Rome, 25 October 2007 – QUOVADIS Consortium Meeting 1 QUOVADIS Validation Exercise From raw materials to ready results An overview on the identification, sampling, preparation of test samples until the statistical evaluation of measurement results for the evaluation of performance criteria of CEN Draft Technical Specifications. by: S. Vaccaro, G. Roebben, G. Locoro, E. Sobiecka and B. M. Gawlik* * To whom correspondence should be sent NOTES 1. PLACE, DATE AND EVENT NAME 1.1. Access the slide-set place, date and event name text box beneath the JRC logo from the Slide Master Do not change the size nor the position of that text box Replace the mock-up texts for the place (“Place”), the date (“dd Month YYYY”) and the event name (“Event Name”) with your own texts Set it in MetaPlus Book Roman, if you own the typeface. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (white) Keep the original font body size (7 pt) and the text on one single line. 2. SLIDE NUMBER 2.1. The slide number on the banner’s lower right-hand side is automatically generated. 3. SLIDES 3.1. Duplicate the first slide as needed Do not change the size nor the position of the slide’s text box Try not to place more text on each slide than will fit in the given text box Replace the mock-up heading text (“Joint Research Centre (JRC)”) with your own text heading Set it in Eurostile Bold Extended Two or in Helvetica Rounded Bold Condensed, if you own one of these typefaces. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (100c 80m 0y 0k) Keep the original font body size (28 pt) and the heading on one single line whenever possible. Reduce the font body size if needed Replace the mock-up text (“The European Commission’s Research-Based Policy Support Organisation)”) with your own text Set it in MetaPlus Book Roman, if you own the typeface. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (100c 80m 0y 0k). Use black if you need a second colour Keep the original font body size (22 pt) or reduce it if unavoidable Replace the EU-27 map mock-up illustration with your own illustration(s) Try to keep your illustration(s) right- and top- or bottom-aligned with the main text box whenever possible. NOTES 1. PLACE, DATE AND EVENT NAME 1.1. Access the slide-set place, date and event name text box beneath the JRC logo from the Slide Master Do not change the size nor the position of that text box Replace the mock-up texts for the place (“Place”), the date (“dd Month YYYY”) and the event name (“Event Name”) with your own texts Set it in MetaPlus Book Roman, if you own the typeface. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (white) Keep the original font body size (7 pt) and the text on one single line. 2. SLIDE NUMBER 2.1. The slide number on the banner’s lower right-hand side is automatically generated. 3. SLIDES 3.1. Duplicate the first slide as needed Do not change the size nor the position of the slide’s text box Try not to place more text on each slide than will fit in the given text box Replace the mock-up heading text (“Joint Research Centre (JRC)”) with your own text heading Set it in Eurostile Bold Extended Two or in Helvetica Rounded Bold Condensed, if you own one of these typefaces. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (100c 80m 0y 0k) Keep the original font body size (28 pt) and the heading on one single line whenever possible. Reduce the font body size if needed Replace the mock-up text (“The European Commission’s Research-Based Policy Support Organisation)”) with your own text Set it in MetaPlus Book Roman, if you own the typeface. Otherwise, keep the original typeface – Arial Keep the original flush-left justification Keep the original font colour (100c 80m 0y 0k). Use black if you need a second colour Keep the original font body size (22 pt) or reduce it if unavoidable Replace the EU-27 map mock-up illustration with your own illustration(s) Try to keep your illustration(s) right- and top- or bottom-aligned with the main text box whenever possible.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 2 Validation Why and How? The QUOVADIS Validation Exercise Raw materials Identification, Sampling Treatment Ruggedness testing The validation intercomparison Organisation Data collection Statistical treatment Conclusions Presentation Outline

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 3 Validation: Why and How Why?: Validation is a pre-requisite to transform a Technical Specification into a legal document, e.g. an European Standard (EN); Validation quantifies the performance characteristics of a standard method; Validation helps to rule out the most frequent problems in the use of a method. How?: Analytical methods: Determination of performance characteristics (range, linearity, robustness, accuracy, precision, LoD, LoQ (ISO 17025); Standard Methods: according to ISO 5725 (1+2+5) using intercomparison approach; Management Standards: check “fit-for-purpose” criteria.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 4 Raw materials identification Based on the gathered information among the project consortium as well as based on the requirements formulated by CEN TC 343, the following locations for the validation materials were identified: - QV-A: SRF from Shredded Car Tyres NORVALO, Dompierre- Bequincourt, France; - QV-B: SRF from Demolition Wood – Lassila &Tikanoja, Helsinki, Finland; - QV-C: SRF from Sewage Sludge Treatment Plant – Seneffe, Belgium; - QV-D: SRF from Mixed Municipal Waste – ECODECO, Milan, Italy; - QV-E:SRF from Mixed Municipal Waste, high plastics – Erfstadt, Germany; - QV-F: SRF from Mixed Municipal waste with Tyre Material – Pirelli IDEA Granda Cuneo, Italy.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 5 Raw materials sampling Sampling of QV-A SRF from Shredded Car Tyres – NORVALO, Dompierre-Bequincourt, France After plant inpection, five 60 litres PE barrels have been filled with the tyre pieces (mixture of iron, rubber and cotton textile) from the open air stocks of semi-processed material. Samples were collected in different parts of the stocks in order to preserve representativeness.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 6 Raw materials sampling Sampling of QV-B SRF from Demolition Wood – Lassila &Tikanoja, Helsinki, Finland Twelve 60 litres PE barrels have been filled from the process output after plant inspection.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 7 Raw materials sampling Sampling of QV-C SRF from Sewage Sludge Treatment Plant – Seneffe, Belgium Some 100 kg of suitable sludge SRF were obtained from SCORIBEL, Belgium. After collection this material were delivered to IRMM in Geel for storage and processing.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 8 Raw materials sampling Sampling of QV-D SRF from Mixed Municipal Waste – ECODECO, Milan, Italy Six PE barrels of SRF (soft pellets) were sampled and shipped to the JRC for further processing.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 9 Raw materials sampling Sampling of QV-E SRF from Mixed Municipal Waste, high plastics – Erfstadt, Germany; Five 60 litres barrel plus one 40 litres box of sample were collected according to the plant’s QA/QC sampling procedures

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 10 Raw materials sampling Sampling of QV-F SRF from Mixed Municipal waste with Tyre Material – Pirelli IDEA GRANDA Cuneo, Italy. Two PE barrels of SRF from the Pirelli IDEA GRANDA plant were sampled in Cuneo, Italy and transported to JRC IES for further processing. From this material 5 L of acidic digest were produced following the draft TS for mineralisation (Figure 2). The digest was sent to JRC IRMM for ampouling.

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 11 Raw materials Treatment

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 12 Raw materials Treatment Ruggedness (QR) and Validation Test Samples (QV)

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 13 Homogeneity of the ruggedness test materials was assessed in terms of: – ash content (IVD, Stuttgart) – calorific value (SLU, Umeå) – Content of Al, S, Cl and Cr by XRF (IES-JRC-EC, Ispra) All QR-materials (QR-A, QR-A2, QR-B, QR-C, QR-E) met the agreed ‘between-sample’ homogeneity criterion (30 %) using a 1 mm sieve insert in the mill This result was a prerequisite for processing the validation test materials along the same protocol Homogeneity test of the materials

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 14 Homogeneity test of the materials Between-samples: sbb = 100 * 4.45 / = 17.4 % Within-samples: swb = 100 * 7.28 / = 32.0 % Between-samples: sbb = 100 * 2.04 / = 9.0 % Within-samples: swb = 100 * 4.32 / = 19.0 %

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 15 The interlaboratory experiment: organization Expression of interest from 30 laboratories Preparation of samples dispatch according to samples’ characteristics (grainsize (<1mm) and typical /minimum quantities for each test) as identified after ruggedness testing statistical design: 2 bottles/sample, 3 repetitions/bottle for most of the parameters, 6 repetitions/bottle for “key” parameters (Cl, Hg, Calorific Value) Design of a Excel® template for the invoice of results and of a RDBMS-based application for data managementtemplate Interlaboratory experiment

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 16 The interlaboratory experiment: results collection and statistical treatment On October 22, the number of responding laboratories was 20 Data need to be consolidated in order to be suitable for statistical treatment Statistical treatment to be carried out according to the standard ISO 5725, especially referring to parts 1, 2 and 5. The latter includes in particular the treatment of data from non- homogeneous samples. Interlaboratory experiment

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 17 The interlaboratory experiment: statistical treatments according to ISO Mandel h and k tests for the between-laboratory consistence of averages and variances Cochran and Grubbs statistics for the identification of outliers ANOVA-based treatment for the assessment in-homogeneity and of the within- and between laboratory contribution to variance Interlaboratory experiment

Rome, 25 October 2007 – QUOVADIS Consortium Meeting 18 Conclusions Suitable testing materials identified, sampled and disseminated; First impression in scattering of data: ok; To be discussed: trace element and digestion Scrutinised data sets and report to be published in early 2008; EUR (ISBN)-Monograph and peer-reviewed journals.