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EU Document on Analytical Quality Control and Method Validation Procedures for Pesticide Residues Analysis in Food and Feed - An Update

Authors:
Antonio Valverde at University of Almería
Antonio Valverde
Tuija Pihlström at The National Food Agency
Tuija Pihlström
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Invited lecture at the 6th Latin America Pesticide Residue Workshop ”LAPRW 2017”
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Antonio Valverde
Pesticide Residues Research Group
University of Almería, Spain
EU Document on Analytical Quality Control and
Method Validation Procedures for Pesticide
Residues Analysis in Food and Feed – An update
Tuija Philström
Swedish National Food Agency
Uppsala, Sweden
Analytical Quality Control and Method
Validation Procedures for Pesticide
Residues Analysis in Food and Feed
Document «AQC EU-SANCO/SANTE»
-Introduction
-Revision/Updating of the EU-SANTE AQC Document
-Document SANTE/11945/2015
-Most Discussed Points / Next revision (2017)
Document AQC – EU SANCO/SANTE
The original document was elaborated by Alan Hill (CSL, MAFF, UK), in 1997
“Quality Control Procedures for Pesticide Residue Analysis”
“Guidelines for Residues Monitoring in the EU”
Doc. 7826/VI/97 (EU Monitoring Programme) (1st EU AQC Meeting,1997, Portugal)
2. Doc. SANCO/3103/2000 (2nd EU AQC Meeting ,1999, Greece)
3. Doc. SANCO/10476/2003 (3rd EU AQC Meeting, 2003, UK)
4. Doc. SANCO/10232/2006 (4th EU AQC Meeting, 2005, Sweden)
5. Doc. SANCO/2007/3131 (2007 EURL Joint Workshop, Spain)
6. Doc. SANCO/10684/2009 (2009 EURL Joint Workshop, Denmark)
7. Doc. SANCO/12495/2011 (2011 EURL Joint Workshop, Germany)
8. Doc. SANCO/12571/2013 (2013 EURL Joint Workshop, Spain)
9. Doc. SANTE/11945/2015 (2015 EURL Joint Workshop, Germany)
Year 2014
Results
Samples
WITHOUT
Residues
Samples
WITH
Residues
53.6 %
Analysis of 82,649 Samples
EU Official Monitoring Programmes for
Pesticide Residues in Food
(EU + Norway + Iceland)
46.4 %
Samples WITH Residues > MRL 2.9 %
Reporting Country
Pesticides with the highest number of Detections exceeding the MRL
Nº of Detections Exceeding the MRL
Chlorpyrifos
Third Countries EU+Norway+Iceland Unknown
Origin of samples
Carbendazim
Acetamiprid Dimethoate
Imidacloprid
N
Cl
Cl
Cl
O P
SOCH
2
CH
3
OCH
2
CH
3
EU Official Monitoring Programmes for
Pesticide Residues in Food
(EU + Norway + Iceland) Year 2014
Multi-Residue Methods
Extracción
Clean-up
GC LC
NPD - FPD - PFPD - ECD UV/DAD FluorescenceMS
Sample Preparation
Extraction
Chromatographic Determination
«Single-Residue Methods»
Ethephon, Glyphosate,
Amitraz, Abamectin,
-quats, Organotins,
Acidic Pesticides,
Dithiocarbamates,
… & more
AQC SANCO/SANTE Document
Quality Control Procedures for Pesticide
Residues Analysis
“Guidelines for Residues Monitoring in the EU”
EUPTs
EU Proficiency Tests
for Pesticide Residues in Food and Feed
EU Pesticide Residues Monitoring Programmes
Main tools to Assure the Quality of the Analytical Results
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Pesticide Residues
EUPTs
Pesticide Residues
EUPTs
Animal Origin
EUPT- AO
Animal Origin
EUPT- AO
Cerals & Feed
EUPT- CF
Cerals & Feed
EUPT- CF Fruits-Vegetables
EUPT- FV
Fruits-Vegetables
EUPT- FV Single Residue
EUPT- SRM
Single Residue
EUPT- SRM
AQC Procedures for Pesticide
Residues Analysis
National Reference Laboratories (NRLs)
European Union Reference Laboratories (EURLs)
Revisions of the Document AQC – EU SANCO/SANTE
1. Doc. 7826/VI/97 (1st EU AQC Meeting,1997, Portugal)
2. Doc. SANCO/3103/2000 (2nd EU AQC Meeting ,1999, Greece)
3. Doc. SANCO/10476/2003 (3rd EU AQC Meeting, 2003, UK)
4. Doc. SANCO/10232/2006 (4th EU AQC Meeting, 2005, Sweden)
5. Doc. SANCO/2007/3131 (2007 EURL Joint Workshop, Spain)
6. Doc. SANCO/10684/2009 (2009 EURL Joint Workshop, Denmark)
7. Doc. SANCO/12495/2011 (2011 EURL Joint Workshop, Germany)
8. Doc. SANCO/12571/2013 (2013 EURL Joint Workshop, Spain)
9. Doc. SANTE/11945/2015 (2015 EURL Joint Workshop, Germany)
http://www.eurl-pesticides.eu
Revisions of the Document AQC – EU SANCO/SANTE
http://www.eurl-pesticides.eu
http://www.eurl-pesticides.eu
Revisions of the Document AQC – EU SANCO/SANTE
Revisions of the Document AQC – EU SANCO/SANTE
http://www.eurl-pesticides.eu
Revisions of EU-SANTE – AQC Document
1. Doc. 7826/VI/97
9. Doc. SANTE/11945/2015
- Harmonization with other international guidelines
- Updating criteria to include new technical developments
- Updating criteria to include the real labs experiences
- Improving the practical application of criteria
- Clarifying doubts and misinterpretations from labs
- Keeping the document as simple, practical and flexible as possible
Reasons to justify the revisions
Revisions of EU-SANCO – AQC Document
SANCO/10232/2006 Paragraph 73: …The RRT of the analyte, should
correspond to that of the calibration solution with a
tolerance of ± 0.5% for GC and ± 2.5% for LC.
Just an EXAMPLE:
SANCO/12571/2013
SANTE/11945/2015
Analyte Identification
Requirement for Chromatography
D2 ... the retention time of the analyte
should correspond to that of the
calibration standard with a tolerance of
±0.2 min for both GC and LC.
D2 ... the retention time of the analyte
should correspond to that of the
calibration standard with a tolerance of
±0.1 min for both GC and LC.
«Analytical Quality Control and Validation Procedures for
Pesticide Residues Analysis in Food and Feed»
Document SANTE/11945/2015
Discussed and consensued at
the «Joint EURLs-NRLs WS»
(Stuttgart, October - 2015)
Revised by the «AQC-SANTE
Advisory Board 2014-2015»
Structure of Document SANTE/11945/2015
A.- Introduction and legal background
B.- Sampling, transport, traceability and storage of samples
C.- Sample Analysis
D.- Identification of analytes and confirmation of results
E.- Reporting results
F.- Pesticide standards, stock and calibration solutions
G.- Analytical method validation and performance criteria
H.- Additional recommendations
Annex A and Appendices
Annex A (Commodity groups and representative commodities)
Appendix A (Method validation procedure: outline and example approaches)
Appendix B (Examples of conversion factors)
Appendix C (Examples for the estimation of measurement uncertainty)
Appendix D (Glossary)
Validation
Quality Control
Document SANTE/11945/2015
On-going validation
Analytical Calibration
Routine Recovery Determination
(On-going Performance Verification/Validation)
Identification of Analytes
Reporting Results
Key Activities/Criteria for Quality Control
SANTE/11945/2015
C.- Sample Analysis
D.- Identification of analytes and confirmation of results
E.- Reporting results
G.- Analytical Method Validation
- Standards in matrix, if appropriate
- Alternative use of “analyte protectants” in GC
- Alternative (recommended) use of “standard addition”
- Calibration in each batch of analysis
- Bracketing calibration (< 30% drift)
-LCL* ≤RL (RL ≥ LOQ)
*LCL = Lowest Calibrated Level; RL = Reporting Limit; LOQ = Limit of Quatification
Analytical Calibration
Document SANTE/11945/2015
Multilevel Calibration Function (preferred)
- Individual residuals must not deviate more than ±20%
Interpolation between 2 Calibration Levels
- Difference between levels not greater than a factor of 10
- RFs at each level should not differ by more than 20%
Single-Level Calibration
- May also provide accurate results
- Sample response should be within ±30% of the standard
Analytical Calibration
Document SANTE/11945/2015
y = 4.546.905,6604x
R² = 0,9664
0
10.000.000
20.000.000
30.000.000
40.000.000
50.000.000
60.000.000
70.000.000
80.000.000
90.000.000
100.000.000
0 5 10 15 20 25
(relative diference)
RESIDUAL
(relative diference)
«Back Concentration»
RESIDUAL
Multilevel Calibration Function
- Individual residuals must not deviate more than ±20%
Document SANTE/11945/2015
This point must be clarified
in the next revision!?
D2 ... the retention time of the analyte
should correspond to that of the
calibration standard with a tolerance
of ± 0.1 min for both GC and LC.
Identification of Analytes
Requirements for Chromatography
Document SANTE/11945/2015
1. Doc. 7826/VI/97 Paragraph 67: …Intensity ratios for principal ions
should be within 80-120% of those obtained from
the standard …
Ion ratios tolerances for confirmation by MS
7. Doc. SANCO/12495/2011
8. Doc. SANCO/12571/2013
Identification of Analytes
Requirements for Mass Spectrometry (MS)
SANTE/11945/2015 Identification requirements for MS
Representative matrices may be used
As a minimun, one matrix from each Commodity Group
Complementary validation during routine analysis
Document SANTE/11945/2015
G.- Analytical method validation and performance criteria
- High water content
- High acid content (high water content)
- High sugar content (low water content)
- High oil content (very low water content)
- High oil content (intermediate water content)
- High starch and/or protein content (low water & fat content)
- “Difficult or unique commodities”
VEGETABLES, FRUITS, and CEREALS
Validation
11 Commodity Groups for Representative Food Commodities
(Annex A)
Document SANTE/11945/2015
- Meat (muscle) and Seafood
- Milk and milk products
- Eggs
- Fat from food of animal origin
FOOD OF ANIMAL ORIGIN
Similar groupes for «Feed»
2 Fortification Levels for each Representative Commodity:
- Reporting Limit / LOQ (n = 5)
- Another higher level / MRL (n = 5)
Method Performance Acceptability Criteria
(Quantitative Methods)
For each Fortification Level/Representative Commodity*:
- Mean Recovery = 70-120 %
- RDSr& RSDwR ≤20 %
* In certain justified cases different values may be accepted
Document SANTE/11945/2015
Minimun requirements - Initial validation
n = 5
Routine Single Recovery Determination
(On-going method performance verification/validation)
This AQC tool is used to:
- Ensure the validity of the results during routine analysis
- Determine within-laboratory reproducibility (RSDwR)
- Determine acceptable limits for single recoveries
- Demonstrate applicability to other commodities / levels
- Demostrate robustness
- Collect information for uncertainty estimation
Document SANTE/11945/2015
Mean Recovery ± 2 x RSD
(Initial and on-going validation)
but
a generalized range of 60-140 % may be used
Acceptable Limits for Routine Recovery
Document SANTE/11945/2015
To be used for «intra-laboratory» estimation
of measurement uncertainty (MU)
- Different matrices / same commodity group
- Different spiking levels
Single recovery
Acceptable Limits for Routine Recovery
(mean recovery ±2xRSD)
Mean recovery*
70% 80% 90% 100% 110% 120%
RSD* Acceptable recovery range for individual recoveries (%)
5% 63 - 77 72 - 88 81 - 99 90 - 110 99 - 121 108 - 132
10% 56 - 84 64 - 96 72 - 108 80 - 120 88 - 132 96 - 144
15% 49 - 91 56 - 104 63 - 117 70 - 130 77 - 143 84 - 156
20% 42 - 98 48 - 112 54 - 126 60 - 140 66 - 154 72 - 168
* From on-going / initial validation
Need of introducing of a new recovery criteria?
(i.e.: n>10; different levels/commodities at initial/on-going validation) For example:
80% - 110%?
Current active discussion:
E10 A default expanded MU of 50% … is
recommended to be used by regulatory
authorities in cases of enforcement
decisions (MRL-exceedances).
Reporting of results
Interpretation of results for enforcement purposes
Document SANTE/11945/2015
E10 … A prerequisite for the use of 50% default
expanded MU is that the laboratory must
demosntrate that its own expanded MU
is less than 50%...
- Mean Recovery = 80-110 %
- Mean Recovery = 70-120 %
OK
- Mean Recovery = 80-120 %
RSDwR ≤20 %
?
Reporting of results
Expression of results
E1 … Where the residue definition includes more than one
analyte, the respective sum of analytes must be
calculated as stated in the residue definition … (if not
possible) … a part of the sum may be calculated but this
should be clearly indicated in the report …
E1 The results from the individual analytes measured must
always be reported …
E2 … residues of individual analytes below the RL must
be reported as < RL …
E1 … concentrations of all individual analytes and their LOQs
must be submitted. (in case of electronic submission of results for samples
that are part of a monitoring programme)
These paragraphs were amended (clarified) in the last revision
Document SANTE/11945/2015
Document N°SANCO/12571/2013
Reporting of results
Expression of results
Current active discussion in EU
Is it appropiate to stablish a RL (or LOQ) value for
the (sum) whole residue definition?
No reference to the LOQ (sum) in
the SANTE-AQC Document!!!
AQC Advisory Board conclusion:
NOT appropiate!!!
Is the SANTE-AQC Document in contradiction with the
«Working document on the summing up of LOQs»?
FORMAL and HARMONISED approach for reporting
results of pesticide monitoring analysis to EFSA
(using the «Standard Sample Description» - SSD)
Reporting of results
All individual
components need to be
reported separately
together with their
individual LOQ
(Such as it is indicated in the
data elements described in the
«Standard Sample Description»)
Sensivity check for LOQs for MRLs are set at the LOQ*: LOQ (legal RD)
LOQ (legal RD) = sum of individual LOQs (Residue Definition)
LOQ (legal RD) ≤MRL*
Key Point
EXAMPLE: «Sensivity chek» for ALDICARB
Aldicarb resLOQ = 0.01 mg/kg
Aldicarb sulfone resLOQ = 0.01 mg/kg
Aldicarb sulfoxide resLOQ = 0.01 mg/kg
LOQ (Legal RD) = 0.0277 mg/kg
> MRL*
Do not Pass
Sensivity check
Working Document Summing up LOQs
«Standard Sample Description»
How to report the result for the «sum» if some
component result is either Not Analized or < RL
How to report the result for the «sum» if some
component result is either Not Analized or < RL
A consistent proposal for Non-Official Laboratories:
Endosulfan I < RL (0.01) (All analytes < RL)
Endosulfan II < RL (0.01)
Endosulfan-sulf = NA (not Analyzed) Result for the sum: = NA (Not Analyzed)
Endosulfan I = 0.01 mg/kg
Endosulfan II = 0.03 mg/kg Result for the sum: = NA (Not Analyzed)
Endosulfan-sulf = NA (not Analyzed) Sum of Endosulfan I + Endosulfan II = 0.04 mg/kg
B) Some component was Not analyzed
A) All the components were analyzed
Endosulfan I < RL (0.01) (All analytes < RL)
Endosulfan II < RL (0.01)
Endosulfan-sulf < RL (0.02) Result for the sum: < highest RL
Endosulfan I = 0.01 mg/kg (Sum of quantitative results)
Endosulfan II = 0.03 mg/kg
Endosulfan-sulf < RL (0.02) Result for the sum: = 0.04 mg/kg
«Conversion Factor»
Many Thanks for Your Attention!
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Article
  • Jan 2019
In this study, several calystegines (A3, A5, B1, B2, B3, B4 and C1) have been determined in tomato. A simple extraction followed by a derivatization step with silylating agents has been performed prior to their analysis by gas chromatography coupled to high resolution mass spectrometry (GC-HRMS-Q-Orbitrap), which allowed the monitoring of several ions at accurate mass. The validation of the method has provided suitable values of linearity, trueness (73.7-120.0%) and precision (≤ 20.0%, except for calystegines B3 and B4 at 0.5 mg/kg). The limit of quantitation (LOQ) was set at 0.5 mg/kg for all analytes. The validated method was successfully applied to the analysis of nine different tomato varieties, and calystegines A3, A5, B2 and C1 were found at concentrations ranging between 0.65 mg/kg (C1) and 12.47 mg/kg (B2). Tomato varieties were classified according to their calystegines content applying an analysis of variance (ANOVA).
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