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Thomas Meisel , Johann Moser and Peter Kettisch , Department of General and Analytical Chemistry 2 University of Leoben, Franz-Josef-Strasse 18, A-8700 Leoben/Austria, Anton Paar GmbH, A-8054 Austria e-mail: meisel@unileoben.ac.at and johann.moser@unileoben.ac.at Goal: Development of a simple method for the determination of Ru, Pd, Os, Ir, Pt (PGE) and Re concentrations in chromitites
1 1 2 1
Problems:
l l l l Chromitites are difficult to digest in acids, but acids are cleaner than flux chemicals. Low PGE abundances and high matrix concentration. PGE concentrations variable. 5 0 5 Molecular interferences of transition element argides (e.g. 6 Cu4 Ar on 1 0Pd) are problematic. 1 5 6 1 Oxide interferences e.g. 8 5 1 6 on 1 0Ru or 1 7Lu1 O on 1 9Ir should be of a lesser problem Rb O since their abundances in chromitites are low. l OsO4 is volatile (BP ca. 105C).
extract OsO4
HBr
N-TIMS
Final procedure for the digestion and determination of Ru, Pd, Re, Os, Ir and Pt in chromitite.
yes reduce volume
conc. low?
Strategy:
l Complete digestion of chromitites at high pressure and temperature in sealed quartz tubes to replace Carius tubes l Extraction of OsO4 with CCl4 l Ion exchange to separate matrix (either cation or anion exchange resin) 7 8 l Measurement of Os with N-TIMS for isotope dilution and isotopic composition (1 8Os/1 8Os) l Measurement of the remaining PGE and Re with ICPQMS or ICPSFMS.
1.8 1.6
rel. units, isotope ratio
conc. low?
ICPMS HP4500+MCN6000
13.5M HNO3
Instrumentation:
HPA-S (Perkin Elmer-Anton PAAR) high pressure asher HP4500 (Hewlett Packard) MCN6000 (FMS-Cetac) RF 1150W, 0.9 L/min carrier gas flow, MCN, PTFE spray chamber. 0 0.02% CeO+/Ce, 0.4 Mcps 1 4Ce.
ELEMENT (Finnigan MAT) RF 1300 W, low flow pneumatic nebulizer in selfaspiration. 1.0% 0 CeO+/Ce. 1.4 Mcps 1 4Ce
0.2 0.0 0 10 20
mL
30
40
50
PGE isolation by anion exchange does not separate them from remaining Cr(VI). The isotopic composition of Pd and Ru are greatly influenced if measured without membrane desolvation.
1.6 1.4 rel. units, isotope ratio 1.2 1.0 0.8 0.6 0.4
natural ratio
Procedure:
Digestion: 0.3 to 0.4 g of powdered or crushed chromitite sample with 5 mL HNO3 conc. 2 mL HCl conc. and an appropriate amount of a mixed spike solution containing Ru, Pt, Re, Os and Ir in 50 mL quartz tubes goes completely into solution at 125 bar and 320C in 3 to 5 hours. Only a colorless residue (leached silicates) remains. The digest is diluted to a final volume of 50 mL and is ready for the ion exchange step. Separation: Os. After opening the HPA-S tubes OsO4 is extracted in 2x3 mL and 1x2 mL CCl4 at room temperature. The combined organic phases are heated with 4 mL HBr 48%(w/w) overnight at 80C. After discarding the CCl4 the HBr is dried down and microdistilled into 5l HBr. The Os is now ready for N-TIMS measurement. Other PGE and Re. There are two possibilities: Removing the matrix with an anion exchange column (e.g. AG1X8). Most matrix elements pass the column directly. The PGE chloro complexes are eluted with HCl and HNO3 conc. Problems are: the low recoveries of Pt and Ir, the need of large amounts of strong acids ( resin attack and blank), the control of oxidation state (Ir), Cr(VI) and Cu also elute with the PGEs. Loading the sample solution directly onto a cation exchange column (e.g. AG50WX8) and elution with 0.5 M HCl retains the matrix on the column and the chloro complexes pass through the column. Although some transition elements also elute with the sample they are reduced to a negligible amount. Only little dilute acid is needed thus blanks and the amounts of organics are low. Problems occur when the column is overloaded with cations, thus the sample amount loaded is limited unlike the anion exchange columns. In either case any Cr(VI) that formed during digestion needs to be reduced to Cr(III) with H2O2 since CrO42 -behaves similar to the PGE chloro complexes.
0.2 0.0 0 10 20
mL
RM K
N S
30
40
50
Only dilute and small amounts of acid is used for matrix separation. Desolvation makes accurate isotope ratio determination possible.
... measured isotope ratio ... mass discrimination correction factor ... sample mass ... spike mass ... concentration (w/w) of the natural iridium in the sample ... concentration (w/w) of the iridium in the spike ... atomic abundance (mol/mol) of isotope A in the sample ... atomic abundance (mol/mol) of isotope A in the spike ... atomic abundance (mol/mol) of isotope B in the sample ... atomic abundance (mol/mol) of isotope B in the spike
cN cS
A(N ) A(S ) B(N ) B(S )
AW(N ) ... atomic weight of the iridium in the sample AW(S ) ... atomic weight of the iridium in the spike
cS standard uncertainties 111.5 cS N 0.32971 S 0.67644 AW(S) 191.00 AW(N) 192.21 A(N) 0.6236 B(N) 0.3764 A(S) 0.0184 B(S) 0.9816 RM 0.7025 K 1 cN 430 cN [ng/g] 430 differences squares sum of squares 481 square root 22 %RSD 5.1 5.7 117.2 0.32971 0.67644 191.00 192.21 0.6236 0.3764 0.0184 0.9816 0.7025 1 452.3 430.4 21.90 479.55
Measurement:
Although most of the matrix was removed, traces of Cr remain. ELEMENT Very sensitive in the high mass range. Problems occurred with the formation of CrxOxHx species interfering with Ru, Pd and also Re. The following species have been identified:
5 2
N 0.0001 111.5 0.32981 0.67644 191.00 192.21 0.6236 0.3764 0.0184 0.9816 0.7025 1 430.2 430.4 -0.13 0.02
S 0.0001 111.5 0.32971 0.67654 191.00 192.21 0.6236 0.3764 0.0184 0.9816 0.7025 1 430.4 430.4 0.06 0.00
AW(S) 0.016 111.5 0.32971 0.67644 191.01 192.21 0.6236 0.3764 0.0184 0.9816 0.7025 1 430.3 430.4 -0.04 0.00
AW(N) A(N) B(N) A(S) B(S) RM K 0.016 0.000058 0.000058 0.000058 0.000058 0.0008 0.0011 111.5 111.5 111.5 111.5 111.5 111.5 111.5 0.32971 0.32971 0.32971 0.32971 0.32971 0.32971 0.32971 0.67644 0.67644 0.67644 0.67644 0.67644 0.67644 0.67644 191.00 191.00 191.00 191.00 191.00 191.00 191.00 192.23 192.21 192.21 192.21 192.21 192.21 192.21 0.6236 0.6236 0.6236 0.6236 0.6236 0.6236 0.6236 0.3764 0.3764 0.3765 0.3764 0.3764 0.3764 0.3764 0.0184 0.0184 0.0184 0.0185 0.0184 0.0184 0.0184 0.9816 0.9816 0.9816 0.9816 0.9816 0.9816 0.9816 0.7025 0.7025 0.7025 0.7025 0.7025 0.7033 0.7025 1 1 1 1 1 1 1.0011 430.4 430.3 430.4 430.3 430.4 431.2 431.2 430.4 430.4 430.4 430.4 430.4 430.4 430.4 0.04 -0.07 0.05 -0.04 0.03 0.87 0.84 0.00 0.00 0.00 0.00 0.00 0.75 0.70
Example for the calculation of combined standard uncertainty of the concentration of iridium in a chromitite sample. The uncertainty associated with the concentration of the spike has the greatest influence.
CrO2 > CrO > CrO3H interference with 5 2 1 8 5 CrO8H3 interference with Re The isotope ratios
1 0 1
5 2
5 2
1 0 1
Ru
Ru/ Ru and
9 9
1 0 6
1 0 5
1 8 7
1 8 5
HP4500 and MCN6000 Although less sensitive in the high mass range (Re, Ir and Pt) good results for all elements were obtained due to low molecular interferences of the transition elements. Problems were memories in the MCN6000 system and drift effects. Recalibration and background corrections were necessary more frequently.
l Cation exchange resin is most effective for matrix separation. l Membrane desolvation is essential for ICPMS measurement. l Isotope dilution is reliable and simple.