Smart Solid Sample Trace Analysis by...
Transcript of 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
mass fraction [ng abs.]
mass fraction [ng abs.]
mass fraction [ng abs.]
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
mass fraction [ng abs.]
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
mass fraction [ng abs.]
mass fraction [ng abs.]
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
mass fraction [ng abs.]
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
mass fraction [ng abs.]
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
mass fraction [ng abs.]
Intensity
Silicon Carbide
Components
Graphite-Boats
Graphite-Tubes
Examples for Metal, Graphite, Organic and Ceramic Material