11th Needle Leaf InterlaboratoryComparison Test

Results & Re-Qualifikation

Forest Foliar Co-ordinating Centre

2nd Labhead Meeting

Warsaw/Poland 2009-10-12

Alfred Fürst

11th Ringtest - Timetable

• Information of the participants (April 2008)

• Deadline registration (2008-07-04)

• Submission of the test samples (July 2008)

• Deadline of data submission (2009-01-04)

• First results (2009-01-19)

• Qualification Reports (Febuary/March 2009)

• Final Report / QA-Rfoliar09 (February/March 2009)

• Re-qualification started (decided in Hamburg in January

2009)

• Re-qualification finished (Deadline 2009-10-01)

Sample material

• Pine branches - Finland

• Pine needles (Pinus brutia) - Turkey

• Maple leaves - Austria

• Spruce needles – Finland (= Sample 1

from 3rd Test)

Special thank to John Derome (Finland) and Mehmet

Sayman (Turkey) and their employees for sampling

and preparing samples for this ringtest!

Countries/Laboratories

562811th

542910th

53289th

52308th

43237th

46266th

53295th

52294th

51293rd

39252nd

24211st

Number of

laboratories

Number

of countries

Interlaboratory

Comparison Test

Accreditation status (EN 17025)

yes now

in 1-2 years

later

not planned

n=40

23

labs

Usage of contol chats

Average

Others

no

n=40

30

labs

3

Comparison between 3rd and 11th

Interlaboratory Comparison Test

5050(mg/g)

5,235,18Potassium

5149(mg/g)

1,331,33Magnesium

5149(mg/g)

3,483,55Calcium

5150(mg/g)

1,591,56Phosphorus

4746(mg/g)

0,910,91Sulphur

4845(mg/g)

11,7311,74Nitrogen

Number of LabsMeanNumber of

Labs

Mean(Unit)

11th

Interlaboratory Comparison

Test 2008/09 (Sample 4)

3rd

Interlaboratory Comparison

Test 1997/98 (Sample 1)

Element

Comparison between 3rd and 11th

Interlaboratory Comparison Test

3717(g/100g)

51,3850,96Carbon

2123(µg/g)

7,918,58Boron

1613(ng/g)

20,4936,60Cadmium

1218(µg/g)

0,210,40Lead

4138(µg/g)

2,522,65Copper

4045(µg/g)

44,5645,45Iron

4246(µg/g)

334,9338,2Manganese

4145(µg/g)

25,0924,75Zinc

Number of LabsMeanNumber of LabsMean(Unit)

11th

Interlaboratory Comparison Test

2008/09 (Sample 4)

3rd

Interlaboratory Comparison Test

1997/98 (Sample 1)

Element

Comparison between 3rd and 11th

Interlaboratory Comparison Test

• Most of the results are very good comparable

• Only the Cd and Pb results show smalldifferences (lowerer results in 2008/2009)

– Low concentration

– Progress in analytical chemistry (1997 to 2008) (instrumentation and knowledge)

– Avoid open digestion method, use of GF-AAS and ICP-MS

25

50

75

100

125

150

175

200

225

250

275%

3rd Test - 1997/1998 („0.40 Pb mg/kg“)

Flameless-AAS ICP-OES

ICP

-OE

S +

Ultraso

nic

Flame

AAS

1525%

*

*

**

*

* **

* *

*

* Outside of the tolerable limits

50

75

100

125

150

175

200%

11th Test - 2008/2009 („0.21 Pb mg/kg“)

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

<L

OQ

Flameless

AAS

ICP-OES ICP-MS

ICP

-OE

S +

Ultraso

nic

*

*

**

Flam

eAA

S

Tolerable limits

-95-105C

-70-130Cd

Element Tolerable deviation from

mean in %

for concentrations above

N 90-110 5mg/g

S 85-115 0.5mg/g

P 90-110 0.5mg/g

Ca 90-110 3mg/g

Mg 90-110 0.5mg/g

K 90-110 1mg/kg

Mn, Zn 85-115 20 g/g

Cu 80-120 -

Fe 80-120 20 g/g

Pb 70-130 0.5 g/g

B 80-120 5 g/g

Tolerable limits for

low concentrationsElement Tolerable deviation from

mean in %

for concentrations below

N 85-115 5mg/g

S 80-120 0.5mg/g

P 85-115 0.5mg/g

Ca 85-115 3mg/g

Mg 85-115 0.5mg/g

K 85-115 1mg/kg

Zn 80-120 20 g/g

Mn 80-120 20 g/g

Fe 70-130 20 g/g

Pb 60-140 0.5 g/g

B 70-130 5 g/g

Element Tolerable 10th Labtest 11th Labtest

limits 2007/2008 2008/2009

( %) Non Number of

mean values

Non Number of

mean valuestolerable tolerable

(%) (%)

N 10 2,6 196 10,4 192

S 15 15,4 188 14,4 188

P 10 13,2 204 14,2 204

Ca 10 17,2 204 19,1 204

Mg 10 10,8 204 18,6 204

K 10 16,8 208 17,5 200

Zn 15 10,2 176 6,7 164

Mn 15 2,8 180 6,5 168

Fe 20 5,7 176 13,1 160

Cu 20 4,9 164 17,1 164

Pb 30 13,0 100 9,8 92

B 20 13,5 96 12,5 88

Cd 30 17,0 100 7,7 104

C 5 3,2 156 16,9 148

Mean element concentrations and

percentage of non-tolerable results

12,0016,0014,0028,00%

5,239,184,270,38mg/gK

13,7313,7317,6429,41%

1,333,051,850,23mg/gMg

17,6515,6923,5319,61%

3,4822,126,152,67mg/gCa

9,8011,7611,7623,53%

1,591,371,460,14mg/gP

10,6412,7712,7721,28%

0,912,631,810,43mg/gS

6,256,258,3322,92%

11,7321,1512,63,23mg/gN

Pinus brutia

Spruce

needles

Maple leavesPine needles-Pine branches

Sample 4Sample 3Sample 2Sample 1Parameter

Unit

Mean element concentrations and

percentage of non-tolerable results

16,2216,2216,2218,92%

51,3848,351,6752,01g/100gC

18,180,009,0922,73%

7,9160,7219,353,43µg/gB

15,383,853,853,85%

20,4962,89161,8246,2ng/gCd

17,398,704,358,70%

0,210,495,416,93µg/gPb

21,954,8817,0724,39%

2,527,392,882,96µg/gCu

12,55,002,532,50%

44,56108,6243240,2µg/gFe

9,524,764,767,14%

334,997,5152,37104,4µg/gMn

9,764,884,887,32%

25,0934,1430,6428,73µg/gZn

Pinus brutia

Spruce needlesMaple leavesPine needles-Pine branches

Sample 4Sample 3Sample 2Sample 1Element

Unit

40

60

80

100

120

140

160

180

200

220

240

260

280%

Sulphur - Determination (Sample 1)

0,43 g/kg

Pine branches

Element-analyzer

ICP-OES

ICP-MS

X-Ray

Turbidimetry

CNS Analyzer

30

40

50

60

70

80

90

100

110

120

130%

Calcium - Determination (Sample 2)

6.15 g/kg

Pine needles (pinus brutia)

Flame-AAS

ICP-OES

X-Ray

Buffer against chemical interferences (La2+ or EDTA)?

Iron – Pretreatment methods

(pine branches)

9273Pellets and X-Ray (3)

35270Pressure digestion (9)

46229Microwave (20)

44222Open digestion (4)

39195Dry ashing (3)

Std.dev.

mg/kg

MeanMethod

Iron - Digestion method (Sample 1)

50

60

70

80

90

100

110

120

130

140

150%

Open digestion

Pressure digestion

Microwave

Dry ashing

Pellets (X-Ray)

240,2 mg/kg

Pine branches

Fe + SiO2

50

60

70

80

90

100

110

120

130

140

150%

Iron - Digestion method (Sample 2)

Open digestion

Pressure digestion

Microwave

Dry ashing

Pellets (X-Ray)

243,0 mg/kg

Pine needles (pinus brutia)

50

60

70

80

90

100

110

120

130%

Potassium - Digestion (Sample 3)

Open digestion

Pressure digestion

Microwave

9.18 g/kg

Maple leaves

Dry ashing

Pellets (X-Ray)

Element losses are possible

• Zn (6.7% non tolerable)

– avoid of contamination

– avoid of open digestion methods

• Pb (9.8% non tolerable)

– avoid of contamination

– avoid of open digestion methods

– LOQ fixed and used from more laboratories(ICP-OES not sensitive enough!)

• Cd (7.7% non tolerable)

– avoid of contamination

– avoid of open digestion methods

– LOQ fixed and used from more laboratories

Decrease of non-tolerable Results

Feedback from the laboratories -

Reasons for wrong results

• New instrument / methodic problem (4 labs)

• Too small sample weight for element-analyzer

„wrong“ instrumentation (2 labs)

• Old instrumentation (2 labs)

• Wrong calibration (4 labs)

• No reason found (3 labs)

• Wrong blanks / contamination (3 labs)

• Submit results in wrong units (5 labs)

• Wrong/no moisture correction (5 labs)

„Common“ Instrumentation

• N, C and (S): Element-analyzers

• S, P, Ca, Mg, K, Mn, Zn, Fe, Cu, B:

Pressure or Microwave digestion &

ICP-OES

• Pb and Cd: Pressure or Microwave

digestion & ICP-MS, Flameless-AAS

Instrumentation

• Buy „good & common“ well known instrumentswhich is used from other laboratories too

• Use Google group QA/QC to inform yourselfabout different instruments

• Laboratory assistance programme

• 40 laboratories submit their instrumentationinformation for the needle/leaf Interlaboratorytest – each participant get detailed informationabout the instrumentation (type & companies)

• For a new instrument a training course isneeded!

Wrong Units

Moisture Correction

• All results should be reported on

dry matter 105 C

• Moisture correction factor must be always

greater than 1!

Factor = wet weight / dry weight

Re-Qualification Process

Laboratories which have analysed

monitoring samples 2008/2009

FutMon Labs

ICP-Forests Labs

Other Labs

Participating Laboratories

11th Ringtest / Percentage of correct results

ICP-Forests labs *)

0

10

20

30

40

50

60

70

80

90

100F

05

A6

1

A5

2

F1

2

A5

5

F1

6

F2

0

F2

5

A6

9

F0

2

A6

0

F0

8

F0

6

F1

0

F0

7

A5

8

F1

5

F1

8

F1

3

F2

7

A6

2

A4

7

F2

4

F2

2

Labcode number

%

*) Laboratories which have analysed 2008/2009 monitoring samples for ICP-Forests

Results per Laboratory

Laboratories with „problems“

162-3 elements

6151 element

„ICP-Forests“

labs *)all labsfailed with

*) Laboratories which have analysed 2008/2009 monitoring samples for ICP-

Forests

ICP-Forests*) Laboratories

with problems

*) Laboratories which have analysed 2008/2009 monitoring samples for ICP-Forests

Ca, Mg, KCroatiaA62

NCuDenmarkA60

CuGermanyF08

CGermanyF15

CEstoniaF18

CBegium/WalloniaA47

SLatviaF24

P, K, CaItalyF22

Madatory param.

not analyzedfailed withCountryNew Code

Re-Qualification ProcessFutMon labs

FutMon Labs

ICP-Forests Labs

Other Labs

Participating Laboratories

Re-qualification

• The laboratory must participate for all

mandatory parameters (N, S, P, Ca, Mg, K, C)

• It has been decided to qualify the results of

each parameter separately

• If 50% or more of the results for this parameter

for all the samples of the ringtest are within the

tolerable limits, the laboratory is qualified.

• Re-qualification is mandatory for

laboratories of the FutMon partners and

recommended for ICP-Forests laboratories

Re-qualification

• The report should be sent to FFCC (add the laboratorycode number on your report!). A form for the re-qualification report can be downloaded fromwww.ffcc.at

• In case there is not enough sample material left –FFCC will send additional ringtest sample material.

• The ringtest samples should be re-analyzed and allprintouts, sample weights, dilution factors andcalibration factors should be submitted too.

• If the reason for the wrong results is a decimal error in the data submission or some other miscalculation, a short statement is enough.

• FFCC will send an updated qualification report to thelaboratory and inform PCC.

Labs of the FutMon Beneficiaries

• 33 laboratories

• 19 are qualified and 14 laboratories failed

(not tolerable results or no participation)

• 10 of the 14 laboratories has passed the

re-qualification

• What is with the rest (4 laboratories)???

Status 1st of October 2009

FutMon Beneficiaries - Problems

with Mandatory Parameters

<<<<<<<<<><F22040

<<<<<<<>F24038

n.a.n.a.n.a.n.a.n.a.n.a.F17023

><<>F28021

<<<<<<<>>n.a.>F01020

<<>><<<><<<>>>>>>>>>>>>F26020

<>>>><<n.a.>>>F21013

>>><<<>>>><<n.a.A43012

<>n.a.A60008

>>>F03003

mandatory parameters

newBeneficiaryKMgCaPSN

LabcodeFutMon

n.a. = not analyzed

FutMon Beneficiaries - Problems

with Optional Parameters

>n.a.<>><<<F11034

>>>F08031

<<<<n.a.F15028

n.a.<<n.a.>>>>>>F28021

>>>>n.a.n.a.n.a.n.a.n.a.n.a.n.a.F21013

n.a.n.a.n.a.n.a.n.a.<<<>>>>A43012

<<<<n.a.<<<F18009

n.a.n.a.<<<A60008

optional parameters

CCdBPbCuFeMnZnLab-

codenew

FutMonBeneficiary

n.a. = not analyzed

Not qualified FutMon labs

• Denmark (A60): Cu

• Greece (A43): S, Ca, Mg, K, Zn, Mn

• Hungary (F21): S

• Romania (F01): S

Status 1st of October 2009

12th Needle Leaf InterlaboratoryComparison Test

Forest Foliar Co-ordinating Centre

2nd Labhead Meeting

Warsaw/Poland 2009-10-12

Alfred Fürst

12th Ringtest -Timetable

• Information of the participants (March/April 2009)

• Deadline registration (2009-07-06)

• Submission of the test samples (July 2009)

• Deadline of data submission (Deadline 2010-01-03)

• First results (January 2010)

• Qualification Reports (Febuary/March 2010)

• Final Report / QA-Rfoliar09 (February/March 2010)

• Requalification finished (2010-10-01)

Sample material

1. Spruce needles

2. Oak leaves

3. Bears garlic

4. Spruce needles

Special thank to John Derome (Finland), Mireille

Barbaste (France), Peter Waldner (Switzerland) and

their employees for collecting and prepairing samples

for this ringtest.

Good luck for your 12th ringtest participation!

Your good results in the 12th ringtest

will be based on:

•Your better kowledge,

•Your good instrumentation and

•QA/QC in daily routine

Thank you for

your attention!

alfred.fuerst@bfw.gv.at