smart solid sample trace analysis by...

1 Spectral Systems, D-82256 Fürstenfeldbruck, Germany; [email protected] 2 D-87471 Durach, Germany

Smart Solid Sample Trace Analysis by ETV-ICPSome examples for direct analysis by Electrothermal Vaporisation as add-on for ICP

P. Perzl1, J. Hassler2

Instead of diluting solid samples (time consuming, pure and often dangerous agents needed, contaminations..) some mg (<1 to 20mg, up to 300mg for carbon matrices) are weighed directly into a graphite boat to be evaporated accordingly in a special graphite tube furnace, continuously adding some halogenated modifier gas. This halogenisation transfers carbide forming elements into volatile halogenides. Even elements like W, Mo, V can be analysed easily. The resulting vapour is transfered into an aerosol by an additional Argon stream and is lead directly into an ICP-injector by a short tube. Here the excitation takes place. Arbitrary temperature programs can be run to separate elements in time, for example to avoid spectral interferences or to determine species of an element (e.g. sulfur).

One of the most important aspects of each analytical method are its possibilities of calibration, especially for solid sampling methods. How difficult is a calibration, are reference materials available, or is it even possible to work without solid SRM´s ? While liquid analysis (like ICP-OES) is mostly free of such issues, for many applications solid SRMs are not available. But in ETV calibration can be done easily using common aquaeous standards, dried directly in a boat, and frequently even without matrix-compensation.The results below demonstrate that this easy procedure helps to achieve excellent results in a wide field of applications of ETV-ICP. Analysing different materials such as copper, graphite, SiC, boron-nitride and apple-leaves (as an example for many organic samples) the calibration-functions of some elements show that a convenient calibration using solid as well as aquaeous standards is common.

Calibration in ETV-analysis

The method ETV - how does it work?

ETV 4000c (Spectral Systems):Temperature-controlled evaporation of the sample (1-20 mg) in a graphite boat, placed in a graphite-tube furnace under argon atmosphere , electronic controlled gas-flow and addition of a halogenated reaction-gas (modifier). Transport of the aerosole to the ICP-plasma by an optimised gas guide with high transport-efficiency. Integrated microprocessor-control with graphic LCD-display, electronic gas-mixing, synchronisation with the spectrometer by electronic interface. Real-time touchless temperature-measurement of the boat itself (integrated pyrometer) and automatic temperature control (up to 3000°C). Compact modern power-supply (5 kW). Autosampler AD-50-III (Spectral Systems):Automatic boat handling from a tray with 50 boats, about 2 hours needed for analysis of 50 samples with arbitrary number of elementsICP-Spectrometer (here: OES):IRIS intrepid (Thermo), Arcos-EOP (Spectro): simultaneous data acquisition, possibility to display and evaluate the transient signals delivered by the excitated elements, start triggered by the ETV (for automatic runs)Microbalance: Mettler M2P

Instrumentation

F e2338

0 ,0 0

5 ,0 0

1 0 ,0 0

1 5 ,0 0

2 0 ,0 0

2 5 ,0 0

3 0 ,0 0

3 5 ,0 0

4 0 ,0 0

4 5 ,0 0

5 0 ,0 0

0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0

Konze ntra tion [ng abs .]

Inte nsitä t

bn-std -5

bn-1792

bn-490bn-910bn-131

Std6Std7

Std8Std9

bwTrend

Boron Nitride

Mn26 05

0 ,0 0

1 0 ,0 0

2 0 ,0 0

3 0 ,0 0

4 0 ,0 0

5 0 ,0 0

6 0 ,0 0

7 0 ,0 0

8 0 ,0 0

0 ,0 0 2 ,0 0 4 ,0 0 6 ,0 0 8 ,00 1 0 ,00 1 2 ,0 0 1 4 ,0 0 1 6 ,0 0

K onzen tra tio n [n g abs.]

Inten sität

bn-s td-5bn-179 2bn-490bn-910bn-131Std6Std7Std8Std9bwTren d

ETV 4000C with Autosampler

Te 170.000

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

0 20 40 60 80 100 120 140 160

mass fraction / ng

Int./ arbit Units

BAM-381

BCR-074

BAM-382

BAM-383

BAM-383

BAM-384

Trend

High-Purity Copper

Si 152

0

5000

10000

15000

20000

0 200 400 600 800 1000 1200 1400

C-Si-dot-4C-Si-dot-26

SGL-1NBG-18

H2O-STD-25C-spexSTD10,7

C-spexSTD20C-Sidot-250

blancTrend

B 208.959

0

10000

20000

30000

40000

50000

60000

0 50 100 150 200

C-B-dot-4

C-B-dot-26

SGL 1

NBG 18

H2O-STD-4

C-spexSTD 10,7

bw

Trend

Graphite

LOD‘s (3s) in µg/kgwith Maxi-Tubes (large volume)

Intensity

mass fraction [ng abs.]

Intensity

Si25 28

0 ,0 0

1 0 ,0 0

2 0 ,0 0

3 0 ,0 0

4 0 ,0 0

5 0 ,0 0

6 0 ,0 0

7 0 ,0 0

8 0 ,0 0

0 ,00 5 0 ,00 10 0 ,0 0 150 ,0 0 2 0 0 ,0 0 2 50 ,0 0 3 0 0 ,0 0

K onz entr ation [ng abs .]

Intens itä t

bn-s td -5bn-1 792bn-4 90bn-9 10bn-1 31Std6Std7Std8Std9bwTre nd

Intensity




A l2263

0 ,0

10 ,0

20 ,0

30 ,0

40 ,0

50 ,0

60 ,0

70 ,0

80 ,0

0 ,0 5 0 ,0 1 00 ,0 1 5 0 ,0 2 0 0 ,0 2 5 0 ,0 30 0 ,0 3 5 0 ,0 4 0 0 ,0 45 0 ,0

K onz en trat io n [ng ab s]

Intensität

A pfe l

A lg e

ls g a lg e

ls g a p fel

T re n d

Apple LeavesIntensity


P_185 8

0 ,0

20 ,0

40 ,0

60 ,0

80 ,0

1 0 0 ,0

1 2 0 ,0

1 4 0 ,0

0 ,0 2 00 ,0 40 0 ,0 60 0 ,0 8 0 0 ,0 1 00 0 ,0 1 2 0 0 ,0 1 4 00 ,0 1 60 0 ,0 1 8 0 0 ,0

K onz en tra t io n [ng ab s]

Intensitä t

A pfe l

A lg e

ls g a lg e

ls g a p fel

T re n d

Intensity



Fe2 591

0 ,0

20 ,0

40 ,0

60 ,0

80 ,0

10 0 ,0

12 0 ,0

14 0 ,0

16 0 ,0

0 ,0 50 ,0 1 00 ,0 1 50 ,0 2 0 0 ,0 2 50 ,0 30 0 ,0 3 5 0 ,0 4 00 ,0 4 5 0 ,0

K onz entr at ion [ng abs]

Intensität

A pfel

A lg e

lsg alge

lsg apfel

Trendmass fraction [ng abs.]

Intensity

ETV-ICP: principle of operation

H He

Li 5

Be 1

B 30

C N O F Ne

Na 10

Mg 0.1

Al 10

Si 50

P 20

S 30

Cl Ar

K 10

Ca 1

Sc 1

Ti 2

V 2

Cr 5

Mn 1

Fe 2

Co 2

Ni 5

Cu 2

Zn 1

Ga 5

Ge 50

As 20

Se 20

Br Kr

RbSr 1

Y 1

Zr 1

Nb 5

Mo 10

TcRu 20

Rh 5

PdAg 10

Cd 5

In 30

Sn 10

Sb 50

Te 20

I Xe

CsBa 1

La 1

Hf 1

Ta 10

W 10

Re 5

Os Ir PtAu 50

Hg 100

Tl 30

Pb 10

Bi 5

Po At Rn

Fr Ra Ac Rf Db

Ce 5

Pr 10

Nd 5

PmSm 5

Eu 5

Gd 5

TbDy 5

Ho Er Tm Yb Lu

Th 5

PaU 10

Np Pu Am Cm Bk Cf Es Fm Md No Lr

LOD´s by ETV-ICP OESprovis. by ETV-ICP OESnot analysed yetnot possible by ICP used

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

0 10 20 30 40 50 60 70

Zeit

IntensityAs 189.042

Bi 190.241

Pb 168.215

Sb 187.115

Se 196.090

Te 170.000

Cu 169.1_2

T [sec]

CRM BAM 385

Intensities versus Time

Cr2835

0 ,0 0

2 ,0 0

4 ,0 0

6 ,0 0

8 ,0 0

1 0 ,0 0

1 2 ,0 0

1 4 ,0 0

1 6 ,0 0

1 8 ,0 0

2 0 ,0 0

0 ,0 0 0 ,5 0 1 ,0 0 1 ,5 0 2 ,0 0 2 ,5 0 3 ,0 0 3 ,5 0 4 ,0 0 4 ,5 0 5 ,0 0

Konze ntra tion [ng a bs.]

Inte nsit ät

sic std19338517hpStd4Std5Std6Std7Std8Std9Std10Trend

Intensity


V _2715

0 ,0 0

5 ,0 0

1 0 ,0 0

1 5 ,0 0

2 0 ,0 0

2 5 ,0 0

3 0 ,0 0

0 ,0 0 5 ,0 0 1 0 ,0 0 1 5 ,0 0 2 0 ,0 0 2 5 ,0 0 3 0 ,0 0 3 5 ,0 0 4 0 ,0 0 4 5 ,0 0 5 0 ,0 0

Ko nze ntrat ion [n g abs .]

Inten sit ät

s ics td19338517hpStd4Std5Std6Std7Std8Std9Std10Trend

Intensity


C a3158

0,00

20,0 0

40,0 0

60,0 0

80,0 0

100,00

120,00

140,00

160,00

180,00

0,00 5,00 10,00 15,00 20,00 25,0 0 30,00 35,00 40,00 45 ,0 0 50 ,0 0

Ko nzentration [ng ab s.]

Inten sitä t

s ics td19338517hpStd4Std5Std6Std7Std8Std9Std10Trend


Intensity

Silicon Carbide

Components

Graphite-Boats

Graphite-Tubes

Examples for Metal, Graphite, Organic and Ceramic Material

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