Summary of Analytical protocolsused for

Dye and organic pigment analysis

Maarten van Bommel

Analytical protocols

Evaluation of techniques used

- Not standardization of the techniques

- Determine pro’s and con’s of the different techniques

- Establish a standard format of how to describe an analytical technique

- So that others can reproduce it

All partners submitted the analytical protocols in the format they are used to

Analytical protocols

Non-destructive:- X-ray fluorescence (XRF)- Fibre optic mid-FTIR- Fibre optic micro-Raman UNI-PG- UV-VIS fluorescence- UV-VIS colorimetry

- 3D fluorescence KIK / IRPA- SEM-EDX (samples are coated) ICN

Not comparable equipment, except fluorescence

Analytical protocolsDestructive:- HPLC-PDA (6 protocols)

OADCKIK-IRPANGLICNGCINMS/UoE

- HPLC-MS (2 protocols)GCI (combined with PDA)NMS/UoE

- HPLC-FluorescenceICN (combined with PDA)

Sample pre-treatmentMicroscopic examination

KIK / IRPANGLICN

Weight samplesOADCKIK / IRPANMS / UoEICN (not paint samples)

Colorant extractionMethanolic HCl all partners except NGLMethanolic BF3 NGL

Sample pre-treatment

EvaporationNitrogen flow

OADC (60 °C)ICN

Vacuum desiccatorsKIK / IRPAGCI

Rotary evaporatorNMS / UoE (40 °C)

NoneNGL

Dissolve Methanol / water

KIK / IRPAGCINMS / UoE

Di-methyl formamideOADCICN

Add methanolNGL

Sample pre-treatmentRemoval of particles / precipitationFiltering prior evaporation

GCIKIK / IRPA

Centrifugation after evaporation and dissolutionICN

HPLC analysisAll partners uses RP-HPLC with silica C18 based materials

However, all partners uses different column materials and columns with different dimensions (length and id).As a results, flow rate varies from

0.01 ml/min to 1.20 ml/min

Injection volumes varies as well

Columns are thermo stated at 25 – 40 °C (except KIK / IRPA)

HPLC analysisHPLC solvent composition Runtime (min)H2O / ACN / TFA

OADC 35NGL* 240

H2O / MeOH/ phosphoric acidKIK / IRPA 35NMS / UoE 35ICN 50

H2O / MeOH / formic acidGCI 45

H2O / MeOHNMS / UoE (HPLC-MS) 40

Accuracy of solvent preparation? (ICN and NMS / UoE)

Photo diode array detection (PDA)RangeStart 191, 200, 210 or 250 nmEnd 700, 750 or 800 nm

ResolutionVaries from 1.0 to 2.5 nm

Specific wavelengthsUV250 nm, 254 nm, 255 nm, 270 nm, 275 nm, 288 nm, 290 nmVIS330 nm, 350 nm, 370 nm, 420 nm, 435 nm, 491 nm 495 nm,500 nm, 530 nm, 540 nm and 610 nm

Note: OADC, GCI and NMS focus only on UV

Mass spectrometry (MS)

Only GCI and NMS / UoENegative ESINitrogen sheath gasNo sheath flowInterface 200 °C NMS / UoE

350 °C GCI

Scanning 50 – 1000 m/z GCI? NMS / UoE

Conclusions

Everybody uses different systems, question remains:

- How are the results affected by the different parameters?

- Can we establish a standard format for description ofprotocols for (HPLC) analysis

And do we want that?

Proposed format- Name of protocol

- Aim of protocol

- Author(s)

- Date of latest version or revision

- Chemicals- reagent, grade, concentration, supplier, product number

- Materials- Vials- Columns (and pre-columns)- Filters- Glassware- Pipettes- etc

- Equipment- Pump- Degasser- Autosampler / injector- Column oven- Detector

Proposed format, continue

TypeSpecificationSupplierProduct number?

- Solvent preparation

- Pre-examination

- Sample pre-treatment

- Analysis

- Blank and standards

- Detection parameters

- Data evaluation

Proposed format, continue