H2O; Environmental H2O;
Wastewater
10 ppm NH4Cl; sample : modifier = 1:1

Seawater
1% Mg(NO3)2 or 1% HNO3

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

Serum and blood


Dilute Triton X-100

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Calcium nitrate

Cobalt (Co)

0.5% Fe(NO3)2

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Effective with alloying.

Reduces background
interferences.

signal,

minimises

Permits a higher ashing temperature.

Low concentrations of Ca and/or phosphate


may cause interferences. At above 200 mg/L,
Cas effect is constant and eliminates the
effect of phosphate.

Do not use N2 as purge gas because of a


possible CN band interference.

May require background correction because


non-specific absorption and scattering can be
significant at analytical wavelength.

To prevent coexistence of halogenide.

Permits a higher ashing temperature.

Verify that interference caused by excess


chloride is absent by standard additions.

Copper (Cu)
La(NO3)3
Soil with excess NaCl
40 l of 1% NH4NO3 added to 20 l of
sample.

Effective with alloying.

(PTO)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Copper (Cu) (cont)

Water and seawater


3000 ppm Na2O2

Substantially reduces interferences caused


by NaClO4; alkali metal halides; Al and Mg
halides.

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

Excess NaCl
2% NH4NO3 or 2% NH4 oxalate

500-2000 ppm Pd solution +


reducing agent e.g. ascorbic acid

To aid in low temperature removal of NaCl


through formation of NH4Cl and NaNO3
(reduction in non-atomic absorption).

Permits a higher ashing temperature.

May require background correction for nonspecific absorption and scattering which can
be significant at analytical wavelength.

Gallium (Ga)
Ni
500 ppm Pd or 5 l 100 ppm Pd or
1000 ppm Ni(NO3)2

Ni checks GaO production and avoids


inorganic matter interference.

Permits higher ashing temperature, enhances


signal and increases sensitivity.

Germanium (Ge)
500 ppm Pd or 5 l of 100 ppm Pd

Permits a higher ashing temperature,


enhances signal and improves sensitivity.

Gold (Au)

0.25% Ni(NO3)2

500-2000 ppm Pd solution +


reducing agent such as Acorbic acid

Permits a higher ashing temperature.


Permits a higher ashing temperature.

Indium (In)
Pd
La(NO3)3
$
1% (w/v) ammonium fluoride, NH4F

1000 ppm Pd or 5 l of 1000 ppm Pd

Pd checks production of InO sublimation.


Alloying.
$
Higher ashing temperature can be used.

A higher ashing temperature can be used and


improves sensitivity.

Iron (Fe)

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Permits a higher ashing temperature.

As Fe is a universal contaminant, great care


should be taken particularly at low levels.

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Lead (Pb)
Mg(NO3)2
La(NO3)3 ; Pd, Pt (g level)
*City H2O
10 ppm Pd from Pd(NO3)2 or
10 ppm NH4Cl;
sample : modifier = 1:1
*Environmental H2O; Wastewater
#
Vegetables, fruits, grains, beans,
potatoes, meat, fish, fats, oil, dairy
products, spirits, alcoholic beverages,
processed foods
*10 ppm Pd from Pd(NO3)2;
sample: modifier = 1:1
@
Electrolytic copper ore
200 ppb La from La (NO3)3

Medicines
10 ppm Pd from Pd(NO3)2

Excess NaCl
2% NH4NO3 or 2% NH4 oxalate

Seawater
10% ascorbic acid

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

Blood
0.1% Triton X-100

Infant formula, skim milk powder;

Streams, Effluents
0.5% (w/v) (NH4)H2PO4

1000 or 5000 ppm H3PO4 or


5000 ppm (NH4)H2PO4

0.5-1% (v/v) EDTA or


0.5-1% (v/v) citrate or
0.5-1% (v/v) oxalate

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Phosphoric acid

Coexistence with NaCl, KCl, MgCl, etc


prevents PbCl2 sublimation.
Effective by addition of HNO3, high
sensitivity obtained by alloying.

To aid in low temperature removal of NaCl


through formation of NH4Cl and NaNO3
(reduction in non-atomic absorption).

Suppresses matrix interferences.

Dispersing agent -facilitates dispersing.

Permits a higher ashing temperature and


stabilises the signal.

Stabilises Pb which atomises at a lower


temperature than does a nitrate or chloride
matrix.

Permits a higher ashing temperature.

Require background correction.


May be necessary if poor recoveries are
obtained.

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM

REMARKS

Manganese (Mn)
La(NO3)3

HNO3

Effective with alloying.

Ashing temperature can be increased from


1100 to 1150oC.

*City H2O; Waste H2O


10 ppm Mg(NO3)2 or 10 ppm NH4Cl;
sample : modifier = 1:1

Seawater
10% ascorbic acid

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

Serum and blood


Dilute Triton X-100

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Suppresses matrix interferences.

Permits a higher ashing temperature.

Must use background correction.

Mercury (Hg)
Soil
Organic acid (succinic acid, tartaric acid)
Sulfide + HNO3
HCl + H2O2
K2Cr2O7 + Na2S
Au, Pt, Pd (g level)
Se
$
Ammonium Sulfide
$

For diluent, use:


1) 1000 ppm Te in 1% HCl or
2) 0.1% K2Cr2O7 in 0.5% HNO3
$
Organo-sulfur compounds such
cysteine.

Excess (NH4)2S
500-2000 ppm Pd solution +
reducing agent such as ascorbic acid or
1000 ppm Pd

as

Volatization prevention as HgS.


For prevention of reduction in vaporisation as
HgS.
To prevent volatization by amalgamation.
$

Volatization prevention as HgS which is


stable at 150oC to prevent loss of mercury
vapour during drying cycle.

As complexing agents to increase ashing


temperature to 500oC to minimise chemical
and bulk matrix interference.

Stabilises the signal.

Permits a higher ashing temperature and


enhances the signal.

Molybdenum (Mo)
*City H2O
10 ppm asorbic acid;
sample : modifier = 1:1

Seawater
10% ascorbic acid

Suppresses matrix interferences.


(PTO)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

ELEMENT/SAMPLE/MM
Molybdenum (Mo) (cont)

REMARKS

Use pyrolytically coated graphite tube as Mo


is prone to carbide formation.

May require cleaning of furnace after


analysis of more concentrated samples or
standards as memory effects are possible.

Nickel (Ni)
*City H2O
10 ppm Mg(NO3)2 or 10 ppm NH4Cl;
sample : modifier = 1:1

Seawater
1% Mg(NO3)2 or 1% HNO3

Seawater
2-10% NH4NO3 or 2% NH4 oxalate

500-2000 ppm Pd solution +


reducing agent such as ascorbic acid

Reduces background
interferences.

signal,

minimises

Permits a higher ashing temperature.

Background
correction
is
strongly
recommended as Ni can suffer from severe
non-specific absorption and scattering caused
by matrix components during atomisation.

The use of separate graphite furnace tubes


and contact rings from those used in analysis
of As and Se where nickel nitrate MM is used
is strongly recommended to minimise severe
memory effects.

Phosphorus (P)

La(NO3)3 e.g. $0.1% La from La(NO3)3


or

0.2% from nitrate


$
200 ppm Ni from Ni(NO3)2 or

2000 ppm Ni from Ni(NO3)2

5 l of 1000 ppm La

Sensitivity improves 6 times.

Permits a higher ashing temperature and


improves precision.
$
Higher ashing temperature can be used.

Improves precision.

Selenium (Se)
Mg(NO3)2
Al, Cu, Ni, Pd, Pt

Cu, Mo and Ni
*City H2O
10 ppm Pd; sample : modifier = 1:1
$
10 ppm from Ni(NO3)2

Coexistence with Ni is effective (NiSe


produced).
Pd particularly good, PdSe produced.

Ashing temperature can be increased from


1000 -1100oC.
$

Formation of nickel selenide which is stable


up to 900 or 1000oC.
(PTO)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

10

ELEMENT/SAMPLE/MM

REMARKS

Selenium (Se) (cont)

Whole blood
Dilute blood 5 times in diluting agent
consisting of:
0.5% Triton X-100
+ 0.125% Dow Corning Antifoam B
+ 0.25% ascorbic acid.
Add 0.05% Pd as MM.

1% Ni(NO3)2 or 10 l of 500 ppm Pd

Nickel nitrate

1% Ni from nickel nitrate

Permits a higher ashing temperature and


enhances the signal.

Samples may be subjected to losses of Se


during sample preparation as elemental Se and
many of its compounds are volatile. Process
spiked samples and relevant standard
reference materials to determine if the chosen
dissolution method is appropriate.

Employ with caution the selection of


temperatures and times for drying and ashing
cycles.

To minimise volatilisation losses during


drying and ashing.

Requires
simultaneous
background
correction to avoid erroneously high results
due to severe non-specific absorption and light
scattering caused by matrix components
during atomisation because of its low
analytical wavelength (196.0 nm).

Zeeman background correction is useful


when high Fe levels can give overcorrections
with D2 background.

Clean tube by operating furnace at full power


at regular intervals to remove memory effect
caused by analyte that is not completely
volatilised and removed from furnace during
atomisation.

To lessen interferences caused by chlorides


(> 800 mg/L) and sulfate (> 200 mg/L).

Silicon (Si)
La(NO3)3
$
2 ppm Ba and 100 ppm La, both from
chloride salts

Effective with alloying.


$
Minimise silicon carbide formation and
ashing temperature can be increased to
1000oC.

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

11

ELEMENT/SAMPLE/MM

REMARKS

Silver (Ag)

1% (NH4)H2PO4

500-2000 ppm Pd +
reducing agent such as ascorbic acid

Permits a higher ashing temperature.


Permits a higher ashing temperature.

Employ simultaneous background correction


to avoid erroneously high results due to severe
non-specific absorption and light scattering
caused by matrix components during
atomisation.

Should clean tube by operating furnace at


higher atomisation temperature to remove
memory effect caused by analyte that is not
completely volatilised and removed from
furnace during atomisation.

Store Ag standards in brown bottles as they


are light sensitive and have the tendency to
plate out on container walls.

Avoid HCl as silver chloride is insoluble


unless the Ag is already in solution as a
chloride complex.

Tellurium (Te)
$

10 ppm Ni from Ni(NO3)2

0.1% or 1% Ni(NO3)2
5 l 1000 ppm Pd

To maximize ashing temperature.


Permits a higher ashing temperature and
enhances the signal.

Permits a higher ashing temperature and


enhances the signal.

Terbium (Tb)
$

0.02 mg Ni from Ni(NO3)2

Thallium (Tl)
Pd + HClO4
La(NO3)3

1% H2SO4

500-2000 ppm Pd +
reducing agent such as ascorbic acid

Coexistence with ascorbic acid is effective, Pd


checks TlCl production.
Alloying.

Stabilises the signal.

Permits a higher ashing temperature.

Require background correction.


HCl or excessive chloride will cause
volatilisation of Tl at low temperature. Verify
that losses are not occurring by spiking
samples or using standard additions method.

A suitable MM.

Pd

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

12

ELEMENT/SAMPLE/MM

REMARKS

Tin (Sn)
Mg(NO3)2, (NH4)2HPO4
La(NO3)3
K2MO4
NH4NO3, (NH4)2C2O4
Spirits, alcoholic beverage, processed
foods
10 ppm Pd using Pd(NO3)2
$
0.2% (w/v) K2Cr2O7 + 1% HCl or
3% HNO3 + 10% (1 : 1) NH4OH

0.1% diammonium hydrogen citrate


#

500-2000 ppm Pd solution + reducing


agent such as ascorbic acid

500 ppm Pd or 5 l of 100 ppm Pd

Use with ascorbic acid to prevent interference.


Effective by alloying.
Sensitivity improves remarkably but chloride
interference exists.
No chloride interference.

Complexes with Sn and enhances


sensitivity.

Stabilises the Sn in solution and facilitates


production of a single peak.

Permits a higher ashing temperature and


enhances the signal.

Permits a higher ashing temperature and


enhances the signal.

Vanadium (V)

Seawater
10% ascorbic acid

Suppresses matrix interferences.

Require background correction.


Clean furnace before and after analysis as Va
is refractory and prone to form carbides.

Do not use N2 as purge gas.

Yttrium (Y)
$

0.02 mg Ni from Ni(NO3)2

Zinc (Zn)
Succinic acid, oxalic acid

MaCl2 produces ZnCl2 and sublimation.


Organic acid checks it.

Should use background correction.

As Zn is a universal contaminant, great care


should be taken.

Notes:
The information is mainly taken from Shimadzu AAS Cookbook Section 2. The rest are taken
from the following:

Shimadzu AAS Cookbook Section 4 (Measuring Conditions of Elements of


Furnace Analysis Method)
Shimadzu AAS Cookbook Section 5 (Water Analysis and Air Analysis)

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore

13
Notes (cont):
#

=
=
=
=
=
=

(PTO)

Shimadzu AAS Cookbook Section 6 (Foodstuffs Analysis, Fertilizer and Feed


Analysis)
Shimadzu AAS Cookbook Section 8 (Non-ferrous Metals Analysis)
Shimadzu AAS Cookbook Section 10 (Medicines and Biological Substances)
CRC Handbook Of Furnace AAS
Analytical Methods for Zeeman Graphite Tube Analysers
USEPA SW-846
Continue on following page

For seawater, NH4NO3 is added to aid in the low temperature removal of NaCl by the formation
of NH4Cl and NaNO3.

_____________________________________________________________________________

Shimadzu (Asia Pacific) Pte Ltd, Singapore