consortium meeting, december 14, 2006 1 quovadis grant - agreement eie/031/s07.38597 quality...

Consortium meeting, December 14, 2006 1

QUOVADISGRANT - Agreement EIE/031/S07.38597

Quality Management Organisation, Validation of standards, Developments and Inquiries for SRF

QUOVADIS PROGRESS REPORT WP6 Ispra, December 14 2006

Silvana Iacobellis ([email protected], [email protected])

Project supported by the “Intelligent Energy - Europe” Programme of the European Community


Objectives

1. Evaluation of robustness of TS for chemical parameters through ruggedness testing on selected reference materials from WP 3

2. Support supervision of the intercalibration exercise for the validation of TS for chemical analysis upon input from TC 343 WG5. Identification and selection of the participant laboratory for the intercalibration

3. Validation of TS on sample reduction from laboratory sample to test portion


Test methods to be validated

• prCEN/TS 15407 (WI 343020) Methods for the determination of carbon (C), hydrogen (H) and nitrogen (N) content

• prCEN/TS 15408 (WI 343022) Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F) and bromine (Br)

• prCEN/TS 15410 (WI 343024) Method for the determination of the content of major elements (Al, Ca, Fe, K, Mg, Na, P, Si, Ti)

• prCEN/TS 15411 (WI 343025) Methods for the determination of the content of trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Mn, Ni, Pb, Sb, Se, Tl, V and Zn)

• prCEN/TS 15412 (WI 343026) Methods for the determination of metallic aluminium

• prCEN/TS 15413 (WI 343027) Methods for the preparation of the test sample from the laboratory sample


Description of tasks

Task 6.1: Ruggedness testing for main factors influencing the procedures for the determination of chemical parameters upon input from TC 343 WG 5

Task 6.2: Identification, selection and contractual arrangements with participant laboratories in the intercomparison exercise

Task 6.3: Support and supervision of the validation intercomparison exercise, including the organization of ad hoc meetings and final meetings for the presentation and the discussion of the results of the intercomparison

Task 6.4: Validation of the sample reduction procedure from laboratory sample to test portion, comparing different preparation techniques

Task 6.5: Validation of the TS for the determination of metallic Al, through the execution of ruggedness testing for main factors of influence


Samples

SRF produced from industrial non hazardous waste like a combination of plastic, cardboard and paper.QR-E

SRF produced from the combustible fraction of municipal solid waste.QR-D

SRF produced with dried waste water sewage sludge, filtercake and coal or lignite residues.QR-C

SRF produced from demolition wood.QR-B

SRF produced from shredded tyres.QR-A


Task 6.1: Ruggedness testing for main factors influencing the procedures for the determination of chemical parameters upon input from TC 343 WG 5

• Key variables must be selected among the main degrees of freedom of each method

• For each key variable, conservative conditions should be met; i.e. when the methods “passes” the ruggedness testing in those conditions, it will be actually “robust” in most real life cases.

• The kind of sample to be assigned to each method should emphasize the influence of the key variable under control

Criteria for the selection of sample/variable pairs for the evaluation of ruggedness:

Robustness is the ability of a method to give consistent results under controlled variations of key analytical parameters/conditions


prCEN/TS 15407 Methods for the determination of carbon (C), hydrogen (H) and nitrogen (N) content

QR-A Shredded tyres sample3Grain size

5

QR-A shredded tyre sampleQR-C dried sludge sampleQR-E paper plastic fluff sample

3CompositionFlash combustion

Total levelsNotesNo of levelsKey variablesMethod

Activity performed at VTT



For nitrogen, the average values at 0.5 mm tend to be higher than at larger grain sizes suggesting a higher relative recovery.

RSD values are generally good, and appear to be higher at 1mm grain size

Effect of grain size (QR-A shredded tires)

0

1

2

3

4

5

6

7

8

C/10 H N

con

c %

QR-A 0.5mm

QR-A 1mm

QR-A 1.5mm

Carbon concentration is shown divided by 10 in order to better compare values at the same scale



The results clearly show that for “difficult” samples such as QR-A and QR-A2 (shredded tires), the RSD% values are higher while for the other investigated SRFs the RSD values are lower than 5%.

The RSD values are higher for N due to the lower concentration level comparing to C and H.

Effect of sample type / matrix on repeatability1 mm grain size (for sample QR-C only a fine grain size was available due the origin of the sample itself).

For CHN analysis on 1 mm grain size is adequate for most cases for the analysis of SRF samples of different origin, even if better results can be obtained in terms of precision by using larger amounts or lower grain size.


prCEN/TS 15408 Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F), bromine (Br)

QR-E paper plastic fluff sample3grain size

5

QR-A shredded tyre sampleQR-C dried sludge sampleQR-E paper plastic fluff sample

3compositionCombustion

Total levelsNotesNo of levelsKey variablesMethod

This study shown that the method is not applicable on samples containing rubber, such as QR-A, because it is not possible to prepare

suitable pellets for the combustion: this has to be taken into account for the next revision of the method.

Activity performed at CESI


prCEN/TS 15408 Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F), bromine (Br)

• Recovery appear to be influenced only for sulfur, while for chlorine no clear statements can be done, because of repeatability issues.

• Repeatability is worse at larger grain size for Br and Cl, while it is similar for S. In the case of F the situation is more difficult to explain, with RSD value decreasing from 0.5 to 1 mm, and increasing from 1 to 1.5 mm grain size.

0

5

10

15

20

25

F Br Cl SR

SD (

%)

QR-E (0,5 mm)QR-E (1,0 mm)QR-E (1,5 mm)

Effect on repeatabilityEffect on recovery

QR-E: paper-plastic fluff – effects of grain size

0

100

200

300

400

500

600

F Br Cl /10 S/10

mg

/kg

QR-E 0.5mmQR-E 1.0mmQR-E 1.5mm


prCEN/TS 15410 Method for the determination of the content of major elements (Al, Ca, Fe, K, Mg, Na, P, Si, Ti)

5QR-E paper plastic fluff sample4time of heatingMethod C (perchloric acid at 190

°C) + ICP-OES/MS QR-E paper plastic fluff sample2grain size

2QR-E paper plastic fluff sample2grain sizeMethod B - Ashing (prCEN/TS 15403) + ASTM D4326 (XRF)

3QR-A shredded tyre sample3grain sizeMethod B - Ashing (prCEN/TS 15403) + EN 13656 + ICP-OES/MS

QR-E paper plastic fluff sample3+3grain size

QR-E paper plastic fluff sample3+3amount of test portion

8+8

QR-A shredded tyre sampleQR-B demolition wood QR-C sample dried sludge sampleQR-E paper plastic fluff sample

4+4compositionMethod A - EN 13656 (aqua regia + HF + boric, microwave) + ICP-OES/MS

+Method A - EN 13657 (aqua regia only, microwave) + ICP-OES/MS

Total levels

NotesNo of Levels

Key variablesMethod


prCEN/TS 15411 Methods for the determination of the content of trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Mn, Ni, Pb, Sb, Se,

Tl, V and Zn)

5QR-D MSW sample3amount of test portion

Hg direct - AMAQR-D MSW sample3grain size

5QR-E paper plastic fluff sample4time of heatingMethod C (perchloric acid at

190 °C) + ICP-OES/MS QR-E paper plastic fluff sample2grain size

3QR-A shredded tyre sample3grain sizeMethod B – Ashing (prCEN/TS 15403) + EN 13656 + ICP-OES/MS

QR-E paper plastic fluff sample3+3grain size

QR-E paper plastic fluff sample3+3amount of test portion

8+8

QR-A shredded tyre sampleQR-B demolition wood QR-C sample dried sludge sampleQR-E paper plastic fluff sample

4+4composition

Method A - EN 13656 (aqua regia + HF + boric, microwave) + ICP-OES/MS

+Method A - EN 13657 (aqua regia only, microwave) + ICP-OES/MS

Total levels

NotesNo of Levels

Key variablesMethod


prCEN/TS 15410 - prCEN/TS 15411 Method A - EN 13656 (aqua regia-HF-boric, microwave)

Activity performed at ENEL

No significant influence in recovery. Larger amount of test portion gives generally lower RSD values.

Same behavior for minor elements (prTS 15411)

variable: amount of test portion

0

0.2

0.4

0.6

0.8

1

Al Ca Fe K Mg Na P Si Ti

Co

nc

%

QR-E 0.1g

QR-E 0.2g

QR-E 0.4g

variable:grain size

0

0.2

0.4

0.6

0.8

1


Co

nc

%

QR-E 0.5mm

QR-E 1mm

QR-E 1.5mmEffect of grain size (QR-E)

Effect of amount of test portion (QR-E)

Some influences can be observed for someelements, but they don't appear to be dramatic.


prCEN/TS 15410 - prCEN/TS 15411 Method A - EN 13657 (aqua regia, microwave)

Activity performed at ENEL

Ratio of recovery between EN 13657 and EN 13656 (aqua regia vs “total” HF)

Recovery rate isn’t significantly different between the two digestion procedures for almost all elements, except for Si, Ti and Sb (and Al in sewage sludge QR-C only).Note: recovery of Si with EN 13656 is not guaranteed because of volatility of SiF4.

Ratio mean conc- EN 13657 / EN 13656

0

0.2

0.40.6

0.8

1

1.21.4

1.6

1.8


QR-A

QR-B

QR-C

QR-E

ratio mean conc EN13657 / EN 13656

00.20.40.60.8

11.21.41.61.8

Cr As Sb Pb Ba Co Cu Mn Mo Ni V Zn

QR-A

QR-B

QR-C

QR-E


prCEN/TS 15410 - prCEN/TS 15411 Method B - Ashing (prCEN/TS 15403) + EN 13656

0

0.1

0.2

0.3

0.4

0.5

Al Ca K Mg Na P Ti

con

c %

QR-A 0.5mm

QR-A 1mm

QR-A 1.5mm

0

5

10

15

20

25

Si Fe

con

c %

0

20

40

60

80

100

Cr As Cd Sb Pb Ba Ni Zn

mg

/kg

QR-A 05

QR-A 1

QR-A 15

0

200

400

600

800

1000

1200

Co Cu Mn

mg

/kg

Significant, not dramatic, influence of grain size for many elements (Fe, Ca, Al, K, Mg, P and minor elements)This behaviour was expected for this kind of matrix (oxides, refractory).

Note: recovery of Si with EN 13656 is not guaranteed because of volatility of SiF4

Effect of grain size (QR-A) - Activity performed at ENEL


prCEN/TS 15410 Method B - Ashing (prCEN/TS 15403) + ASTM D4326 (XRF)

Activity performed at CESI – APAT – ENELSample E - ash plastic-paper fluff bott 1

0

5

10

15

20

25

30

35

Na Mg Al Si S K Ca Ti Cr Mn Fe Co Ni Cu Zn As Se Sr Ba Pb V Sb Sn Tl P

RSD

(%

)

lab 1lab 2lab 3

Grinded ash shows generally lower RSD%.

The average concentration values for the major and minor elements are similar for grinded and non grinded ash, thus showing that the ash is sufficiently fine to be analysed as such by XRF.

Differences are observed between XRF results from the three labs even if calibrants and samples were prepared in same lab; this might be due to the different technologies of the instruments used. Furthermore, it appears that there is no “best” XRF technology for this kind of application.

ED-XRFLab 3

EDP-XRFLab 2

WD-XRFLab 1

Sample E - grinded ash plastic-paper fluff bott 1

0

5

10

15

20

25

30

35

Na Mg Al Si S K Ca Ti Cr Mn Fe Co Ni Cu Zn As Se Sr Ba Pb V Sb Sn Tl P

RSD

(%

)

lab 1lab 2lab 3


prCEN/TS 15410 - prCEN/TS 15411 Method C (perchloric acid at 190 °C)

The results obtained in this work show that:• 10 hours heating time is generally sufficient for major and minor element

recovery from paper/plastic SRF sample; but for some elements (Ti, Ba, Ca, Mg, K, Al) this is not true, a longer digestion time is required; Mg, Ba, Ca, Ti and P show also a significant interbottle difference

• It seems that generally RSD values are better at 0.5 mm in comparison to 1 mm grain size, but this is not so evident

• Differences are observed for the average values at 0.5 and 1 mm grain size: these differences are larger at 10 hours heating time, while the results are more similar at 20 hours time of heating

• This method requires the use of suitable closed bombs in order to stand the high pressure during digestion due to CO2 generation and to liquid vapour pressure of the acid mixture upon heating up to 190 °C. Not all the types of teflon bombs can be used, as clearly demonstrated in this work: stainless steel bombs are seldom used in the laboratories, because of the replacement with microwave digestion systems.

Activity performed at VTT/ CESI


xx x xx xCHN by macro instr method

x xx xx x CHN by micro instr method

x Cl, F, S, Br by other methods

xxxxxxxx xxCl, F, S, Br by oxygen combustion + ICP or IC

xx x x xAl metal by alkaline digestion

xxx xAl metal by thermogravimetry

x x xxx major elements by XRF

xxxx xxxxxmajor element after acid dissolution

xx xx xx xx Hg by automatic analizer

xxxxxxxxxxxxminor element after acid dissolution

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Task 6.2: Identification, selection and contractual arrangements with participants in the intercomparisons.


Task 6.3: Support to and supervision of the validation. The validation exercise itself is organised within WP 3.

• JRC will prepare and send the materials for testing to the laboratory as identified in Task 2.

• CESI will give to JRC all the information for mailing the materials and the name of contact persons

• CESI will provide all the technical procedures for the execution of the laboratory experimental work. Technical support will be sent for example by E-mail.

• Meeting organization

• CESI will have the supervision of the organization of the database of the results.


Task 6.4 Validation of the sample-reduction procedure fromlaboratory sample to test portion

Preliminary tests (done):

identification of applicable treatment procedures

evaluation of most interesting chemical parameters to be tested, and their approximate levels

approximate assessment of the actual homogeneity of the sample with respect to several parameters

Actual evaluation of ruggedness (done for sample of SRF from MSW):

Application and verification of the statistical formula for the determination of the minimum mass of sample in function of particle size, for a number of analytes (Ash, Moisture, several elements)

Evaluation of effect of different particle size reduction devices on: loss of analytes (mostly volatile ones, like moisture, mercury, other volatile elements…), mass recovery, resulting homogeneity

QR-E Plastic paper fluff sample3

QR-D MSW sample3particle size reduction system 6

2composition

Total levelsNotesNo of levelsKey variables


prCEN/TS 15413 Methods for the preparation of the test sample from the laboratory sample

Loss of analytes: the temperature developed within the mills were almost always less than 60 °C, so volatile compounds (mainly moisture and mercury) don’t show any significant loss due to the system used for particle size reduction.

For all parameters, differences between the three treatment procedures (Low, Mid and High stress) are due just to the intrinsic heterogeneity of the sample.

Mass recovery: the “Low-stress” treatment procedure shows the best mass recovery (> 90%), while the “Mid” and “High” stress procedures perform somehow worse (about 80%). This is due to the different particle size reduction used: the cutting mill used in the low-stress procedure develops less dust during processing compared to the rotor-beater mills, so it should be preferred when possible.

Resulting micro-homogeneity (between the 15 portions of about 1 gram each) appear not to be influenced by the system used for particle size reduction.

Resulting macro-homogeneity (between the 3 portions of about 20 grams each) appear not to be influenced as well.


Task 6.5 Validation of the TS for the determination of Al metal through the execution of ruggedness testing for main factors of

influence and laboratory tests for the definition of a suitable size-reduction

Activity performed at VTT

3Still in progress

3grain sizeMethod B - ashing + DTA

3grain size

3amount of test portion

73boiling timeMethod A – extraction with nitric acid + ICP

Total levels

NotesNo of levels

Key variablesMethod


prCEN/TS 15412 Methods for the determination of metallic aluminium

Due to heterogeneous nature of SRF samples containing elements in metallic form it is recommended that as large test portions are used as practically possible.This is specially the case with low concentrations of metallic aluminium. Our recommendation is to use larger, up to 5 g test portion, if metallic aluminium is not visible in the sample. Lower amount may be used if metallic aluminium is clearly visible.

It is recommended that laboratory samples are homogenized properly before extracting of test portion. Due to high particle density variation in samples and test portions attention should be paid on possible segregation of particle during transportation, handling and even when removing a test portion from laboratory sample.

Recovery rate can be checked by spiking with metallic aluminium.


List of deliverables

30Technical ReportFinal Report on the validation of TS for sample reduction including recommendations to TC 343 for the eventual revision of the TS before its

upgrade to a European Standard (EN)

D6.5

18Technical ReportProgress Report on the validation of TS for sample reduction - Month 18

D6.4

30Technical ReportFinal Report on ruggedness testing on chemical parameters including

recommendations to TC 343 for the eventual revision of the TS before its upgrade to a European Standard (EN)

D6.3

18Technical ReportProgress Report on

ruggedness testing on chemical parameters

D6.2

6Technical ReportMethod Manual for the intercomparison of chemical parameter, including draft methods and parameters

D6.1

MonthType of documentContentDeliverable


Timetable

Validation of TS for sample reduction from

laboratory sample to test portion

WP 6 Task 4

Supervision of the intercomparison; meetings organisation for the

discussion of the results

WP 6 Task 3

Contractual arrangements with laboratories participating in the

intercomparison exercise

WP 6 Task 2

Ruggedness testing on TS for chemical

parameters

WP 6Task 1-5

3633302724211815129631

• List of participant laboratories - Month 3• End of ruggedness testing - Month 26• End of validation for size reduction - Month 26

Milestone

consortium meeting, december 14, 2006 1 quovadis grant - agreement eie/031/s07.38597 quality...

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