Advances in Determinations of metals by ICPMS, from ultra-small sampling to ultra- trace analysis. AES Department Dr. Otto Herrmann Teresa Switzer May 11, 2009

Historical Background and Application l 1980’s atomic absorption – graphite furnace to low ppb and some fractional ppb l 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 l 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 l 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 l LASER ABLATION SAMPLING ATTACHMENT l 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 Al

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

LA5 LASER ABLATION Faults versus Bulk Analysis l 20um to 600 um spot size determined by application l 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