Advances in Determinations of metals by ICPMS, from ultra-small

sampling to ultra-

trace analysis.

AES Department

Dr. Otto HerrmannTeresa Switzer

May 11, 2009

Historical Background and Application

1980’s atomic absorption – graphite furnace to low ppb and some fractional ppb

LATE 1980’S – introduction of ICPAES with routine 5 to 20 ppb – ultrasonic nebulization to improve about 10x (overlap with graphite

- Pb in boiler water – Bruce

2000+ ICPMS with DRC– routine compromise conditions 0.1 ppb and optimized to 0.01 ppb

- trace metals in moderator water; TIFAC at Darlington

- Gd precipitation and isotopic distribution in moderator

2009 next generation ICPMS – about 100x more sensitive and multiple sample introduction methods

OPERATION AND MAINTENANCE

↑

ICPMS-bare

↑

↑

ICPMS#2 – with attachments

ICPAES

AAS -GRAPHITE

↑

AAS - FLAME

THE NEXT GENERATION STARTREK

Varian 820-MS Instrument Design Features such as 90 degree mirror leading to superior sensitivity and

detection limits

Interference reduction capabilities – new mechanism not fully characterized

Isotope measurement as “radioanalytical” technique (direct -1500yr half-life;

indirect –neutron absorption capability B, Gd); non-active tracers

Laser Ablation- ICP-MS

Use of technique as a semi-quantitative tool and quantitative tool (more

difficult)

“non-destructive” analysis

HPLC and GC interfaces for speciation and matrix separation

Varian 820-MS

LA1 LASER ABLATION

LASER ABLATION SAMPLING ATTACHMENT NEW WAVE 266 NM LASER

LA2 LASER ABLATION +/-

No sample digestion required – direct analysis of solid material.

Relatively “non-destructive” analysis if sample cannot be destroyed.

Interferences and contamination from sample handling and digestion protocols are eliminated

BUT Difficult to calibrate for accurate quantitation

(standards – both physical form and composition critical)

Design special cells for large samples

LA3 Contamination via Handling – 5n AlICP ICP ICP ICPMS LA

Goodfellow Goodfellow Goodfellow Goodfellow Goodfellow

ZrN-old ZrN new drillTi new drillZrN-old NILB <16 <30 <30 <0.2 0.04

Ba <2 <2 <2 0.45

Ca <4 36 2 <2 0.06

Co <6 <5 <5 <0.2

Cr <6 <5 <5 7.08

Cu 29 <4 <2 26.9 0.87

Fe 150 46 21 151 13.1

Mg <2 2 1 4.0 4.7

Mn <2 <2 <2 4.25 0.59

Mo <10 <6 <3 0.64

Nd 0.04

Ni <10 <10 <10 7.25

P <40 <40 <40 <20 0.80

Pb <20 <20 <20 8.42 0.41

Sb <44 0.31 0.04

Sc 0.03

Si <20 <20 <20 <20 0.14

Sn <8 <8 <8 1.59 0.27

V <10 <10 <10 <2 0.02

Zn <2 11 <2 3.74

Zr <6 0.80 0.13

LA4 High Purity Aluminum (5n) Analysis by LA-ICPMS

ppm LA LA LASample 09-01551-1 09-01551-2 09-01551-3

isotope Goodfellow Ekain - China Giang&I -China

As75 <0.02 0.042 <0.02B11 0.039 0.037 0.035Ca43 0.064 0.072 0.088Ce140 0.645 0.220 0.792Cu65 0.863 0.940 0.869Fe57 13.080 21.408 20.951Mg24 4.688 5.694 5.519Mn55 0.585 1.012 0.750Nd146 0.044 0.031 0.038P31 0.798 1.121 1.262Pb208 2.275 0.170 2.393Sb121 0.039 0.025 0.028Sc45 0.032 0.042 0.043Si28 0.136 0.189 0.192Si29 0.110 0.155 0.180Sn118 0.267 0.428 0.271V51 0.017 0.019 0.031Zr90 0.127 0.040 0.647TOTAL 23.809 31.645 34.0895n=99.999% = <10 ppm impurities

LA5 LASER ABLATION Faults versus Bulk Analysis

20um to 600 um spot size determined by application Ablate in preset pattern – target vs. scan

PENNY WITH TARGET MARKING

BURN

BURN TRACK-20um

Combined Techniques

HPLC-ICPMS best known

- speciation (AS+3, AS+5, organo-As such as arsenobetaine); EPA legislation tributyl tin

- matrix removal or species concentration

GC-ICPMS – volatile species; Hg species; organometallics; least familiar