Heavy Metals and Trace Elements 2018/PT - DLA 49-2018...July 2018 DLA 49/2018 – Heavy Metals and Trace Elements Table 1: Composition of DLA-Samples Ingredients Content Supplementary

July 2018 DLA 49/2018 – Heavy Metals and Trace Elements

Proficiency Tests

DLAfood

cosmeticsconsumer goodswww.dla-lvu.de

Evaluation Reportproficiency test

DLA 49/2018

Heavy Metals and Trace Elements:

in dietary food with milk and soy protein

Dienstleistung Lebensmittel Analytik GbRWaldemar-Bonsels-Weg 17022926 Ahrensburg, Germany

[email protected] www.dla-lvu.de

Coordinator of this PT: Dr. Gerhard Wichmann

Reprint, also in part, only with written permission from DLA-AhrensburgPage 1 of 104


Allgemeine Informationen zur Eignungsprüfung (EP)General Information on the proficiency test (PT)

EP-AnbieterPT-Provider

DLA - Dienstleistung Lebensmittel Analytik GbRGesellschafter: Dr. Gerhard Wichmann und Dr. Matthias Besler-Scharf

Waldemar-Bonsels-Weg 170, 22926 Ahrensburg, Germany

Tel. ++49(0)171-1954375 Fax. ++49(0)4102-9944976eMail. [email protected]

EP-NummerPT-Number

DLA 49/2018

EP-KoordinatorPT-Coordinator

Dr. Gerhard Wichmann

Status des EP-BerichtStatus of PT-Report

Abschlussbericht / Final report (17 July 2018) Gültig ist die jeweils letzte Version/Korrektur des Berichts. Sie ersetzt alle vorangegangenen Versionen.Only the latest version/correction of the report is valid. It replaces all preceding versions.

EP-Bericht FreigabePT-Report Authorization

Dr. Matthias Besler (Technischer Leiter / Technical Manager)- gezeichnet / signed M. Besler-ScharfDr. Gerhard Wichmann (QM-Beauftragter / Quality Manager)- gezeichnet / signed G. Wichmann Datum / Date: 17 July 2018

UnteraufträgeSubcontractors

Falls im Rahmen der Eignungsprüfung eine Prüfung der Gehalte, Homogenität undStabilität von EP-Parametern durchgeführt wurde, hat DLA diese im Unterauftrag vergeben.In case the analysis of the content, homogeneity and stability of PT-parameters was part of the proficiency test, the determinations were subcontracted by DLA.

VertraulichkeitConfidentiality

Die Teilnehmerergebnisse sind im EP-Bericht in anonymisierter Form mit Auswertenummern benannt. Daten einzelner Teilnehmer werden ausschließlich nach vorheriger Zustimmung des Teilnehmers an Dritte weitergegeben.Participant result are named anonymously with evaluation numbers in the PT report. Data of individual participants will be passed on to third parties only with prior consent of the participant.



Inhalt / Content1. Introduction..................................................52. Realisation...................................................5

2.1 Test material...........................................52.1.1 Homogeneity............................................72.1.2 Stability..............................................72.2 Sample shipment and information to the test..............82.3 Submission of results....................................8

3. Evaluation...................................................93.1 Consensus value from participants (assigned value).......93.2 Robust standard deviation................................93.3 Repeatability standard deviation.........................93.4 Reproducibility standard deviation......................103.5 Exclusion of results and outliers.......................103.6 Target standard deviation (for proficiency assessment). .113.6.1 General model (Horwitz)...............................113.6.2 Precision experiment..................................123.6.2 Precision experiment..................................123.6.3 Value by perception...................................143.6.3 Value by perception...................................143.7 z-Score.................................................143.8 z'-Score................................................163.9 Reproducibility coefficient of variation (CVR)..........163.10 Quotient S*/σpt........................................173.11 Standard uncertainty of the assigned value.............17

4. Results......................................................184.1 Al – Aluminium in mg/kg.................................204.2 Ba – Barium in mg/kg....................................224.3 Ca – Calcium in mg/kg...................................244.4 Cd – Cadmium in mg/kg...................................264.5 Co – Cobalt in mg/kg....................................284.6 Cr – Chrom / Chromium in mg/kg..........................304.7 Cu – Kupfer / Copper in mg/kg...........................324.8 Fe – Eisen / Iron in mg/kg..............................344.9 I – Iod / Iodine in mg/kg...............................364.10 K – Kalium / Potassium in mg/kg........................384.11 Mg – Magnesium in mg/kg................................404.12 Mn – Mangan / Manganese in mg/kg.......................424.13 Mo – Molybdän / Molybdenum in mg/kg....................444.14 Na – Natrium / Sodium in mg/kg.........................464.15 Ni – Nickel in mg/kg...................................484.16 P – Phosphor / Phosphorus in mg/kg.....................504.17 Rb – Rubidium in mg/kg.................................524.18 Se – Selen in mg/kg....................................544.19 Zn – Zink / Zinc in mg/kg..............................56

5. Documentation...............................................585.1 Details by the participants.............................58



5.1.1 Primary Data and analytical Methods...................585.1.2 Analytical Methods....................................775.2 Homogeneity.............................................965.2.1 Homogeneity of bottled PT-samples.....................965.2.2 Comparison of sample numbers / test results and trend line........................................................965.3 Kernel Density Plots of Results.........................975.4 Information on the Proficiency Test (PT)...............101

6. Index of participant laboratories in alphabetical order.....1027. Index of references.........................................103



1. Introduction

The participation in proficiency testing schemes is an essential elementof the quality-management-system of every laboratory testing food andfeed, cosmetics and food contact materials. The implementation ofproficiency tests enables the participating laboratories to prove theirown analytical competence under realistic conditions. At the same timethey receive valuable data regarding the verification and/or validationof the particular testing method [1, 5].The purpose of DLA is to offer proficiency tests for selected parametersin concentrations with practical relevance.Realisation and evaluation of the present proficiency test follows thetechnical requirements of DIN EN ISO/IEC 17043 (2010) and DIN ISO13528:2009 / ISO 13528:2015 [2, 3].

2. Realisation

2.1 Test material

The material to be tested is a mixture of two supplements containing milkand soy protein, see Table 1. The raw material was homogenized and sieved. The composition is shown inTable 1.Afterwards the samples were portioned to approximately 8 g into metal-lised PET film bags and chronologically numbered.



Table 1: Composition of DLA-Samples

Ingredients Content

Supplementary food 1Ingredients:Milk protein, soy protein, low-fat cocoa powder, flavour-ing, L-ascorbic acid, magnesium hydroxide, sweeteners: so-dium cyclamate, saccharin sodium, beetroot juice powder, L-leucine, L-valine, L-isoleucine, separating agent: Silic-on dioxide, salt, alpha-tocopheryl acetate, nicotinamide, zinc oxide, calcium D-pantothenate, pyridoxine hydrochlor-ide, thiamine mononitrate, riboflavin, folic acid, B-biot-in. Nutrients per 100 g: protein 83 g, salt 1,0 g, fat 1,5 g, carbohydrates 2,9 g

50 g/100g

Supplementary food 2Ingredients:Skimmed milk, whey products, vegetable oils, starch, lactose, calcium carbonate, iron sulphate, emulsifier soya-lecitine, potassium chloride, potassium citrate, L-tyr-osine, vitamin C, sodium chloride, magnesium carbonate, zinc sulphate, L-tryptophan, niacin, pantothenic acid, cop-per sulphate, vitamin A, vitamin B1, vitamin B6, vitamin E,manganese sulphate, vitamin B2, folic acid, potassium iod-ide, vitamin K, sodium selenite, vitamin D, biotin, vitaminB12.

Nutrients per 100 g: protein 10,2 g, salt 0,4 g, fat 25,5 g, carbohydrates 59,1 g

50 g/100g

Note: The metrological traceability of temperature, mass and volume during production of the PTsamples is ensured by DAkkS calibrated reference materials.



2.1.1 Homogeneity

The mixture homogeneity before bottling was examined 5-fold by determina-tion of copper by ICP/MS (DIN EN ISO 17294-2). The repeatability standarddeviation was 2,54% and thus within the range of repeatability standarddeviations of comparable methods (e.g. ASU §64 L 00.00-144, s. 3.6.1).The results of homogeneity analysis are given in the documentation.

The calculation of the repeatability standard deviations Sr of the parti-cipants was also used as an indicator of homogeneity. The coefficient ofvariation (CVr) for all analytes ranges from 0,99% - 7,18%. Cadmium is anexception (CVr 11,5%). Thus they were similar to the repeatability stand-ard deviations of the corresponding official methods (e.g. ASU §64 L00.00-144, s. 3.6.2) (see Tab. 3) [16-19]. The repeatability standard de-viations of the participants' results are given in the documentation inthe statistic data (see 4.1 to 4.19).

Furthermore, the homogeneity was characterized by the trend line functionof participants' results for chronological bottled single samples (see5.2.2).

In case the criterion for sufficient homogeneity of the test items is notfulfilled the impact on the target standard deviation will be verified.If necessary the evaluation of results will be done considering thestandard uncertainty of the assigned value by z'-scores (s. 3.8 and 3.11)[3].

2.1.2 Stability

A water activity (aW) of < 0,5 is an important factor to ensure the sta-bility of dry or dried products during storage. Optimum conditions forstorage is the aW value range of 0,15 - 0,3. In this range the lowestpossible degradation rate is to be expected [16].

The experience with various DLA test materials showed good storage sta-bility with respect to the durability of the sample (spoilage) and thecontent of the PT parameters for comparable food matrices and wateractivity (aW value <0,5).The aW value of the PT samples was approx. 0,23 (19,9C). The stability ofthe sample material was thus ensured during the investigation period un-der the specified storage conditions.



2.2 Sample shipment and information to the test

Two portions of test material were sent to every participating laboratoryin the 17th week of 2018. The testing method was optional. The testsshould be finished at 8st June 2018 the latest.

With the cover letter along with the sample shipment the following in-formation was given to participants:

The two portions contain identical samples of a supplement food mixturewith a mostly natural content of 19 elements to be determinedquantitatively. Please note the attached information on the proficiency test.(see documentation, section 5.4 Information on the PT)

2.3 Submission of results

The participants submitted their results in standard forms, which havebeen handed out with the samples (by email).

The finally calculated concentrations of the parameter as average ofduplicate determinations of both numbered samples were used for thestatistical evaluation. For the calculation of the repeatability– andreproducibility standard deviation the single values of the doubledetermination were used.

Queried and documented were single results, recovery and the used testingmethods. In case participants submitted several results for the sameparameter obtained by different methods these results were evaluated withthe same evaluation number with a letter as a suffix and indication ofthe related method.

Of the 11 participants, 9 gave results.


http://dict.leo.org/ende?lp=ende&p=/gQPU.&search=repeat

http://dict.leo.org/ende?lp=ende&p=/gQPU.&search=retrieval

http://dict.leo.org/ende?lp=ende&p=/gQPU.&search=determination


3. Evaluation

3.1 Consensus value from participants (assigned value)

The robust mean of the submitted results was used as assigned value (Xpt)(„consensus value from participants“) providing a normal distribution.The calculation was done according to algorithm A as described in annex Cof ISO 13528 [3]. If there are < 12 quantitative results and an increaseddifference between robust mean and median, the median may be used as theassigned value (criterion: ∆ median - rob. mean > 0,3 σpt) [3].

The condition is that the majority of the participants' results show anormal distribution or are distributed unimodal and symmetrically. Tothis end, an examination of the distribution is carried out, inter alia,using the kernel density estimate [3, 12].

In case there are indications for sources of higher variability such as abimodal distribution of results, a cause analysis is performed.Frequently different analytical methods may cause an anomaly in results'distribution. If this is the case, separate evaluations with own assignedvalues (Xpti) are made whenever possible.

The statistical evaluation is carried out for all the parameters for aminimum of 7 values are present.

In the present evaluation statistic data for parameters with a minimumof 5 values were given for information also. It should be consideredthat the significance can be limited due to the low number of results.

The actual measurement results will be drafted. Individual results, whichare outside the specified measurement range of the participatinglaboratory (for example with the result > 25 mg/kg or < 2,5 mg/kg) or theindicating “0” will not be considered for the statistic evaluation [3].

3.2 Robust standard deviation

For comparison to the target standard deviation σpt (standard deviationfor proficiency assessment) a robust standard deviation (Sx) was calcu-lated. The calculation was done according to algorithm A as described inannex C of ISO 13528 [3].

3.3 Repeatability standard deviation

The repeatability standard deviation Sr is based on the laboratory´sstandard deviation of (outlier free) individual participant results, eachunder repeatability conditions, that means analyses was performed on thesame sample by the same operator using the same equipment in the samelaboratory within a short time. It characterizes the mean deviation ofthe results within the laboratories [3] and is used by DLA as anindication of the homogeneity of the sample material.

In case single results from participants are available the calculation ofthe repeatability standard deviation Sr, also known as standard deviationwithin laboratories Sw, is performed by: [3, 4].



The relative repeatability standard deviation as a percentage of the meanvalue is indicated as coefficient of variation CVr in the table of stat-istical characteristics in the results section in case single resultsfrom participants are available.

3.4 Reproducibility standard deviation

The reproducibility standard deviation SR represents a inter-laboratoryestimate of the standard deviation for the determination of eachparameter on the bases of (outlier free) individual participant results.It takes into account both the repeatability standard deviation Sr andthe within-laboratory standard deviation SS. Reproducibility standarddeviations of PT´s may differ from reproducibility standard deviations ofring trials, because the participating laboratories of a PT generally usedifferent internal conditions and methods for determining the measuredvalues. In the present evaluation, the specification of the reproducibilitystandard deviation, therefore, does not refer to a specific method, butcharacterizes approximately the comparability of results between thelaboratories, assumed the effect of homogeneity and stability of thesample are negligible.

In case single results from participants are available the calculation ofthe reproducibility standard deviation SR is performed by: [3, 4].

The relative reproducibility standard deviation VKR in percent of themean is given as variation coefficient in the statistical data of parti-cipant for each parameter. The significance of VKR is further explainedin section 3.9.

3.5 Exclusion of results and outliers

Before statistical evaluation obvious blunders, such as those with incor-rect units, decimal point errors, and results for a another proficiencytest item can be removed from the data set [2]. Even if a result clearlydeviates from the robust mean (e.g. factor >10) and has an influence onthe robust statistics, a result can be excluded from statistical evalu-ation [3].

All results should be given at least with 2 significant digits. Specify-ing 3 significant digits is usually sufficient.

Results obtained by different analytical methods causing an increasedvariability and/or a bi- or multimodal distribution of results, aretreated separately or could be excluded in case of too few numbers ofresults. For this results are checked by kernel density estimation [3,12].

Results are tested for outliers by the use of robust statistics (al-gorithm A): If a value deviates from the robust mean by more than 3 timesthe robust standard deviation, it can be classified as an outlier (seeabove) [3]. Due to the use of robust statistics outliers are not ex-cluded, provided that no other reasons are present [3]. Detected outliersare only mentioned in the results section, if they have been excludedfrom the statistical evaluation.



3.6 Target standard deviation (for proficiency assessment)

The target standard deviation of the assigned value σpt (= standard devi-ation for proficiency assessment) can be determined according to the fol-lowing methods.

If an acceptable quotient S*/σpt is present, the target standard devi-ation of the general model by Horwitz is preferably used for the profi-ciency assessment. It is usually suitable for evaluation of interlaborat-ory studies, where different methods are applied by the participants. Onthe other hand the target standard deviation from the evaluation of pre-cision data of an precision experiment is derived from collaborativestudies with specified analytical methods.

In cases where both above-mentioned models are not suitable, the targetstandard deviation is determined based on values by perception, see under3.6.3.

For information, the z-scores of both models are given in the evaluation,if available.

For the evaluation of the results, the target standard deviation wasused for all elements except Ca and Cr according to the general model ofHorwitz was applied (see 3.6.1). For the evaluation of Ca and Cr thetarget standard deviation according to a precision experiment was used(see 3.6.2).

Additionally for Al the standard uncertainty was considered by evaluat-ing with z'-scores (see 3.8).

Due to the number of < 5 the results for I and Rb were not evaluatedwith z-scores.

3.6.1 General model (Horwitz)

Based on statistical characteristics obtained in numerous PTs for differ-ent parameters and methods Horwitz has derived a general model for estim-ating the reproducibility standard deviation σR [6]. Later the model wasmodified by Thompson for certain concentration ranges [10]. The reprodu-cibility standard deviation σR can be applied as the relative targetstandard deviation σpt in % of the assigned values and calculated accord-ing to the following equations [3]. For this the assigned value Xpt isused for the concentration c.

Equations Range of concentrations corresponds to

σR = 0,22c c < 1,2 x 10-7 < 120 µg/kg

σR = 0,02c0,8495 1,2 x 10-7 ≤ c ≤ 0,138 ≥ 120 µg/kg

σR = 0,01c0,5 c > 0,138 > 13,8 g/100g

with c = mass content of analyte (as relative size, e.g. 1 mg/kg = 1 ppm = 10-6 kg/kg)



3.6.2 Precision experiment

Using the reproducibility standard deviation σR and the repeatabilitystandard deviation σr of a precision experiment (collaborative trial orproficiency test) the target standard deviation σpt can be derivedconsidering the number of replicate measurements m of participants in thepresent PT [3]:

The relative repeatability standard deviations (RSDr) and relative repro-ducibility standard deviation (RSDR) given in Table 2 were determined inring tests using the indicated methods. The resulting target standard deviations σpt, which were identifiedthere, were used to evaluate the results and to provide additional in-formation for the statistical data.



Table 2: Relative repeatability standard deviations (RSDr) and relativereproducibility standard deviations (RSDR) according to selected evalu-ations of tests for precision and the resulting target standard devi-ation σpt [16-26]

Para-meter

Matrix Mean RSDr RSDR σpt Method / Literature

Al Cocoa powder 205 3,25% 5,83% 5,36%1 ICP-MS [16]

Cocoa powder 210 1,91% 8,71% 8,61% ICP-OES [17]

As Fish homogenate 1,6 4,6% 8,8% 8,18% ICP-MS [18]

Mussels 9,3 4,5% 13% 12,6% ICP-MS [18]

Pb Fish homogenate 2,1 5,0% 8% 7,18% ICP-MS [18]

Mussels 2,5 13% 16% 13,1% ICP-MS [18]

Ca Lobster 183 4,90% 6,31% 5,27% ICP-OES [22]

Baby food soya 6191 3,41% 7,97% 7,60%1 ICP-OES [22]

Cd Fish homogenate 0,87 7,3% 11% 9,71%1 ICP-MS [18]

Mussels 1,7 3,9% 9,5% 9,09% ICP-MS [18]

Cr Baby food 0,17 7,3% 19% 18,3% GF-AAS [20]

Rice powder 0,11 19,2% 35% 32,3%1 GF-AAS [20]

Cu Lobster 16,40 5,72% 6,82% 5,49% ICP-OES [22]

Baby food soya 4,51 4,30% 11,06% 10,6%1 ICP-OES [22]

Fe Lobster 12,1 6,45% 8,59% 7,28% ICP-OES [22]


I Cod muscle 4,15 0,7% 8,9% 8,89% ICP-MS (16)

Soya food 1,26 3,7% 6,7% 6,17% ICP-MS (16)

K Lobster 871 3,63% 6,27% 5,71% ICP-OES [22]


Mn Lobster 1,20 4,74% 7,95% 7,21% ICP-OES [22]

Baby food soya 2,19 4,67% 13,7% 13,3%1 ICP-OES [22]

Mg Lobster 85 3,73% 8,63% 8,21% ICP-OES [22]


Mo Baby food 0,50 6,6% 21% 20,5% GF-AAS [20]

Rice powder 0,56 8,7% 20% 19,0%1 GF-AAS [20]

Na Lobster 186 3,31% 6,60% 6,17% ICP-OES [22]


P Lobster 973 3,16% 7,13% 6,78% ICP-OES [22]


S Lobster 876 3,13% 7,54% 7,21% ICP-OES [22]

Baby food soya 1234 3,86% 10,71% 10,4% ICP-OES [22]

Se Catfish 1,797 9,85% 10,1% 7,31% AAS [21]

Rice powder 0,374 2,41% 11,8% 11,7%1 AAS [21]

Zn Lobster 13,9 4,63% 7,90% 7,19% ICP-OES (22)

Baby food soya 43,5 2,60% 6,89% 6,64%1 ICP-OES (22) 1 used in evaluation (s. chapter 4)



3.6.3 Value by perception

The target standard deviation for proficiency assessment can be set at avalue that corresponds to the level of performance that the coordinatorwould wish laboratories to be able to achieve [3].

For the present evaluation the target standard deviation according to3.6.1 was regarded suitable partly using the z'-scores.

Table 3 shows selected statistic data of participants results of presentPT compared to PT results of previous years.

3.7 z-Score

To assess the results of the participants the z-score is used. Itindicates about which multiple of the target standard deviation (σpt) theresult (xi) of the participant is deviating from the assigned value (Xpt)[3].Participants’ z-scores are derived from:

The requirements for the analytical performance are generally consideredas fulfilled if

-2 ≤ z ≤ 2 .

The valid z-Score for each parameter is indicated as z-Score (σpt). Thevalue indicated as z-Score (Info) only obtains a informative character.The both z-Scores were calculated with the different target standarddeviations in accordance with 3.6.

3.7.1 Warning and action signals

In accordance with the norm ISO 13528 it is recommended that a resultthat gives rise to a z-score above 3,0 or below −3,0, shall be consideredto give an “action signal” [3]. Likewise, a z-score above 2,0 or below−2,0 shall be considered to give a “warning signal”. A single “actionsignal”, or “warning signal” in two successive PT-rounds, shall be takenas evidence that an anomaly has occurred which requires investigation.For example a fault isolation or a root cause analysis through the exam-ination of transmission error or an error in the calculation, in thetrueness and precision must be performed and if necessary appropriatecorrective measures should be applied [3].

In the figures of z-scores DLA gives the limits of warning and actionsignals as yellow and red lines respectively. According to ISO 13528 thesignals are valid only in case of a number of ≥ 10 results [3].



Table 3: Characteristics of the present PT (on grey) in comparison toprevious PTs since 2016 (SD = standard deviation, CV = coefficient ofvariation)

Parameter Matrix(Powder)

robust Mean[mg/kg]

rob. SD (S*)

[mg/kg]rel. SD (VKS*)

[%]QuotientS*/σpt

DLA-report

Al Mussels-fish 444 143 32,2% 2,21 DLA 58/2016

Al Potatoes 0,527 0,283 53,7% 1,51 DLA 46/2017

Al Food supplement 5,86 2,08 35,5% 1,71 DLA 49/2018

Ba Mussels-fish 2,35 0,832 35,5% 1,81 DLA 58/2016

Ba Potatoes 0,220 - - - DLA 46/2017

Ba Food supplement 0,708 0,0791 11,2% 0,66 DLA 49/2018

Ca Potatoes 238 12,0 5,04% 0,72 DLA 46/2017

Ca Food supplement 6540 259 3,97% 0,93 DLA 49/2018

Cd Mussels-fish 1,03 0,0616 5,97% 0,37 DLA 58/2016

Cd Potatoes 0,0399 0,0029 7,30% 0,28 DLA 46/2017

Cd Food supplement 0,0116 0,00263 22,7% 0,73 DLA 49/2018

Cr Mussels-fish 1,23 0,266 21,6% 1,4 DLA 58/2016

Cr Potatoes ** - - - DLA 46/2017

Cr Food supplement 0,218 0,0594 27,2% 1,4 DLA 49/2018

Co Mussels-fish 0,586 0,0347 5,91% 0,34 DLA 58/2016

Co Potatoes 0,0110 0,00223 20,3% 0,64 DLA 46/2017

Co Food supplement 0,0388 0,00564 14,5% 0,56 DLA 49/2018

Cu Mussels-fish 5,75 0,439 7,63% 0,62 DLA 58/2016

Cu Potatoes 1,98 0,117 5,90% 0,41 DLA 46/2017

Cu Food supplement 4,28 0,611 14,3% 1,1 DLA 49/2018

Fe Mussels-fish 305 22,1 7,24% 1,1 DLA 58/2016

Fe Potatoes 15,0 1,22 8,10% 0,76 DLA 46/2017

Fe Food supplement 60,3 4,41 7,31% 0,85 DLA 49/2018

K Potatoes 13162 604 4,59% 1,2 DLA 46/2017

K Food supplement 3931 347 8,83% 1,9 DLA 49/2018

Mg Potatoes 736 27,1 3,68% 0,62 DLA 46/2017

Mg Food supplement 1149 36,3 3,16% 0,57 DLA 49/2018

Mn Mussels-fish 8,79 0,696 7,93% 0,69 DLA 58/2016

Mn Potatoes 3,66 0,327 8,9% 0,68 DLA 46/2017

Mn Food supplement 3,58 0,326 9,10% 0,69 DLA 49/2018

Mo Mussels-fish 0,536 0,0400 7,45% 0,42 DLA 58/2016

Mo Potatoes 0,197 0,0161 8,2% 0,40 DLA 46/2017

Mo Food supplement 0,830 0,130 15,7% 0,95 DLA 49/2018

Na Potatoes 195 13,7 7,03% 1,0 DLA 46/2017

Na Food supplement 2944 154 5,23% 1,1 DLA 49/2018

Ni Mussels-fish 1,40 0,232 16,6% 1,1 DLA 58/2016

Ni Potatoes 0,0398 0,00645 16,2% 0,62 DLA 46/2017

Ni Food supplement 0,418 0,0590 14,1% 0,77 DLA 49/2018

P Potatoes 1451 49,1 3,38% 0,63 DLA 46/2017

P Food supplement 4870 386 7,92% 1,8 DLA 49/2018

Se Food supplement 0,219 0,0461 21,1% 1,0 DLA 49/2018

Zn Mussels-fish 51,0 5,17 10,2% 1,1 DLA 58/2016

Zn Potatoes 7,83 0,726 9,3% 0,79 DLA 46/2017

Zn Food supplement 109 15,2 14,0% 1,8 DLA 49/20181 with target standard deviation σpt'** no statistical evaluation (< 7 or < 5 results)



3.8 z'-Score

The z'-score can be used for the valuation of the results of theparticipants, in cases the standard uncertainty has to be considered (s.3.8). The z'-score represents the relation of the deviation of the result(x) of the participant from the respective consensus value (X) to thesquare root of quadrat sum of the target standard deviation (σpt) and thestandard uncertainty (Uxpt) [3].

The calculation is performed by:

If carried out an evaluation of the results by means of z 'score, we havedefined below the expression in the denominator as a target standarddeviation σpt'.

The requirements for the analytical performance are generally consideredas fulfilled if

-2 ≤ z' ≤ 2 .

For warning and action signals see 3.7.1.

3.9 Reproducibility coefficient of variation (CVR)

The variation coefficient (CVR) of the reproducibility (= relativereproducibility standard deviation) is calculated from the standarddeviation and the mean as follows [4, 13]:

CVR = SR * 100

X

In contrast to the standard deviation as a measure of the absolute varia-bility the CV gives the relative variability within a data region. Whilea low CV, e.g. <5-10% can be taken as evidence for a homogeneous set ofresults, a CV of more than 50% indicates a “strong inhomogeneity ofstatistical mass”, so that the suitability for certain applications suchas the assessment of exceeded maximum levels or the performance evalu-ation of the participating laboratories possibly can not be done [3].



3.10 Quotient S*/ σ pt

Following the HorRat-value the results of a proficiency-test (PT) can beconsidered convincing, if the quotient of robust standard deviation S*and target standard deviation σpt does not exceed the value of 2.A value > 2 means an insufficient precision, i.e. the analytical methodis too variable, or the variation between the test participants is higherthan estimated. Thus the comparability of the results is not given [3].

3.11 Standard uncertainty of the assigned value

Every assigned value has a standard uncertainty that depends on theanalytical method, differences between the analytical methods used, thetest material, the number of participating laboratories (P) and on otherfactors. The standard uncertainty (U(Xpt)) for this PT is calculated asfollows [3]:

If U(Xpt) ≤ 0,3 σpt the standard uncertainty of the assigned value needsnot to be included in the interpretation of the results of the PT [3].Values exceeding 0,3 imply, that the target standard deviation could betoo low with respect to the standard uncertainty of the assigned value.

The Quotient U(Xpt)/σpt is reported in the characteristics of the test.



4. Results

Comments to the distribution of the results:

The kernel density plots showed for all elements nearly a symmetricaldistribution of results (figures see documentation 5.3). Partly slightshoulders and separate smaller peaks can be seen, which are due toindividual values and outliers.For the element phosphorus, two peaks of approximately the same size wereobserved. This bimodal distribution cannot be explained by differentmethods. Since a non-conspicuous coefficient of variation (CVR) ispresent and the quotient S*/σpt (1,8) is acceptable, statisticalevaluation could be carried out for phosphorus.

Comments to the statistic data:

For I and Rb there were < 5 results, therefore no statistical evaluationcould be done.

For Ba, Cd, Co, Mo, Ni, P and Se there were < 7 results, thus the signi-ficance of the statistical evaluation is limited due to the low number ofresults.

The target standard deviations were calculated for all parameters exceptCa and Cr according to the model of Horwitz. For Ca and Cr the targetstandard deviation was calculated using statistical data obtained fromprecision experiments (ASU §64 method). For information the target stand-ard deviation using statistical data obtained from precision experiments(ASU §64 method) was additionally given, when available. For Ca and Cr,the target standard deviation was additionally calculated according tothe model of Horwitz for information purposes.

For Al the distribution of results showed an increased variability. Thequotient S*/σpt was clearly higher than 2,0. Thus the parameter was eval-uated considering the standard uncertainty by z'-scores. The quotientS*/σpt' was then 1,7 (s. Tab. 3).

For the other parameters the distribution of results showed a low to nor-mal variability. The quotients S*/σpt were all in the range of 0,6 to 1,9(s. Tab. 3).

The robust standard deviation as well as the repeatability and reprodu-cibility standard deviations were in the range of established values forthe applied methods (see 3.6.2).

The comparability of results is given.

The quotient U(Xpt)/σpt was increased for Al, Ba, Cd, Co, Cr, Cu, Fe, K,Mo, Na, Ni, P, Se and Zn with > 0,3 (0,4 to 0,6). For all other paramet-ers the quotient was low (< 0,3).

70% to 100% of results were in the regarding target range.



All following tables are anonymized. With the delivering of theevaluation report the participants are informed about their individualevaluation number.

In the first table the characteristics are listed:

Statistic Data

Number of results

Number of outliers

Mean

Median

Robust mean(Xpt)

Robust standard deviation (Sx)

Number with m replicate measurements

Repeatability standard deviation (Sr)

Coefficient of Variation (CVr)in %

Reproducibility standard deviation (SR)

Coefficient of Variation (CVR)in %

Target range:

Target standard deviation σpt or σpt'

Target standard deviation for information

lower limit of target range (Xpt – 2σpt) or (Xpt – 2σpt') *

upper limit of target range (Xpt + 2σpt) or (Xpt + 2σpt´) *

Variation coefficient VK in %

Quotient S*/σpt or S*/σpt'

Standard uncertainty U(Xpt)

Quotient U(Xpt)/σpt or U(Xpt)/σpt'

Number of results in the target range

Percent in the target range* Target range is calculated with z-score or z'-score

In the table below, the results of the participating laboratories areformatted in 3 valid digits**:

** In the documentation part, the results are given as they were transmitted by theparticipants.


Abweichung Hinweis

Deviation Remark

Auswerte- nummer Parameter

[Einheit / Unit] z-Score

σpt

z-Score (Info) Evaluation

number


4.1 Al – Aluminium in mg/kg

Vergleichsuntersuchung / Proficiency Test

Abb. / Fig. 1: Ergebnisse Aluminium / Results Aluminium


Statistic DataNumber of results 7Number of outliersMean 6,48Median 5,80Robust Mean (X) 5,86Robust standard deviation (S*) 2,08Number with 2 replicates 7

0,179

2,75%

3,24

49,8%Target range:

1,22

0,314

lower limit of target range 3,43upper limit of target range 8,29

1,70,9820,81

Results in the target range 5Percent in the target range 71%

Repeatability SD (Sr)

Repeatability (CVr)

Reproducibility SD (SR)

Reproducibility (CVR)

Target standard deviation σpt´Target standard deviation (for Information)

Quotient S*/σpt´Standard uncertainty U(Xpt)Quotient U(Xpt)/σpt´

12

34

56

78

9

0,0

2,0

4,0

6,0

8,0

10,0

12,0

14,0

Ergebnisse / Results

Aluminium [mg/kg]Obergrenze upper limitrobuster Mittelwert robust meanUntergrenze lower limit

Auswertenummer / evaluation number


Ergebnisse der Teilnehmer:Results of Participants:

Abb. / Fig. 2: Z´-Scores Aluminium


z´-Score z-Score Hinweis

Remark

1 7,22 1,36 1,1 4,32 5,80 -0,0610 -0,050 -0,193 5,89 0,0290 0,024 0,0924 13,3* 7,44 6,1 24567 5,10 -0,761 -0,63 -2,48 4,80 -1,06 -0,87 -3,49 3,24 -2,62 -2,2 -8,3

* Mean calculated by DLA

Auswerte- nummer

Aluminium [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

98

72

31

4-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z´-Scores

6,1



4.2 Ba – Barium in mg/kg


Abb. / Fig. 3: Ergebnisse Barium / Results Barium



0,0170

2,41%

0,0706

10,0%Target range:

0,119


0,660,04420,37



Repeatability (CVr)



Target standard deviation σptTarget standard deviation (for Information)

Quotient S*/σptStandard uncertainty U(Xpt)Quotient U(Xpt)/σpt

12

34

56

78

9

0,0

0,2

0,4

0,6

0,8

1,0


Barium [mg/kg]

Obergrenze upper limit

robuster Mittelwert robust mean




Abb. / Fig. 4: Z-Scores Barium


Barium [mg/kg] z-Score Hinweis

Remark

1 0,650 -0,0580 -0,492 0,700 -0,00800 -0,073 0,650 -0,0580 -0,494 0,820* 0,112 0,945678 0,720 0,0120 0,109


Auswerte- nummer

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt)

13

28

4-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.3 Ca – Calcium in mg/kg


Abb. / Fig. 5: Ergebnisse Calcium / Results Calcium


Statistic DataNumber of results 9Number of outliersMean 6470Median 6550Robust Mean (X) 6540Robust standard deviation (S*) 259Number with 2 replicates 9

136

2,11%

537

8,29%Target range:

497

279

lower limit of target range 5550upper limit of target range 7530

0,521080,22



Repeatability (CVr)





12

34

56

78

9

0

1000

2000

3000

4000

5000

6000

7000

8000


Calcium [mg/kg]Obergrenze upper limitrobuster Mittelwert robust meanUntergrenze lower limit




Abb. / Fig. 6: Z-Scores Calcium


z-Score z-Score Hinweis

Remark

1 7210 674 1,4 2,42 6700 160 0,32 0,583 6310 -227 -0,46 -0,814 6430* -112 -0,22 -0,405 6504 -35,5 -0,071 -0,136 5250 -1290 -2,6 -4,67 6690 148 0,30 0,538 6590 53,5 0,11 0,199 6550 11,1 0,022 0,040


Auswerte- nummer

Calcium [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

63

45

98

72

1-5,0

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.4 Cd – Cadmium in mg/kg


Abb. / Fig. 7: Ergebnisse Cadmium / Results Cadmium



0,00133

11,5%

0,00253

21,7%Target range:

0,00362

0,00112


0,730,001340,37



Repeatability (CVr)





12

34

56

78

9

0,0000,0020,0040,0060,0080,0100,0120,0140,0160,0180,020


Cadmium [mg/kg]



Untergrenze lower limit




Abb. / Fig. 8: Z-Scores Cadmium



Remark

<0,01 LOD in the target range0,0130 0,00143 0,40 1,30,0100 -0,00157 -0,43 -1,40,00840* -0,00317 -0,87 -2,80,0120 0,000433 0,12 0,39

<0,050 LOD in the target range0,0110 -0,000567 -0,16 -0,500,0150 0,00343 0,95 3,1


Cadmium [mg/kg]

Abweichung [mg/kg]

Deviation [mg/kg]

(σpt) (Info)

43

85

29

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.5 Co – Cobalt in mg/kg


Abb. / Fig. 9: Ergebnisse Kobalt / Results Cobalt



0,00212

5,43%

0,00579

14,8%Target range:

0,0101lower limit of target range 0,0186upper limit of target range 0,0590

0,560,003150,31



Repeatability (CVr)



Target standard deviation σpt


12

34

56

78

9

0,00

0,01

0,02

0,03

0,04

0,05

0,06

0,07


Kobalt/ Cobalt [mg/kg]Obergrenze upper limitrobuster Mittelwert robust meanUntergrenze lower limit




Abb. / Fig. 10: Z-Scores Cobalt


z-Score Hinweis

Remark

1 0,0390 0,000200 0,0202 0,0470 0,00820 0,813 0,0360 -0,00280 -0,284 0,0340* -0,00480 -0,47

5 <1,19

67 <0,050 LOD in the target range8 0,0380 -0,000800 -0,0799


Auswerte- nummer

Kobalt/ Cobalt [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt)

LOD over the target range

43

81

2-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.6 Cr – Chrom / Chromium in mg/kg


Abb. / Fig. 11: Ergebnisse Chrom / Results Chromium



0,0159

6,94%

0,0715

31,3%Target range:

0,0704

0,0439


0,840,02800,40



Repeatability (CVr)





12

34

56

78

9

0,00

0,05

0,10

0,15

0,20

0,25

0,30

0,35

0,40


Chrom/ Chromium [mg/kg]






Abb. / Fig. 12: Z-Scores Chrom/ Chromium



Remark

1 0,220 0,00191 0,027 0,0442 0,180 -0,0381 -0,54 -0,873 0,150 -0,0681 -1,0 -1,64 0,263* 0,0444 0,63 1,0567 0,370 0,152 2,2 3,58 0,200 -0,0181 -0,26 -0,419 0,207 -0,0111 -0,16 -0,251011


Auswerte- nummer

Chrom/ Chromium

[mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

32

89

14

7-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.7 Cu – Kupfer / Copper in mg/kg


Abb. / Fig. 13: Ergebnisse Kupfer / Results Copper



0,207

4,80%

0,617

14,3%Target range:

0,550

0,455


1,10,2550,46



Repeatability (CVr)





12

34

56

78

9

0,0

1,0

2,0

3,0

4,0

5,0

6,0


Kupfer/ Copper [mg/kg]






Abb. / Fig. 14: Z-Scores Kupfer / Copper



Remark

1 4,30 0,0233 0,042 0,0512 4,22 -0,0567 -0,10 -0,123 3,91 -0,367 -0,67 -0,814 4,02* -0,262 -0,48 -0,585 5,48 1,20 2,2 2,66 4,80 0,523 1,0 1,27 3,90 -0,377 -0,69 -0,838 4,70 0,423 0,77 0,939 3,45 -0,825 -1,5 -1,81011


Auswerte- nummer

Kupfer/ Copper [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

97

34

21

86

5-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.8 Fe – Eisen / Iron in mg/kg


Abb. / Fig. 15: Ergebnisse Eisen / Results Iron



1,12

1,84%

4,50

7,41%Target range:

5,20

4,04


0,851,840,35



Repeatability (CVr)





12

34

56

78

9

0

10

20

30

40

50

60

70

80


Eisen/ Iron [mg/kg]Obergrenze upper limitrobuster Mittelwert robust meanUntergrenze lower limit




Abb. / Fig. 16: Z-Scores Eisen / Iron



Remark

1 64,7 4,45 0,86 1,12 58,0 -2,25 -0,43 -0,563 54,3 -5,95 -1,1 -1,54 69,4* 9,13 1,8 2,35 63,2 2,90 0,56 0,726 58,5 -1,75 -0,34 -0,437 59,0 -1,25 -0,24 -0,318 59,0 -1,25 -0,24 -0,319 58,8 -1,50 -0,29 -0,37


Auswerte- nummer

Eisen/ Iron [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

32

69

78

51

4-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.9 I – Iod / Iodine in mg/kg


Due to the low number of available results (<5), no statistical evaluation wasperformed.


Statistic DataNumber of results 3Number of outliersMean 1,44Median 1,45Robust Mean (X) 1,44Robust standard deviation (S*) 0,0365Number with 2 replicates

Target range:

lower limit of target rangeupper limit of target range

Results in the target rangePercent in the target range


Repeatability (CVr)






Abb. / Fig. 17: Ergebnisse Iod / Results Iodine



12

34

56

78

91,36

1,38

1,40

1,42

1,44

1,46

1,48


Iod/ Iodine [mg/kg]Obergrenze upper limit




z-Score Hinweis

Remark

1 1,45 0,01332 1,46 0,02333 1,40 -0,0367456789

Auswerte- nummer

Iod/ Iodine [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt)


4.10 K – Kalium / Potassium in mg/kg


Abb. / Fig. 18: Ergebnisse Eisen / Results Iron



40,2

0,989%

632

15,6%

Target range:181

184


1,91450,80



Repeatability (CVr)





12

34

56

78

90

1000

2000

3000

4000

5000

6000


Kalium/ Potassium [mg/kg]






Abb. / Fig. 19: Z-Scores Kalium/ Potassium


94

36

71

58

2-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores 8,7



Remark

1 4110 180 0,99 1,02 5500 1570 8,7 8,53 3760 -169 -0,94 -0,924 3590* -338 -1,9 -1,85 4130 195 1,1 1,16 3840 -88,4 -0,49 -0,487 3890 -45,4 -0,25 -0,258 4140 207 1,1 1,19 3470 -460 -2,5 -2,5


Auswerte- nummer

Kalium/ Potassium

[mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)


4.11 Mg – Magnesium in mg/kg


Abb. / Fig. 20: Ergebnisse Magnesium / Results Magnesium


Statistic DataNumber of results 7Number of outliersMean 1150Median 1150Robust Mean (X) 1150Robust standard deviation (S*) 36,3Number with 2 replicates 7

29,9

2,60%

46,0

4,00%

Target range:63,7

80,5


0,5717,10,27



Repeatability (CVr)





12

34

56

78

9

0

200

400

600

800

1000

1200

1400


Magnesium [mg/kg]







Abb. / Fig. 21: Z-Scores Magnesium



Remark

1 1190 38,9 0,61 0,482 1150 0,908 0,014 0,0113 1160 14,9 0,23 0,194 1140* -14,1 -0,22 -0,175 1180 30,9 0,49 0,3867 1080 -73,1 -1,1 -0,918 1130 -17,1 -0,27 -0,219


Auswerte- nummer

Magnesium [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

78

42

35

1-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.12 Mn – Mangan / Manganese in mg/kg


Abb. / Fig. 22: Ergebnisse Mangan / Results Manganese



0,0529

1,48%

0,285

7,98%Target range:

0,473

0,476


0,690,1360,29



Repeatability (CVr)





12

34

56

78

9

0,000,501,001,502,002,503,003,504,004,505,00


Mangan/ Manganese [mg/kg]






Abb. / Fig. 23: Z-Scores Mangan / Manganese



Remark

1 3,96 0,379 0,80 0,802 3,85 0,269 0,57 0,573 3,22 -0,361 -0,76 -0,764 3,73* 0,145 0,31 0,315 3,91 0,329 0,70 0,696 3,43 -0,151 -0,32 -0,327 3,50 -0,081 -0,17 -0,178 3,40 -0,181 -0,38 -0,389 3,23 -0,350 -0,74 -0,73


Auswerte- nummer

Mangan/ Manganese

[mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

39

86

74

25

1-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.13 Mo – Molybdän / Molybdenum in mg/kg


Abb. / Fig. 24: Ergebnisse Molybdän / Results Molybdenum



0,0442

5,30%

0,127

15,2%

Target range:0,137

0,158


0,950,06660,49



Repeatability (CVr)





12

34

56

78

9

0,00

0,20

0,40

0,60

0,80

1,00

1,20Ergebnisse / Results

Molybdän/ Molybdenum [mg/kg]Obergrenze upper limitrobuster Mittelwert robust mean




Abb. / Fig. 25: Z-Scores Molybdän / Molybdenum


38

41

27

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



Remark

1 0,800 -0,0303 -0,22 -0,192 0,900 0,0697 0,51 0,443 0,7100 -0,120 -0,88 -0,764 0,796* -0,0343 -0,25 -0,22

5 <1,22

67 1,10 0,270 2,0 1,78 0,750 -0,0803 -0,59 -0,519


Auswerte- nummer

Molybdän/ Molybdenum

[mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)



4.14 Na – Natrium / Sodium in mg/kg


Abb. / Fig. 26: Ergebnisse Natrium / Results Sodium



58,0

1,96%

141

4,76%Target range:

142

122


1,172,70,51



Repeatability (CVr)





12

34

56

78

9

2000

2200

2400

2600

2800

3000

3200

3400


Natrium/ Sodium [mg/kg]






Abb. / Fig. 27: Z-Scores Natrium / Sodium



Remark

1 3150 204 1,4 1,72 2900 -43,6 -0,31 -0,363 2840 -102 -0,72 -0,834 2770* -179 -1,3 -1,55 3100 154 1,1 1,367 2920 -22,6 -0,16 -0,198 2930 -11,6 -0,082 -0,0959

*Mean calculated by DLA

Auswerte- nummer

Natrium/ Sodium [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

43

27

85

1-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.15 Ni – Nickel in mg/kg


Abb. / Fig. 28: Ergebnisse Nickel / Results Nickel



0,0236

5,67%

0,0556

13,4%Target range:

0,0763lower limit of target range 0,265upper limit of target range 0,571

0,770,03010,39



Repeatability (CVr)





12

34

56

78

9

0,0

0,1

0,2

0,3

0,4

0,5

0,6


Nickel [mg/kg]







Abb. / Fig. 29: Z-Scores Nickel


Nickel [mg/kg] z-Score Hinweis

Remark

1 0,380 -0,0380 -0,502 0,500 0,0820 1,13 0,380 -0,0380 -0,504 0,443* 0,0250 0,33

5 <1,22 LOD over target range

6

7 <0,50 LOD in the target range

8 0,440 0,0220 0,299 0,365 -0,0530 -0,69


Auswerte- nummer

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt)

93

18

42

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.16 P – Phosphor / Phosphorus in mg/kg


Abb. / Fig. 30: Ergebnisse Phosphor / Results Phosphorus



50,8

1,04%

375

7,65%

Target range:217

365


1,81970,91



Repeatability (CVr)





12

34

56

78

94000

4200

4400

4600

4800

5000

5200

5400


Phosphor/ Phosphorus [mg/kg]






Abb. / Fig. 31: Z-Scores Phosphor / Phosphorus



Remark

1 5130 253 1,2 0,702 5200 327 1,5 0,903 4730 -148 -0,7 -0,404 4440* -436 -2,0 -1,25 4560 -312 -1,4 -0,8567 5190 314 1,4 0,86891011


Auswerte- nummer

Phosphor/ Phosphorus

[mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

45

31

72

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.17 Rb – Rubidium in mg/kg


Due to the low number of available results (<5), no statistical evaluation wasperformed.


Statistic DataNumber of results 2Number of outliersMean 2,54Median 2,54Robust Mean (X) 2,54Robust standard deviation (S*) 0,449Number with 2 replicates

Target range:

lower limit of target rangeupper limit of target range

Results in the target range


Repeatability (CVr)






Abb. / Fig. 32: Ergebnisse Rubidium / Results Rubidium



12

34

56

78

9

0,00

0,50

1,00

1,50

2,00

2,50

3,00


Rubidium [mg/kg]





z-Score Hinweis

Remark

12 2,82 0,2803456 2,26 -0,280789

Auswerte- nummer

Rubidium [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt)


4.18 Se – Selen in mg/kg


Abb. / Fig. 33: Ergebnisse Selen / Results Selen



0,0154

7,18%

0,0341

15,9%Target range:

0,0440

0,0256


1,00,02360,54



Repeatability (CVr)





12

34

56

78

9

0,00

0,05

0,10

0,15

0,20

0,25

0,30

0,35


Selen [mg/kg]







Abb. / Fig. 34: Z-Scores Selen


Selen [mg/kg] z-Score z-Score Hinweis

Remark

1 0,180 -0,0388 -0,88 -1,52 0,280 0,0612 1,4 2,43 0,200 -0,0188 -0,43 -0,744 0,253* 0,0342 0,78 1,3

5 <1,22

6 0,180 -0,0388 -0,88 -1,578 0,220 0,00117 0,027 0,0469


Auswerte- nummer

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)


61

38

42

-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores



4.19 Zn – Zink / Zinc in mg/kg


Abb. / Fig. 35: Ergebnisse Zink / Results Zinc


Statistic DataNumber of results 9Number of outliersMean 109Median 106Robust Mean (X) 109Robust standard deviation (S*) 15,2Number with 2 replicates 8

4,19

3,93%

12,3

12%Target range:

8,57

7,20

lower limit of target range 91,4upper limit of target range 126

1,86,320,74



Repeatability (CVr)





12

34

56

78

9

0

20

40

60

80

100

120

140


Zink/ Zinc [mg/kg]Obergrenze upper limitrobuster Mittelwert robust meanUntergrenze lower limit




Abb. / Fig. 36: Z-Scores Zink / Zinc



Remark

1 108 -0,506 -0,059 -0,0702 100 -8,51 -0,99 -1,23 91,8 -16,7 -1,9 -2,34 118* 9,34 1,1 1,35 105 -4,01 -0,47 -0,566 128 19,5 2,3 2,77 106 -2,51 -0,29 -0,358 93,1 -15,4 -1,8 -2,19 127 18,8 2,2 2,6


Auswerte- nummer

Zink/ Zinc [mg/kg]

Abweichung [mg/kg]

Evaluation number

Deviation [mg/kg]

(σpt) (Info)

38

25

71

49

6-4,0

-3,0

-2,0

-1,0

0,0

1,0

2,0

3,0

4,0z-Scores


5. Documentation

5.1 Details by the participants

Note: Information given in German were translated by DLA to the best of our knowledge (without guarantee of correctness).

5.1.1 Primary Data and analytical Methods

5.1.1.1 Aluminium


Teilnehmer Ergebnis 1 Ergebnis 2 Inkl. WF

Incl. RR

mg/kg mg/kg mg/kg mg/kg in %

1 17 79 29.05.18 7,22 7,39 7,04

2 18 78 03.05.18 5,8 6,1 5,9 0,1 100

3 10 86 07.05. 5,89 5,83 5,94 3

4 76 20 30.04. 13,2 13,4 1

5 29 67

6 28 687 46 50 09.05.18 5,1 5,1 5,1 0,5 -

8 77 19 4,8 4,9 4,7 n/a

9 32 64 27.05.18 3,239 3,019 3,458 0,3

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

ParticipantSample No.1

Sample No. 2

Date of analysis

Result (Mean)

Result 1 Result 2Limit of

determinati-on

Recovery rate [%]

yes/no

no

yes

no

no

no03.05-

01.06.2018no

no

5.1.1.2 Barium



Incl. RR


1 17 79 16.05.18 0,65 0,65 0,65

2 18 78 3,5,2018 0,7 0,7 0,7 0,05 100

3 10 86 15.05. 0,65 0,65 0,65 0,09

4 76 20 30.04. 0,81 0,83 0,015 29 67

6 28 68

7 46 50 - - - - - - -

8 77 19 0,72 0,69 0,74 n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)


determinationRecovery rate [%]

yes/no

no

yes

no

no

03.05-01.06.2018

no

5.1.1.3 Calcium



Incl. RR


1 17 79 29.05.18 7214 7202 72262 18 78 3,5,2018 6700 6800 6750 100 100

3 10 86 16.05. 6313 6276 6349 18

4 76 20 30.04. 6412 6444 2005 29 67 25.05.18 6504 6527 6481

6 28 68 31.05.18 5250 5183 5316

7 46 50 09.05.18 6688 6648 6728 25 -

8 77 19 6593 6864 6322 n/a

9 32 64 27.05.18 6550,6 6588,48 6512,782 30

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Participant

Sample No.1

Sample No. 2

Date of analysis

Result (Mean) Result 1 Result 2Limit of


yes/no

noyes

no

no

no

no03.05-

01.06.2018no

no

5.1.1.4 Cadmium


Teilnehmer Ergebnis 1 Ergebnis 2

mg/kg mg/kg mg/kg mg/kg

1 17 79 16.05.18 <0,01 <0,01 <0,012 18 78 3,5,2018 0,013 0,014 0,014 0,01 1003 10 86 07.05. 0,010 0,010 0,010 0,034 76 20 30.04. 0,0081 0,0087 0,0025 29 67 29.05.18 0,012 0,014 0,016 28 68

7 46 50 09.05.18 <0,050 <0,050 <0,050 0,05

8 77 19 0,011 0,01 0,012 0,007 n/a

9 32 64 27.05.18 0,015 0,014 0,015 0,006

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Inkl. WF

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean) Result 1 Result 2Limit of

determinationIncl. RR

Recovery rate [%]

yes/no

noyes nono

no03.05-

01.06.2018no

no

5.1.1.5 Kobalt/ Cobalt



Incl. RR


1 17 79 16.05.18 0,039 0,037 0,0412 18 78 3,5,2018 0,047 0,047 0,05 0,01 100

3 10 86 15.05. 0,036 0,036 0,036 0,03

4 76 20 30.04. 0,033 0,035 0,015 29 67 29.05.18 <1.19 <1.22

6 28 68

7 46 50 09.05.18 <0,050 <0,050 <0,050 0,05 -

8 77 19 0,038 0,036 0,04 n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

noyes

no

no

no03.05-

01.06.2018no

5.1.1.6 Chrom/ Chromium



Incl. RR


1 17 79 16.05.18 0,22 0,2 0,23

2 18 78 3,5,2018 0,18 0,19 0,2 0,1 100

3 10 86 07.05. 0,15 0,15 0,15 0,06

4 76 20 30.04. 0,258 0,267 0,025 29 67 25.05.18 <1.19 <1.22

6 28 68

7 46 50 09.05.18 0,37 0,39 0,35 0,05 -

8 77 19 0,2 0,19 0,21 0,02 n/a

9 32 64 27.05.18 0,207 0,197 0,218 0,06

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

no

yes

no

no

no03.05-

01.06.2018no

no

5.1.1.7 Kupfer / Copper



Incl. RR


1 17 79 29.05.18 4,3 4,35 4,242 18 78 3,5,2018 4,22 4,32 4,3 0,1 100

3 10 86 07.05. 3,91 3,8 4,02 0,06

4 76 20 30.04. 3,967 4,063 0,015 29 67 25.05.18 5,48 5,64 5,32

6 28 68 31.05.18 4,8 4,9 4,6

7 46 50 09.05.18 3,9 3,9 3,9 0,5 -

8 77 19 4,7 5,06 4,36 n/a

9 32 64 27.05.18 3,452 3,519 3,386 0,06

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

noyes

no

no

no

no03.05-

01.06.2018no

no

5.1.1.8 Eisen / Iron



Incl. RR


1 17 79 29.05.18 64,7 65,1 64,2

2 18 78 3,5,2018 58 60 59 0,5 100

3 10 86 07.05. 54,3 53,9 54,6 3

4 76 20 30.04. 68,73 70,04 0,1

5 29 67 25.05.18 63,15 64,6 61,7

6 28 68 31.05.18 58,5 58,3 58,6

7 46 50 09.05.18 59 58 59 0,5 -

8 77 19 59 57,5 60,5 n/a

9 32 64 27.05.18 58,75 58,744 58,748 0,6

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)

Result 1 Result 2Limit of deter-

minationRecovery rate [%]

yes/no

no

yes

no

no

no

no03.05-

01.06.2018no

no

5.1.1.9 Iod / Iodine



Incl. RR


1 17 79 16.05.18 1,45 1,44 1,45

2 18 78 3,5,2018 1,46 1,5 1,5 0,05 1003 10 86 18.05. 1,4 1,4 1,41 0,1

4 76 20

5 29 676 28 68

7 46 50 - - - - - - -

8 77 199 32 64

Proben Nr. 1

Proben Nr.2

Datum der

Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

no

yes no

5.1.1.10 Kalium / Potassium



Participant Result 1 Result 2 Incl. RR

mg/kg mg/kg mg/kg mg/kg yes/no in %

1 17 79 00:00:00 4111 4121 4101 no

2 18 78 3,5,2018 5500 5650 5600 50 yes 100

3 10 86 16.05. 3762 3754 3770 18 no

4 76 20 30.04. 3582 3604 100 no

5 29 67 25.05.18 4126,5 4192 4061

6 28 68 31,05.2018 3843 3846 3840 no

7 46 50 09.05.18 3886 3874 3898 25 no

8 77 19 4138 4104 4171 no n/a

9 32 64 27.05.18 3470,9 3498,874 3442,897 3000 no

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Sample No.1

Sample No. 2

Date of analysis

Result (Mean)

Limit of determination

Recovery rate [%]

03.05-01.06.2018

5.1.1.11 Magnesium



Incl. RR


1 17 79 29.05.18 1188 1162 12142 18 78 3,5,2018 1150 1200 1175 20 100

3 10 86 16.05. 1164 1144 1185 64 76 20 30.04. 1130 1140 100

5 29 67 25.05.18 1180 1158 12026 28 687 46 50 09.05.18 1076 1077 1074 25 -

8 77 19 1132 1169 1095 n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

noyes

nono

no03.05-

01.06.2018no

5.1.1.12 Mangan / Manganese



Incl. RR


1 17 79 29.05.18 3,96 3,95 3,97

2 18 78 3,5,2018 3,85 3,81 3,8 0,1 1003 10 86 08.05. 3,22 3,19 3,25 0,034 76 20 30.04. 3,703 3,749 0,025 29 67 25.05.18 3,91 3,93 3,896 28 68 31.05.18 3,43 3,4 3,457 46 50 09.05.18 3,5 3,5 3,5 0,05 -

8 77 19 3,4 3,3 3,5 n/a

9 32 64 27.05.18 3,231 3,231 3,23 0,06

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

no

yes nono

nono

03.05-01.06.2018

no

no

5.1.1.13 Molybdän / Molybdenum



Participant Result (Mean) Result 1 Result 2 Incl. RR


1 17 79 16.05.18 0,8 0,84 0,76 no2 18 78 3,5,2018 0,9 0,9 0,9 0,2 yes 100

3 10 86 15.05. 0,71 0,7 0,72 0,03 no4 76 20 30.04. 0,788 0,804 0,01 no5 29 67 25.05.18 <1.19 <1.22

6 28 687 46 50 09.05.18 1,1 1,1 1 0,5 no -

8 77 19 0,75 0,71 0,79 no n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Sample No.1

Sample No. 2

Date of analysis


Recovery rate [%]

03.05-01.06.2018

5.1.1.14 Natrium / Sodium



Incl. RR


1 17 79 29.05.18 3148 3162 31342 18 78 3,5,2018 2900 3000 2950 20 1003 10 86 16.05. 2842 2808 2876 94 76 20 30.04. 2759 2770 1005 29 67 25.05.18 3097,5 3145 30506 28 687 46 50 09.05.18 2921 2894 2947 5 -

8 77 19 2932 3014 2849 n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of ana-lysis

Result (Mean)



yes/no

noyes nono

no03.05-

01.06.2018no

5.1.1.15 Nickel


Teilnehmer Ergebnis 1 Ergebnis 2


1 17 79 29.05.18 0,38 0,34 0,412 18 78 3,5,2018 0,5 0,5 0,5 0,1 100

3 10 86 07.05. 0,38 0,37 0,38 0,2

4 76 20 30.04. 0,433 0,453 0,015 29 67 25.05.18 <1.19 <1.22

6 28 68

7 46 50 09.05.18 <0,50 <0,50 <0,50 0,5 -

8 77 19 0,44 0,45 0,42 0,02 n/a

9 32 64 27.05.18 0,365 0,375 0,356 0,06

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Inkl. WF

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)


determinationIncl. RR

Recovery rate [%]

yes/no

noyes

no

no

no03.05-

01.06.2018no

no

5.1.1.16 Phosphor/ Phosphorus





1 17 79 29.05.18 5126 5121 5131 no2 18 78 3,5,2018 5200 5400 5300 100 yes 1003 10 86 28.05. 4725 4694 4756 9 no4 76 20 30.04. 4439 4434 100 no5 29 67 25.05.18 4561 4576 45466 28 687 46 50 09.05.18 5187 5123 5250 25 no -8 77 199 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Sample No.1

Sample No. 2

Date of analysis

Result (Mean)

Limit of determinati-

on

Recovery rate [%]

5.1.1.17 Rubidium



Incl. RR


1 17 792 18 78 3,5,2018 2,82 2,86 2,8 0,1 100

3 10 86

4 76 205 29 676 28 68 31.05.18 2,26 2,33 2,187 46 50 - - - - - - -8 77 199 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]


Sample No. 2

Date of analysis

Result (Mean)



yes/no

yes

not analysed

no

5.1.1.18 Selen





1 17 79 31.05.18 0,18 0,18 0,18 no

2 18 78 3,5,2018 0,28 0,25 0,25 0,05 yes 100

3 10 86 15.05. 0,2 0,2 0,2 0,03 no

4 76 20 30.04. 0,249 0,257 0,1 no

5 29 67 25.05.18 <1.19 <1.22

6 28 68 31.05.18 0,18 0,19 0,176 no

7 46 50 - - - - - - -

8 77 19 0,22 0,199 0,25 0,05 no n/a

9 32 64

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Sample No.1

Sample No. 2

Date of analysis

Result (Mean)


Recovery rate [%]

03.05-01.06.2018

5.1.1.19 Zink / Zinc

* Values probably copied in from potassium, were not considered for the evaluation of zinc





1 17 79 29.05.18 108 108 107 no2 18 78 3,5,2018 100 105 103 1 yes 1003 10 86 07.05. 91,8 85,9 97,6 0,9 no4 76 20 30.04. 117,4 118,3 0,1 no5 29 67 25.05.18 104,5 102 1076 28 68 31.05.18 128 132 124 no7 46 50 09.05.18 106 107 104 5 no -

8 77 19 93,1 89,9 96,2 no n/a

9 32 64 27.05.18 127,3 3498,874* 3442,897* 0,3 no

Proben Nr. 1

Proben Nr.2

Datum der Analyse

Ergebnis (Mittel)

Bestimmungs-grenze

Wiederfin-dungsrate

[%]

Sample No.1

Sample No. 2

Date of analysis

Result (Mean)

Limit of determinati-

on

Recovery rate [%]

03.05-01.06.2018

5.1.2 Analytical Methods

5.1.2.1 Aluminium


Teilnehmer Probenvorbereitung Messmethode

Participant Method description Sample preparation Measuring method Further remarks

yes/no yes/no

1 DIN EN 11885 yes

2 EN 17294-2 EN 15763 yes

3 mix ICP-MS ext. with IS In yes

4 DIN EN ISO 17294-2 Microwave Digestion no yes

5 Microwave Digestion AOAC 993.14 no yes

6

7 no yes

8 ICP-MS no no

9 ICP-OES yes

Methodenbeschrei-bung

Kalibrierung und Referenzmaterial

Wiederfindung w urde

mit gleicher Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise

Calibration and reference material

Recovery w ith same

matrix

Method

accredited

Microwave pressure digestion

Al with ICP-MS after

Microwave digestion

Calibration using single element

standardsAOAC 993.14 (modified)

External Calibartion Curve

ICP-OES – internal method

PNTA0141

external calib. curve and internal RM

microwave digestion HNO3/HCl

DIN ISO 11885 (E22)


5.1.2.2 Barium


Teilnehmer Messmethode

1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS

4 DIN EN ISO 17294-2

5

6

7 - - - -

8 ICP-MS

9

Methodenbeschrei-bung

Probenvorberei-tung


Wiederfindung w urde mit gleicher

Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise

Participant Method descriptionSample

preparationMeasuring method


Recovery w ith

same matrix

Method

accredited

Further remarks

yes/no yes/noyes


yes

Ba ICP-MS after Microwave digestion

mix ext. With IS In no

Microwave Digestion

Calibration using single element standards

no yes

Microwave Digestion HNO3/HCl

no no

5.1.2.3 Calcium


Teilnehmer Methodenbeschreibung Messmethode

1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS

4 DIN EN ISO 11885

5

6 100 mg 65% HNO3

7

8 ICP-MS

9 DIN ISO 11885 (E22) ICP-OES

Probenvorberei-tung



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise




Recovery w ith

same matrix

Method

accredited

Further remarks

yes/no yes/no

yesMicrowave pressure digestion

yes

Ca with ICP-MS after Microwave digestion

mix ext. With IS In yes

Microwave Digestion


standardsno yes

total x-ray fluorescence analysis according to in-house

method

manual mixing acid digestioninternal standard / Gallium

no

ICP-OES – internal method PNTA0141


no yes

Microwave Digestion HNO3/HCl

no no


yes

5.1.2.4 Cadmium


Teilnehmer Methodenbeschreibung Messmethode

1 DIN EN 17294

2 EN 17294-2 EN 15763

3 ICP-MS


56

7

8 ICP-MS


Probenvorberei-tung



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise




Recovery w ith

same matrix

Method

accredited

Further remarks

yes/no yes/no

yesMicrowave pressure

digestionyes

Cd with ICP-MS after Microwave digestion

mix ext. with IS In yes

Microwave

Digestion


standardsno yes



no yes


no no


yes

5.1.2.5 Kobalt / Colbat


Teilnehmer Methodenbeschreibung Probenvorbereitung Messmethode

1 DIN EN 17294

2 EN 17294-2 EN 15763

3 ICP-MS


5

6

7

8 ICP-MS

9



Matrix bestimmt

Methode akkreditiert

Sonstige Hinweise

Participant Method description Sample preparation Measuring methodCalibration and

reference materialRecovery w ith

same matrixMethod

accredited

Further remarks

yes/no yes/no

yes


yes

Co with ICP-MS after Microwave digestion

mix ext. with IS In no

Microwave DigestionCalibration using single element

standardsno yes



no yes


no no

5.1.2.6 Chrom / Chromium



1 DIN EN 17294

2 EN 17294-2 EN 15763

3 ICP-MS


56

7

8 ICP-MS




Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no


yes

Cr mit ICP-MS nachMikrowellenaufschluss


Microwave Digestion


no yes



no yes


no no

Microwave pressure digestion-aufschluss

yes

5.1.2.7 Kupfer / Copper



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS


5

6 100 mg 20% HNO3

7

8 ICP-MS



Wiederfindung w urde mit gleicher Matrix

bestimmt

Methode

akkreditiert

Sonstige Hinweise


reference material

Recovery w ith same

matrix

Method accredited

Further remarks

yes/no yes/no


yes

Cu with ICP-MS after Microwave digestion


Microwave Digestion


no yes

total x-ray fluorescence analysis according to in-

house methodmanual mixing

Wet grinding process with ball mill

internal standard / Gallium

no



no yes


no no


yes

5.1.2.8 Eisen / Iron



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS


5

6 100 mg 20% HNO3

7

8 ICP-MS




Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no


yes

Fe with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes


method

manual mixingWet grinding process

with ball mill


no



no yes


no no


yes

5.1.2.9 Iod / Iodine



Participant Method description Sample preparation Measuring method

yes/no yes/no

1 DIN EN 15111 yes

2 EN 17294-2 EN 15763 yes


456

7 - - - -89

Kalibrierung und

Referenzmaterial


Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise


Recovery w ith

same matrix

Method

accredited

Further remarks


Iodine ICP-MS, DIN/EN 15111, mod.

5.1.2.10 Kalium / Pottasium



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS

4 DIN EN ISO 11885

5

6 100 mg 20% HNO3

7

8 ICP-MS




Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no


K with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes


method


with ball mill


no



no yes


no no


yes

5.1.2.11 Magnesium




yes/no yes/no

1 DIN EN 11885 yes

2 EN 17294-2 EN 15763 yes


4 DIN EN ISO 11885 Microwave Digestion no yes

5

6

7 no yes

8 ICP-MS no no

9



Matrix bestimmt


Sonstige Hinweise


Recovery w ith

same matrix

Method

accredited

Further remarks


Mg with ICP-MS after Microwave digestion


standards


external calib. curve and internal

RMmicrowave digestion

HNO3/HCl

5.1.2.12 Mangan / Manganese



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS


5

6 100 mg 20% HNO3

7

8 ICP-MS




Matrix bestimmt


Sonstige Hinweise



same matrixMethod

accredited

Further remarks

yes/no yes/no

yes


yes

Mn with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes


method


with ball mill


no



no yes


no no


yes

5.1.2.13 Molybdän / Molybdenum



1 DIN EN 17294

2 EN 17294-2 EN 15763

3 ICP-MS


56

7

8 ICP-MS

9



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no

yes


yes

Mo with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes



no yes


no no

5.1.2.14 Natrium / Sodium



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS

4 DIN EN ISO 11885

5

6

7

8 ICP-MS

9



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrixMethod accredited

Further remarks

yes/no yes/no

yes


yes

Na with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes



no yes


no no

5.1.2.15 Nickel



1 DIN EN 11885

2 EN 17294-2 EN 15763

3 ICP-MS


5

6

7

8 ICP-MS




Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no


yes

Ni with ICP-MS after Microwave digestion


Microwave DigestionCalibration using single element

standardsno yes



no yes


no no


yes

5.1.2.16 Phosphor / Phosphorus




yes/no yes/no

1 DIN EN 11885 yes

2 EN 17294-2 EN 15763 yes

3 mix ICP-MS ext. with IS In no

4 DIN EN ISO 17294-2 no yes

56

7 no yes

89



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise


Recovery w ith

same matrix

Method

accredited

Further remarks


P with ICP-MS after Microwave digestion

Microwave Digestion


standards



5.1.2.17 Rubidium


Teilnehmer Probenvorbereitung Messmethode

Participant Sample preparation Measuring method

yes/no yes/no

1

2 EN 17294-2 EN 15763 yes/no

345

6 manual mixing 100 mg acid digestion 65% HNO3 no

7 - - - -89

Methoden-beschreibung



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise

Method description


Recovery w ith

same matrix

Method

accredited

Further remarks


total x-ray fluorescence analysis

according to in-house method


5.1.2.18 Selen



1 DIN 38405-D 23

2 EN 17294-2 EN 15763

3 ICP-MS


5

6 100 mg 20% HNO3

7 - - - -

8 ICP-MS

9



Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrix

Method

accredited

Further remarks

yes/no yes/no

yes


yes

Se with ICP-MS after Microwave digestion

mix ext. with IS In

Microwave Digestion


no yes


method


with ball mill


no


no no

5.1.2.19 Zink / Zinc



1 DIN EN 17294

2 EN 17294-2 EN 15763

3 ICP-MS


5

6 100 mg 20% HNO3

7

8 ICP-MS




Matrix bestimmt

Methode

akkreditiert

Sonstige Hinweise



same matrixMethod accredited

Further remarks

yes/no yes/no

yes


yes

Zn with ICP-MS after Microwave digestion


Microwave Digestion


standardsno yes


method


with ball mill


no

ICP-OES – internal mehtod PNTA0141


no yes


no no


yes


5.2 Homogeneity

5.2.1 Homogeneity of bottled PT-samples

Homogeneity test of copper by ICP-MS:

5.2.2 Comparison of sample numbers / test results and trend line

By comparison of the increasing sample numbers and the measurementresults of participants, the homogeneity of the chronological bottled PTitem can be characterized with the help of the trend line function:

Abb./Fig. 37: Trendfunktion Probennummern vs. Ergebnisse (1*20 dargestellt) trend line function sample number vs. results (1*20 shown)


0

50

100

150

f(x) = 0,0943x + 85,3767

Homgenität / homogeneity

Kupfer / Copper

DLA-Nr. / No.

Ergebnis / result * 20

Linear (Ergebnis / result * 20)

mg/kg1 4,522 4,393 4,424 4,685 4,54

4,51

0,114 2,54 %

replicate measurements

general mean:

Repeatability Standard Deviation: ≙


5.3 Kernel Density Plots of ResultsAluminium

Abbildungen: Kerndichte-Schätzungender Einzel-Teilnehmerergebn-isse(mit h = σpt von Xpt)

Figures:Kernel density plotsof participants' single results(with h = σpt of Xpt

Barium Calcium

Cadmium Cobalt


0

0,05

0,1

0,15

0,2

0,25

-5 0 5 10 15 20

Kernel Density PlotFixed h: 1.22

0

0,5

1

1,5

2

2,5

3

3,5

0 0,2 0,4 0,6 0,8 1 1,2 1,4

Kernel Density PlotFixed h: .119

0

0,0001

0,0002

0,0003

0,0004

0,0005

0,0006

0,0007

0,0008

0,0009

0,001

0 2000 4000 6000 8000 10000

Kernel Density PlotFixed h: 279

0

10

20

30

40

50

60

70

80

90

100

-0,005 0 0,005 0,01 0,015 0,02 0,025 0,03


0

5

10

15

20

25

30

35

40

0 0,02 0,04 0,06 0,08 0,1



Chrom/ chromium


Figures:Kernel density plotsof participants' single results(with h = σpt of Xpt)

Kupfer / Copper Eisen / Iron

Iod/ Iodine Kalium / Potassium

< 8 Ergebnisse /< 8 Results


0

1

2

3

4

5

6

7

0 0,1 0,2 0,3 0,4 0,5 0,6


0

0,1

0,2

0,3

0,4

0,5

0,6

0 1 2 3 4 5 6 7 8


0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0 20 40 60 80 100


0

0,0002

0,0004

0,0006

0,0008

0,001

0,0012

0 1000 2000 3000 4000 5000 6000 7000



Magnesium



Mangan / Manganese Molybdän / Molybdenum

Natrium/ Sodium Nickel


0

0,001

0,002

0,003

0,004

0,005

0,006

0 200 400 600 800 1000 1200 1400 1600


0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0 1 2 3 4 5 6


0

0,5

1

1,5

2

2,5

0 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6


0

0,0005

0,001

0,0015

0,002

0,0025

0 500 1000 1500 2000 2500 3000 3500 4000


0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8



Phosphor / Phosphorus



Rubidium Selen

< 8 Ergebnisse /< 8 Results

Zink / Zinc


0

0,0001

0,0002

0,0003

0,0004

0,0005

0,0006

0,0007

0,0008

0,0009

0 1000 2000 3000 4000 5000 6000 7000


0

1

2

3

4

5

6

7

8

0 0,1 0,2 0,3 0,4 0,5


0

0,005

0,01

0,015

0,02

0,025

0,03

0 50 100 150 200



5.4 Information on the Proficiency Test (PT)

Before the PT the participants received the following information in the sample cover letter:



6. Index of participant laboratories in alphabeticalorder

[Die Adressdaten der Teilnehmer wurden für die allgemeine Veröffentlichung des Auswerte-Berichts nicht angegeben.]

[The address data of the participants were deleted for publication of the evaluation report.]


USA

Teilnehmer/ Participant Ort/ Town LandCountryGermanyGermany

EstoniaSouth KoreaGermanyGermanyGermanyGermany

Germany

Spain


7. Index of references

1. DIN EN ISO/IEC 17025:2005; Allgemeine Anforderungen an die Kompetenz von Prüf- und Kalibrierlaboratorien / General requirements for the competence of testing and calibration laboratories

2. DIN EN ISO/IEC 17043:2010; Konformitätsbewertung – Allgemeine Anforder-ungen an Eignungsprüfungen / Conformity assessment – General requirements for proficiency testing

3. ISO 13528:2015 & DIN ISO 13528:2009; Statistische Verfahren für Eignungs-prüfungen durch Ringversuche / Statistical methods for use in proficiency testing by interlaboratory comparisons

4. ASU §64 LFGB: Planung und statistische Auswertung von Ringversuchen zur Methodenvalidierung / DIN ISO 5725 series part 1, 2 and 6 Accuracy (true-ness and precision) of measurement methods and results

5. Verordnung / Regulation 882/2004/EU; Verordnung über über amtliche Kon-trollen zur Überprüfung der Einhaltung des Lebensmittel- und Futtermit-telrechts sowie der Bestimmungen über Tiergesundheit und Tierschutz / Reg-ulation on official controls performed to ensure the verification of com-pliance with feed and food law, animal health and animal welfare rules

6. Evaluation of analytical methods used for regulation of food and drugs; W.Horwitz; Analytical Chemistry, 54, 67-76 (1982)

7. The International Harmonised Protocol for the Proficiency Testing ofAnanlytical Laboratories ; J.AOAC Int., 76(4), 926 – 940 (1993)

8. A Horwitz-like funktion describes precision in proficiency test; M.Thompson, P.J. Lowthian; Analyst, 120, 271-272 (1995)

9. Protocol for the design, conduct and interpretation of method performancestudies; W. Horwitz; Pure & Applied Chemistry, 67, 331-343 (1995)

10.Recent trends in inter-laboratory precision at ppb and sub-ppb concentra-tions in relation to fitness for purpose criteria in proficiency testing;M. Thompson; Analyst, 125, 385-386 (2000)

11.The International Harmonised Protocol for the Proficiency Testing of Ana-lytical Chemistry Laboratories; Pure Appl Chem, 78, 145 – 196 (2006)

12.AMC Kernel Density - Representing data distributions with kernel densityestimates, amc technical brief, Editor M Thompson, Analytical Methods Com-mittee, AMCTB No 4, Revised March 2006 and Excel Add-in Kernel.xla 1.0e byRoyal Society of Chemistry

13.EURACHEM/CITAC Leitfaden, Ermittlung der Messunsicherheit bei analytischenMessungen (2003); Quantifying Uncertainty in Analytical Measurement (1999)

14.GMP+ Feed Certification scheme, Module: Feed Safety Assurance, chapter 5.7Checking procedure for the process accuracy of compound feed with microtracers in GMP+ BA2 Control of residues, Version: 1st of January 2015 GMP+International B.V.

15.MTSE SOP No. 010.01 (2014): Quantitative measurement of mixing uniformityand carry-over in powder mixtures with the rotary detector technique, MTSEMicro Tracers Services Europe GmbH

16.ASU §64 L 00.00-157 (2016-2): Bestimmung von Aluminium in Lebensmittelnmit der Massenspektrometrie mit induktiv gekoppeltem Plasma (ICP-MS)

17.ASU §64 L 00.00-158 (2016-2): Bestimmung von Aluminium in Lebensmittelnmit der optischen Emmissionsspektrometrie mit induktiv gekoppeltem Plasma(ICP-OES)

18.ASU §64 L 00.00-135 (2011-01) / DIN EN 15763:2010: Bestimmung von Arsen, Cadmium, Quecksilber und Blei in Lebensmitteln mit ICP-MS nach Druckauf-schluss / Foodstuffs. Determination of trace elements. Determination of arsenic, cadmium, mercury and lead in foodstuffs by inductively coupled plasma mass spectrometry (ICPMS) after pressure digestion

19.ASU §64 L 00.00-19/2: Bestimmung von Eisen, Kupfer, Mangan und Zink mitder Atomabsorptionsspektrometrie (AAS) in der Flamme

20.ASU §64 L 00.00-19/3 / DIN EN 14083: Bestimmung von Blei, Cadmium, Chrom und Molybdän mit Graphitofen-Atomabsorptionsspektrometrie (GFAAS) nach Druckaufschluss / Foodstuffs. Determination of trace elements. Determina-



tion of lead, cadmium, chromium and molybdenum by graphite furnace atomic absorption spectrometry (GFAAS) after pressure digestion

21.ASU §64 L 00.00-19/5: Bestimmung von Selen mit der Atomabsorptionsspektro-metrie (AAS) -Hydridtechnik

22.ASU §64 L 00.00-144 : Bestimmung der Mineralstoffe Ca, K, Mg, Na, P und S sowie der Spurenelemente Fe, Cu, Mn und Zn in Lebensmitteln mit ICP-OES

23.ASU §64 L 00.00-93 / DIN EN 15111: Bestimmung von Iod in Lebensmitteln - ICP-MS-Verfahren / Foodstuffs. Determination of trace elements. Determina-tion of iodine by ICP-MS (inductively coupled plasma mass spectrometry)

24.ASU §64 L 00.00-127 / EN 15764: Bestimmung von Zinn in Lebensmitteln mit der Flammen- und Graphitrohr-Atomabsorptionsspektrometrie (GFAAS) nach Druckaufschluss / Foodstuffs. Determination of trace elements. Determina-tion of tin by flame and graphite furnace atomic absorption spectrometry (FAAS and GFAAS) after pressure digestion

25.ASU §64 L 00.00-128 / DIN EN 15765: Bestimmung Zinn in Lebensmitteln mit der Massensprektrometrie mit induktiv gekoppeltem Plasma (ICP-MS) nach Druckaufschluss / Foodstuffs. Determination of trace elements. Determina-tion of tin by inductively coupled plasma mass spectrometry (ICPMS) after pressure digestion

26.ASU §64 L 31.00-10: Bestimmung der Gehalte an Natrium, Kalium, Calcium undMagnesium in Frucht- und Gemüsesäften – Atomabsorptionsspektrometrisches Verfahren (AAS) [Determination of sodium, potassium, calcium and magnesiumin fruit and vegetable juices - atomic absorption spectrometry (AAS)]


Documents

Heavy Metals and Trace Elements 2018/PT - DLA 49-2018...July 2018 DLA 49/2018 – Heavy Metals and Trace Elements Table 1: Composition of DLA-Samples Ingredients Content Supplementary