Improving trace metal analysis by dedicated analytical standards, CRMs and reagents

•Dr. Frank Michel, Markus Pfluger

sigma-aldrich.com

1)

Buchs Site, Switzerland, Core Capabilities

500 employees

Automated milligram filling Chiral separation (SMB) GMP custom synthesis Microreaction synthesis Comprehensive analytical capabilities Production from microgram up to 1‘600 L

4,000 products produced

Accreditation acc. to ISO/IEC 17025 & ISO Guide 34

GMP

q-NMR Titration ICP-OES Density

Qua

lity

ISO 9001IS

O17

025

Production of certified reference materials(high purity materials, high precision weighing)

TraceCERT© reference materialswww.sial.com/tracecert

TraceSELECT© high purity productswww.sial.com/traceselect

Systems & QC

Physical data: mp, bp, n, d, viscosity, optical rotation etc. Titration: all kind of titrations, KF Spectroscopy: IR, NIR, UV, NMR (H,C,P,F), X-ray, luminescence Chromatography: GC, GC-MS, GC-HS, HPLC,GPC, TLC Hyphenated techniques: HPLC-MS (Ion Trap), UHPLC-MS (qToF), HPLC-NMR (600 MHz), Elemental analysis: C, H, N, S Biochemical analysis: MALDI-MS, CE, gel electrophoresis (IEF, SDS-PAGE, agarose

gels), enzyme activity, enzymatic content determination, determination of enzyme impurities, protein assay etc.

Trace analysis:AFSAAS (Flame, Graphite furnace with FI) ICP-OES (1x axial, 1x radial)ICP-MS (2x with reaction cell) Polarography, CVIC (2x anion / 1x cation)Wet chemistry

Analytical Expertise

Releases of Mercury in the environment (man related) 1)

stationary combustion (coal-

fired power plants)

65%

non-ferrous metal production

7%

other5%

caustic soda production

3%waste disposal

3%cement production

6%

gold production 11%

Natural sources: Volcanoes, natural mercury deposits, volatilization from the ocean

1) Wikipedia

Mercury compounds are extremely toxic (heavy metal)Monitoring of Hg regulatory necessary (EPA, WHO, …)Chemicals used for ultra trace analyis must be low of Hg

The Mercury Cycle

WHO: Provisional tolerable weekly intake of Hg2µg/kg bodyweight per week (75kg 150µg/week)

WHO: Guideline Values (Total Mercury)< 1 µg/l Water

< 1 µg/m3 Air

< 30 µg/kg Food

< 500 µg/kg Fish

Instrument with lowest detection limits necessary

(specifications of ultra pure chemicals should be « 1 µg/kg)Ultra Pure Chemicals for analyis of Hg necessary

Analytical control of• air • foodstuff • drinking water

Analytical techniques for determination of Hg

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

Analytical techniques for determination of Hg

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

Principles of Optical Spectroscopy

1)

1) G. Glomb, Schlemmer, Labatzke, Analytik Jena

Choice of the right technique at Sigma-AldrichDesign Qualification Part I: Detection Limit [g/l]

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

150

1

0.005

0.01

0.030.1

0.001

Choice of the right technique at Sigma-AldrichDesign Qualification Part II: instrument price [k€]

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

25

6050

30

150

Choice of the right technique at Sigma-Aldrich Design Qualification Part III: different matrices

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

Choice of the right technique at Sigma-AldrichDesign Qualification Part IV: dynamique range

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

Choice of the right technique at Sigma-AldrichDesign Qualification Part IV: dynamique range

FAASCV-AAS

HydrEA(CV+GFAAS)

CV-AFS

GFAAS

1)

2)

1) 2) G. Schlemmer, Analytik Jena

Choice of the right technique at Sigma-AldrichDesign Qualification Part IV: dynamique range

ICP-MS

CV-AAS

HydrEA(CV+GFAAS)

FAAS

CV-AFS

ICP-OES GFAAS

Method of Choice for Sigma-Aldrich

CV-AFS

• budget not more than 25 k€ (additional capacity)

• low maintenance costs

• complex and varying matrices

• lowest detection limits necessary

• wide range of linearity

Existing methods (pharma customers)

CV-AAS

Method of Choice for Sigma-Aldrich

CV-AFS

• budget not more than 25 k€ (additional capacity)

• low maintenance costs

• complex and varying matrices

• lowest detection limits necessary

• wide range of linearity

Existing methods (pharma customers)

CV-AAS

Design Qualification: Assessment

Vendor Assessment:

• general tests (ease of operation, Software, …)

• Parameter tests (detection limit, drift, baseline)

• instrument tests with matrix (HNO3 65%, H2O230%, H2SO4 96%, H3PO4 85%, NaOH 30%, 1ppb solution in HNO3, NaBH4 with MSA)

•Financial aspects

•Service

Decision after Assessment

Mercur DUO Plus® (Analytik Jena):

• Atomic fluorescence and atomic absorption

• Good results for instrument demonstration

• MSA available for NaBH4 application

• Low cost of purchase and maintainance

• Good service availability

MERCUR DUO PLUS ®

Mercur DUO Plus® and corresponding reagents

TraceSELECT®Ultra <0.1 µg/kg (<0.1 ppb)

Metal Contaminations

TraceSELECT® <10 µg/kg (<10 ppb)

Hig

h P

urity

Rea

gent

s

puriss. p.a. <500 µg/kg (<500 ppb)

Highest Purity for successful analysis

What TraceSELECT means for Trace Analysis

Accurate, fast and cost-effective analyses

Highest Purity and long term stability over 60 cation traces specified in the low ppt

(TraceSELECT Ultra) or ppb range (TraceSELECT) long shelf life with consistent purity due to high quality

fluoropolymer bottles

Comprehensive product range AAS (graphite furnace AAS, flame AAS, hydride AAS) ICP-OES, ICP-MS, LC-ICP-MS IC, Voltammetry, Polarography

Reagents and Standards for the whole Analytical Process

Digestion reagents (acids, bases, salts)...for trace analysis (TraceSELECT®)...for ultra-trace analysis (TraceSELECT®Ultra)

Matrix modifiers, buffers, reducing agents for AASSolvents for LC-ICP-MS applicationsEluent concentrates for ICUltra pure reagents for Polarography

TraceCERT®

Certified Reference Materials

SamplePreparation

Calibration

Analysis

Digestion reagents withultra-low blank values

purified by subboiling destillation

stored in high-quality fluoropolymer bottles

(...)

...recommended products for Hg analysis

Brand Product Name Description Pack size

Fluka 44355 Tin(II) chloride TraceSELECT®, 99.999 % metals basis 250g, 2.5kg

Fluka 84415 Hydrochloric acid 37 %, TraceSELECT®, for trace analysis, fuming 100mL, 500mL

Fluka 84385 Nitric acid 69.0 %, TraceSELECT®, for trace analysis 250mL, 1 L

Fluka 95305 Water TraceSELECT®, for trace analysis 500mL, 1L, 2.5L, 10L

Fluka 90737 Potassium bromide TraceSELECT ®, >= 99.9995 % metals basis 50g

Fluka 60085 Potassium bromate puriss. p.a., ACS reagent, >= 99.8 % RT dried material 50g, 250g

Fluka 11514 Hydroxylamine hydrochloride TraceSELECT®, >= 99.9995 % metals basis 100g

Please find the complete product list at www.sigmaaldrich.com/traceselect

...recommended products for Hg analysise.g. Nitric Acid

...recommended products for Hg analysis calibration curve

...selected TraceCERT products for calibration

Brand Product Name Description Pack size

Fluka 16482 Mercury Standard for AAS TraceCERT™, Hg 1000mg/L nitric acid 100mL

Fluka 28941 Mercury Standard for ICP Trace CERT™, Hg 1000mg/L nitric acid 100mL

If you can‘t find the right standard, visit our custom standard platform and design your own:www.sial.com/csp

Brochures for Spectroscopy

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