A new gold standard for Dioxin analysis - 三浦工業 · A new gold standard for Dioxin analysis A...
Transcript of A new gold standard for Dioxin analysis - 三浦工業 · A new gold standard for Dioxin analysis A...
A new gold standard for Dioxin analysisA combined approach ; automated efficient clean-up together with a new Triple Quadrupole GC-MS/MS
Haruhiko Miyagawa, GCMS Product ManagerAnalytical &Measuring Instruments DivisionSHIMADZU Cooperation DIOXIN 2016
Recent demands for Dioxin analysis in food/feed
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Dioxins S3, Smart Solution Systems
Reliable results • Easier and faster operation • Automated procedure• Lower running cost
AnalysisAnalysis
Benefits of the system
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Sample Preparation Extraction Purification Concentration Measurement
FattyAcid
Fat
…
1 day > 2 days 0.5 day> 1 day
>2hr >3hrs
Analysis of12 samples
BUCHI SpeedExtractor E-914 / E-916
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>10x Faster extraction• Extracts the samples at elevated temperature
and pressure
High throughput• Parallel extraction of up to 6 samples
Less solvent use• Sample volumes 10-120 mL, no limitation for
large sample size
Reliable and efficient• Direct sample transfer between extraction and
concentration • Extract collection glassware is compatible to
evaporation instruments from BUCHI
MIURA GO-HT series
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Consumables
Silver Nitrate – Si columnSulfuric Acid – Si columnCarbon columnAlOx column
Total Solvents 110mL
required Solvents Hex, Tol
Cost Sol(¥120/euro) ¥221 (€2)
Final fraction volume 1 ~ 1.5 mL
Max. Sample Weight 3 g fat
Max. Capacity 6 samples
Basic Time 94 mins
No Cross-contaminationReliable Results!Washing the system is not necessary!
Less solventNo DCM use
Small fraction
Less solventNo DCM use
Small fraction
Automated & shorter time
process
Automated & shorter time
process
Ultra-high sensitivity for the fg quantitative analysis
Durable hardware for routine work
Easy to use, simple operation and maintenance
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Shimadzu GCMS-TQ8050
A new GC-MSMS, our latest model!
Foods : Pork meat, Egg, Salmon, Olive oil from the market, 3g fat collected.
Standard Reference Material :Cod liver oil (EDF-5462, EDF-5463 from CIL), 1g fat collected.
Sample were extracted by SpeedExtractor (BUCHI) and purified by GO-HT (MIURA)
Obtain 1.3mL Dioxin fraction and 1.0mL PCB fraction, concentrated to 20uL and 50uL.
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Samples
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GC-MS/MS conditionsGCColumn: DB-5MS (60 m, 0.25 mm I.D., df =0.25 μm) Glass Insert: Custom SkyLiner, Splitless (Restek)Injection Volume: 2 μLInjection Mode: SplitlessInjection Temp: 280 ℃Column Oven Temp. program:150 ℃ (1 min)→(20 ℃/min) → 220 ℃ → (2 ℃/min) → 260 ℃(3 min) → (5 ℃/min) → 320 ℃(8.5min)Flow Control Mode: Constant Linear Velocity 29.4 cm/sec
MS Ionization Mode: EI Acq.Mode: MRM modeIonization Volt.: 70 eVEmission current: 150 μATransision, CE: refer to Smart Env. DatabaseLoop Time: 1 sec (Target: 0.8 sec., ISTD: 0.2 sec.)Pressure of CID gas: 150 kPaMS resolution: Q1 Unit, Q3 UnitDetector volt.: 2.1 kVCalibration range: conc. 0.05 ppb ~ 2 ppb
New RegulationFood Commission Regulation
No 589/2014
30.50 30.75 31.00 31.25 31.50 31.75
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2.00
(x10,000)
375.80>312.90373.80>310.90
1,2,3,4,7,8- HxCDF
1,2,3,6,7,8- HxCDF
Instrument performance check
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compoundRRF at conc. (ppb) LOQ LOD
0.05 0.1 0.2 3σ 10σ2,3,7,8-TeCDD 1.06 1.17 1.26 0.025 0.082 1,2,3,7,8-PeCDD 1.16 1.00 1.09 0.008 0.028 1,2,3,4,7,8-HxCDD 1.15 1.07 1.07 0.013 0.045 1,2,3,6,7,8-HxCDD 1.21 1.07 1.10 0.017 0.058 1,2,3,7,8,9-HxCDD 1.03 0.99 1.07 0.023 0.078 1,2,3,4,6,7,8-HpCDD 1.23 1.24 1.08 0.017 0.057 OCDD 1.05 1.08 1.21 0.044 0.146 2,3,7,8-TeCDF 1.25 1.20 1.12 0.023 0.077 1,2,3,7,8-PeCDF 0.96 1.13 1.07 0.021 0.068 2,3,4,7,8-PeCDF 1.06 1.09 1.03 0.019 0.064 1,2,3,4,7,8-HxCDF 1.13 1.08 1.06 0.020 0.068 1,2,3,6,7,8-HxCDF 1.06 1.12 1.05 0.008 0.028 2,3,4,6,7,8-HxCDF 1.08 1.18 1.07 0.024 0.080 1,2,3,7,8,9-HxCDF 1.00 0.93 0.94 0.031 0.102 1,2,3,4,6,7,8-HpCDF 1.34 1.15 1.17 0.018 0.060 1,2,3,4,7,8,9-HpCDF 1.07 1.07 1.01 0.012 0.042 OCDF 1.09 1.14 1.12 0.029 0.098
20.0 21.0
5000
10000
15000
20000
25000 321.90>258.90319.90>256.90
25.0 26.0 27.0
5000
10000
15000
20000
25000353.90>290.90355.90>292.90
31 0 32 0
5000
10000
15000
20000
25000
30000
391.80>328.80389.80>326.90
2,3,7,8-TeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
0.05ppbStandards15 injectionsStandards15 injections
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Stress test : Stability check
Standards15 injectionsStandards15 injections
Pig fat15 injections
Compound NameInjection number Mean
valueConc(ppb)
%RSD6 7 8 31 47 63 76 89 99
2,3,7,8-TeCDD 0.52 0.53 0.48 0.52 0.50 0.50 0.46 0.50 0.48 0.50 0.50 4.40 1,2,3,7,8-PeCDD 0.47 0.51 0.51 0.50 0.47 0.51 0.49 0.50 0.44 0.50 0.50 3.51 1,2,3,4,7,8-HxCDD 0.93 1.05 1.13 1.21 1.14 1.04 1.21 1.11 1.11 1.10 1.00 8.65 1,2,3,6,7,8-HxCDD 1.14 1.09 0.95 1.08 1.09 1.05 1.03 1.05 1.17 1.06 1.00 5.41 1,2,3,7,8,9-HxCDD 1.03 1.03 0.97 1.09 0.98 1.03 1.09 1.14 1.05 1.04 1.00 5.57 1,2,3,4,6,7,8-HpCDD 0.97 0.98 1.19 1.11 1.07 1.12 1.15 1.06 1.02 1.08 1.00 7.17 OCDD 2.64 2.75 2.84 3.04 2.78 2.73 2.74 2.78 2.73 2.79 3.00 4.17 2,3,7,8-TeCDF 0.54 0.51 0.56 0.55 0.55 0.52 0.56 0.57 0.55 0.55 0.50 4.12 1,2,3,7,8-PeCDF 0.49 0.51 0.53 0.52 0.51 0.52 0.51 0.55 0.49 0.52 0.50 3.26 2,3,4,7,8-PeCDF 0.55 0.54 0.49 0.51 0.51 0.46 0.55 0.52 0.50 0.52 0.50 5.89 1,2,3,4,7,8-HxCDF 1.24 1.03 1.15 1.11 1.16 1.11 1.10 1.08 1.17 1.12 1.00 5.42 1,2,3,6,7,8-HxCDF 0.99 1.03 1.05 1.23 1.05 1.09 1.20 1.14 1.09 1.10 1.00 7.55 2,3,4,6,7,8-HxCDF 1.09 1.11 1.14 1.15 1.13 1.12 1.14 1.12 1.13 1.12 1.00 1.72 1,2,3,7,8,9-HxCDF 1.07 1.01 1.05 1.15 1.02 1.10 1.08 1.03 1.15 1.06 1.00 4.30 1,2,3,4,6,7,8-HpCDF 0.99 1.16 0.96 1.07 1.05 0.99 1.14 1.08 1.15 1.05 1.00 6.95 1,2,3,4,7,8,9-HpCDF 1.08 1.10 1.02 1.12 1.40 1.14 1.19 1.05 1.16 1.14 1.00 10.35 OCDF 2.96 2.64 3.02 3.05 2.79 3.01 2.94 2.93 3.11 2.92 3.00 4.77
Olive15 injections
Egg15 injections
Salmon15 injections
EDF-5462EDF-5463
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Analysis of the food samples (pg/g)
Compound NamePig fat Oliveoil Egg fat Salmon
GC-MS/MS GCHRMS GC-MS/MS GCHRMS GC-MS/MS GCHRMS GC-MS/MS GCHRMS2,3,7,8-TeCDD ND ND ND ND ND ND ND ND1,2,3,7,8-PeCDD ND ND ND ND ND ND ND ND1,2,3,4,7,8-HxCDD ND ND ND ND ND ND ND ND1,2,3,6,7,8-HxCDD ND ND ND ND ND ND ND ND1,2,3,7,8,9-HxCDD ND ND ND ND ND (0.3) ND ND1,2,3,4,6,7,8-HpCDD ND ND ND ND 0.6 (0.5) ND (0.2)OCDD 1.0 (1.1) ND ND 3.0 3.6 ND (0.5)2,3,7,8-TeCDF ND ND ND ND (0.2) (0.3) (0.3) (0.4)1,2,3,7,8-PeCDF ND ND ND ND ND (0.2) ND ND2,3,4,7,8-PeCDF ND ND ND ND (0.1) (0.2) (0.2) (0.3)1,2,3,4,7,8-HxCDF ND ND ND ND ND ND ND ND1,2,3,6,7,8-HxCDF ND ND ND ND ND ND ND ND1,2,3,7,8,9-HxCDF ND ND ND ND ND ND ND ND2,3,4,6,7,8-HxCDF ND ND ND ND ND ND ND ND1,2,3,4,6,7,8-HpCDF ND ND ND ND ND ND ND ND1,2,3,4,7,8,9-HpCDF ND ND ND ND ND ND ND NDOCDF ND ND ND ND ND ND ND ND
Evaluation of quantitative values
( ) : LOD < value < LOQ
Pig fat15 injections
Olive15 injections
Egg15 injections
Salmon15 injections
20.0 21.0
0.0
2.5
5.0
7.5
(x1,000)
305.90>242.95303.90>240.95
2,3,7,8-TeCDF(in Egg fat)
39.0 40.0 41.0
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5(x10,000)
459.70>396.70457.70>394.70
OCDD(in Egg fat)
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Evaluation of quantitative values Quantitative values of EDF-5462Comparison of the individual dioxin concentrations using GC-HRMS and GC-MS/MS.
Compounds NameMean value %RSD(n=3)
GC-MS/MS GCHRMS GC-MS/MS GCHRMS2,3,7,8-TeCDD 16.71 16.25 7.38 5.89 1,2,3,7,8-PeCDD 39.74 43.25 4.66 6.37 1,2,3,4,7,8-HxCDD 43.75 40.25 5.71 3.73 1,2,3,6,7,8-HxCDD 37.59 39.25 5.94 5.65 1,2,3,7,8,9-HxCDD 49.44 43.25 5.32 3.95 1,2,3,4,6,7,8-HpCDD 40.83 40.50 6.30 7.41 OCDD 120.95 110.00 5.87 0.00 2,3,7,8-TeCDF *1069.94 1425.00 3.26 3.51 1,2,3,7,8-PeCDF 355.86 387.50 4.03 3.87 2,3,4,7,8-PeCDF 41.44 40.00 4.50 5.40 1,2,3,4,7,8-HxCDF 45.45 41.00 6.60 1.99 1,2,3,6,7,8-HxCDF 46.63 41.50 2.74 5.74 2,3,4,6,7,8-HxCDF 37.52 41.00 4.50 1.99 1,2,3,7,8,9-HxCDF 44.73 39.25 5.38 1.27 1,2,3,4,6,7,8-HpCDF 41.74 41.00 5.47 3.45 1,2,3,4,7,8,9-HpCDF 38.36 43.00 7.17 4.25 OCDF 82.26 76.00 5.41 1.86
*Peak was saturated
EDF-5462EDF-5463
Dioxins S3, Smart Solution Systems contribute
Speed of the sample preparation
Reduction of running cost
Reliability of the results
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Summary
New RegulationFood Commission Regulation
No 589/2014
Shimadzu Europe
Future work
More evaluationsFaster GC analysis
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48 min.(Column:DB-5MS 60 m))
31 min.(Column:DB-5MS 30 m)
19.0 19.5 20.0 20.5 21.0
100000
200000
300000
400000
500000
600000
700000
800000
900000375.80>312.90373.80>310.90
Peak separation of 1,2,3,4,7,8- HxCDF to 1,2,3,6,7,8-HxCDF is satisfactory to the criteria.
New RegulationFood Commission Regulation
No 589/2014Feed Commission Regulation
(EC) No 709/2014