Table S6: Sample preparation, instrumental analysis, validation parameters and application of sent standard mixture for laboratory coded 6

COMPOUND / SAMPLE PREP. / INTRUM. ANALYSIS / VALIDATION PARAM. / Application of sent mixture
Sample preparation
(sample pre-treatment: pH adjustment, filter pore size, material and trade name, extraction method and conditions, additional clean-up, derivatisation, internal standard,…) / Instrumental analysis
(operational parameters: separation and detection condition,…) / Validation parameters
(sensitivity, accuracy, recovery, reproducibility, repeatability,…) / a. Standard mixture was used for calibration
b. Standard mixture was used for check-up
c.Standard mixture was not used
5-FU / The method is based on on-line Solid-Phase Extraction (SPE) performed with specific instrumentation from Spark Holland (Emmem, The Netherlands).
Filtration of the samples through 0.45 µm polycarbonate membrane filters.
The pH of the samples is adjusted to 2 with acetic acid. Concentration by on-line SPE is carried out with HySphere Resin GP cartridges (10 x 2 mm ID, from Spark Holland).
The determination is controlled by using isoproturon-d6 as surrogate standard and tribromophenol and propanil as internal standard.
The criteria for the recovery of the internal standards are 70-120%. No internal standards correction is applied. / Analysis was performed by LC-MS/MS. The separation of the analytes was performed on a reversed-phase C18 column. The detection was performed by using triple quadrupole MS/MS operating in the MRM (Multiple Reaction Monitoring) mode. Ionisation was carried out by electrospray (ESI) in the positive mode. / Validation parameters:
LOD: 0.1 µg L-1
LOQ: 0.3 µg L-1
Reproducibility: <25 %
Repeatability: <25 %
Recovery: 93% / b
CP / The method is based on on-line Solid- The method is based on on-line Solid-Phase Extraction (SPE) performed with specific instrumentation from Spark Holland (Emmem, The Netherlands).
Filtration of the samples through 0.45 µm polycarbonate membrane filters.
The pH of the samples is adjusted to 2 with acetic acid. Concentration by on-line SPE is carried out with HySphere Resin GP cartridges (10 x 2 mm ID, from Spark Holland).
The determination is controlled by using isoproturon-d6 as surrogate standard and propanil as internal standard.
The criteria for the recovery of the internal standards are 70-120%. No internal standards correction is applied. / After on-line SPE, the extracts were analysed by LC-MS/MS instrument. The separation of the analytes was performed on a reversed-phase C18 column. The detection was performed by using triple quadrupole MS/MS operating in the MRM (Multiple Reaction Monitoring) mode. The ionisation used was electron spray ionisation (ESI) technique in the positive mode. / Validation parameters:
LOD: 0.0012 µg L-1
LOQ: 0.005 µg L-1
Reproducibility: <15 %
Repeatability: <15 %
Recovery: 86 % / b
ETO / The method is based on on-line Solid- The method is based on on-line Solid-Phase Extraction (SPE) performed with specific instrumentation from Spark Holland (Emmem, The Netherlands).
Filtration of the samples through 0.45 µm polycarbonate membrane filters.
The pH of the samples is adjusted to 2 with acetic acid. Concentration by on-line SPE is carried out with HySphere Resin GP cartridges (10 x 2 mm ID, from Spark Holland).
The determination is controlled by using isoproturon-d6 as surrogate standard and propanil as internal standard.
The criteria for the recovery of the internal standards are 70-120%. No internal standards correction is applied. / After on-line SPE, the extracts were analysed by LC-MS/MS instrument. The separation of the analytes was performed on a reversed-phase C18 column. The detection was performed by using triple quadrupole MS/MS operating in the MRM (Multiple Reaction Monitoring) mode. The ionisation used was electron spray ionisation (ESI) technique in the positive mode. / Validation parameters:
LOD: 0.003 µg L-1
LOQ: 0.01 µg L-1
Reproducibility: <20 %
Repeatability: <20 %
Recovery: 89 % / b
IF / The method is based on on-line Solid- The method is based on on-line Solid-Phase Extraction (SPE) performed with specific instrumentation from Spark Holland (Emmem, The Netherlands).
Filtration of the samples through 0.45 µm polycarbonate membrane filters.
The pH of the samples is adjusted to 2 with acetic acid. Concentration by on-line SPE is carried out with HySphere Resin GP cartridges (10 x 2 mm ID, from Spark Holland).
The determination is controlled by using isoproturon-d6 as surrogate standard and propanil as internal standard.
The criteria for the recovery of the internal standards are 70-120%. No internal standards correction is applied. / After on-line SPE, the extracts were analysed by LC-MS/MS instrument. The separation of the analytes was performed on a reversed-phase C18 column. The detection was performed by using triple quadrupole MS/MS operating in the MRM (Multiple Reaction Monitoring) mode. The ionisation used was electron spray ionisation (ESI) technique in the positive mode. / Validation parameters:
LOD: 0.0013 µg L-1
LOQ: 0.005 µg L-1
Reproducibility: <10 %
Repeatability: <10 %
Recovery: 84 % / b
MTX / The method is based on on-line Solid- The method is based on on-line Solid-Phase Extraction (SPE) performed with specific instrumentation from Spark Holland (Emmem, The Netherlands).
Filtration of the samples through 0.45 µm polycarbonate membrane filters.
The pH of the samples is adjusted to 2 with acetic acid. Concentration by on-line SPE is carried out with HySphere Resin GP cartridges (10 x 2 mm ID, from Spark Holland).
The determination is controlled by using isoproturon-d6 as surrogate standard and propanil as internal standard.
The criteria for the recovery of the internal standards are 70-120%. No internal standards correction is applied. / After on-line SPE, the extracts were analysed by LC-MS/MS instrument. The separation of the analytes was performed on a reversed-phase C18 column. The detection was performed by using triple quadrupole MS/MS operating in the MRM (Multiple Reaction Monitoring) mode. The ionisation used was electron spray ionisation (ESI) technique in the positive mode. / Validation parameters:
LOD: 0.05 µg L-1
LOQ: 0.50 µg L-1
Reproducibility: <10 %
Repeatability: <10 %
Recovery: 61% / b