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Meeting the challenges of EU regulations with up-to-date confirmatory solutions 
Lunch Seminar at the 34th International Symposium on Halogenated Persistent Organic Pollutants (Dioxin 2014)
Validation of a triple quadrupole GC-MS/MS technology for detection, quantification and confirmation of low level dioxins in feed and food samples 
Cristian Cojocariu, PhD 
ThermoFisher Scientific, Runcorn, UK
3 
Overview 
•Thermo Scientific™ TSQ 8000™ Evo triple quadrupole GC-MS was used to detect and confirm low level of PCDD/Fs in sample extracts, taking into account the EU Commission Regulation 589/2014 and the new Regulation No. 709/2014 
•A thorough validation of the TSQ 8000 Evo GC-MS/MS for dioxin confirmation was performed. 
•Instrument sensitivity, linearity, chromatography, LOD/LOQs and precision of measurements were assessed. 
•Data acquired using the GC-MS/MS was compared with the GC-HRMS data acquired for the same samples and measurements uncertainties were assessed.
4 
EXPERIMENTAL
5 
TSQ 8000 Evo GC-MS System 
•State of the art triple quadrupole GC-MS system introduced at ASMS 2014 
•Fast collision cell instrument with enhanced velocity optics with EvoCell technology to provide high SRM transition speeds, precision and sensitivity 
•ExtractaBrite™ ion source is heated throughout ensuring high matrix tolerance 
•Ion source fully removable, hot, under vacuum when cleaning is necessary or swapping with a spare; no vent to clean your instrument
6 
GC & MS Conditions 
Thermo Scientific™ TRACE™ 1310 GC Parameters 
Column 
TG-5 SIL MS, 60 m x 0.25 x 0.25 
Injection Volume (mL): 
2 
Liner 
SSL single taper 4mm ID 78.5mm 
Inlet (°C): 
260 
Inlet Module and Mode: 
splitless 
Carrier Gas, (mL/min): 
He, 1.2 
Oven Temperature Program time (min): 
33 
TSQ 8000 Evo Mass Spectrometer Parameters 
Transfer line (°C): 
280 
Ionization type: 
EI 
Ion source(°C): 
300 
Electron energy (eV): 
40 
Acquisition Mode: 
SRM 
Q1 Peak Width (AMU): 
0.7 
Q3 Peak Width (AMU): 
0.7 
GC 
MS
7 
Samples 
•Wellington Lab standards used in the experiments described below: EPA1613 calibration set 
TF-TCDD-MXD 
Compound 
Concentration (fg/μL) 
1368-TCDD 
10 
1379-TCDD 
25 
1378-TCDD 
100 
1478-TCDD 
250 
1234-TCDD 
500 
2378-TCDD 
1000
8 
Samples 
•Matrix samples (previously analysed on a GC-HRMS instrument) provided by EU-RL, Freiburg 
•Samples chosen were naturally contaminated with low level of PCDD/Fs. 
•Used to assess and validate the LOQs in matrix samples as well as to check precision of total dioxin content at low level. 
•Extraction and clean-up was carried out in accordance with the existing methods for food and feed either automatically (PowerPrep™ SPE) or partly manual/partly automated (GPC, multi-layer silica, Florisil®, carbon). 
Mixed animal fat 
Fish meal 
Egg fat 11 
Egg fat 2 
Weighted sample: 
10.0 g fat 
60.2 g sample (= 10.0 g fat) 
0.52 g fat 
0.51 g fat 
Lipid content [%]: 
n/a 
16.6 
n/a 
n/a 
Moisture content [%]: 
n/a 
5.3 
n/a 
n/a 
Final volume: 
40 μl 
40 μl 
10 μl 
10 μl 
13C Internal standard 
13C Internal standard 
13C Internal standard 
13C Internal standard 
2378 TCDF 
50 
50 
10 
10 
12378 PCDF 
50 
50 
10 
10 
23478-PCDF 
200 
200 
40 
40 
123478 HxCDF 
100 
100 
20 
20 
123678 HxCDF 
100 
100 
20 
20 
234678 HxCDF 
50 
50 
10 
10 
123789 HxCDF 
50 
50 
10 
10 
1234678 HpCDF 
100 
100 
20 
20 
1234789 HpCDF 
50 
50 
10 
10 
OCDF 
100 
100 
20 
20 
2378 TCDD 
50 
50 
10 
10 
12378 PCDD 
100 
100 
20 
20 
123478 HxCDD 
100 
100 
20 
20 
123678 HxCDD 
200 
200 
40 
40 
123789 HxCDD 
50 
50 
10 
10 
1234678 HpCDD 
200 
200 
40 
40 
OCDD 
600 
600 
120 
120 
13C Recovery standard 
13C Recovery standard 
13C Recovery standard 
13C Recovery standard 
1234-TCDD 
50 
50 
10 
10
9 
Data Acquisition and Data Processing 
•Data were acquired using timed-Selected Reaction Monitoring (timed-SRM). 
•A minimum of 12 points/chromatographic peak were acquired. 
•Data processing was performed with Thermo Scientific™ TargetQuan 3.1 software.
10 
Linearity of Response 
•Linearity assessed by determining the average RF %RSD values from a six point calibration curve measured at the beginning and at the end of the sample batch. 
•Values represent duplicate measurements of each calibration point, measured at the beginning and end of a batch. 
Compound 
Concentration range (pg/μL) 
Average RF 
stdev 
RF %RSD 
2378-TCDF 
0.1 - 40 
1.0 
0.04 
3.7 
2378-TCDD 
0.1 - 40 
1.4 
0.02 
1.4 
12378-PeCDF 
0.5 - 200 
1.0 
0.01 
0.9 
23478-PeCDF 
0.5 - 200 
1.0 
0.02 
1.8 
12378-PeCDD 
0.5 - 200 
1.2 
0.03 
2.5 
123478-HxCDF 
0.5 - 200 
1.0 
0.01 
0.8 
123678-HxCDF 
0.5 - 200 
1.0 
0.01 
1.3 
234678-HxCDF 
0.5 - 200 
1.0 
0.01 
1.3 
123478-HxCDD 
0.5 - 200 
0.9 
0.01 
0.7 
123678-HxCDD 
0.5 - 200 
1.1 
0.01 
1.3 
123789-HxCDD 
0.5 - 200 
1.0 
0.01 
0.7 
123789-HxCDF 
0.5 - 200 
1.0 
0.05 
4.5 
1234678-HpCDF 
0.5 - 200 
1.1 
0.01 
0.9 
1234678-HpCDD 
0.5 - 200 
1.1 
0.01 
1.0 
1234789-HpCDF 
0.5 - 200 
1.1 
0.02 
1.4 
OCDD 
1.0 - 400 
1.5 
0.02 
1.6 
OCDF 
1.0 - 400 
1.1 
0.02 
1.4
11 Determination of Limit of Quantification 
•LOQ calculated from CSL x5 and CSL x10 dilution and taking into account the ion ratio, response factors and precision limits. 
•LOQ for each native compound was calculated taking into account the student’s-t critical values for the corresponding degrees of freedom (99% confidence). 
Compound 
pg/μL 
2378-TCDF 
0.01 
2378-TCDD 
0.01 
12378-PeCDF 
0.02 
23478-PeCDF 
0.02 
12378-PeCDD 
0.02 
123478-HxCDF 
0.04 
123678-HxCDF 
0.04 
234678-HxCDF 
0.03 
123478-HxCDD 
0.06 
123678-HxCDD 
0.03 
123789-HxCDD 
0.04 
123789-HxCDF 
0.04 
1234678-HpCDF 
0.02 
1234678-HpCDD 
0.05 
1234789-HpCDF 
0.02 
OCDD 
0.05 
OCDF 
0.03
12 
Sensitivity test: stepped standard 
• Overlayed SRM chromatograms (quan ion) of six TCDD congeners in the stepped 
standard. 
• Concentrations represents ‘on column’ amount. 
RT: 13.37 - 14.94 SM: 3B 
13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 
Time (min) 
0 
5 
10 
15 
20 
25 
30 
35 
40 
45 
50 
55 
60 
65 
70 
75 
80 
85 
90 
95 
100 
14.78 
14.57 
14.30 
14.15 
13.65 
13.52 14.86 13.53 13.76 14.38 14.41 14.67 
14.56 
NL: 8.47E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_11 
NL: 8.33E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_03 
NL: 8.49E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_05 
NL: 8.25E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_06 
NL: 8.35E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_07 
NL: 8.38E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_08 
NL: 8.53E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_09 
NL: 8.48E4 
TIC F: + c EI SRM ms2 
321.890@cid20.00 
[258.925-258.935] MS 
19May2014_10 
1368-TCDD 
10 fg 
IR % = 9 
1379-TCDD 
25 fg 
IR % = 6 
1378-TCDD 
100 fg 
IR % = 7 
1478-TCDD 
250 fg 
IR % = 6 
2378-TCDD 
1000 fg 
IR % = 4 
1234-TCDD 
500 fg 
IR % = 11 
Inj. No. Concentration 
10 fg 25 fg 100 fg 250 fg 500 fg 1000 fg 
1 3129 7011 25940 60219 87635 239216 
2 3045 6209 25998 59108 85789 240162 
3 3047 7055 27425 58262 87578 237274 
4 2637 7440 25734 59335 87079 233655 
5 2678 6376 27805 58583 83897 234470 
6 2964 6513 27097 58902 85373 238554 
7 2828 6931 26347 59936 86844 242740 
8 2699 6579 25033 55519 79471 232038 
mean 2878.4 6764.3 26422.4 58733.0 85458.3 237263.6 
STDEV 192.5 411.7 940.7 1452.1 2730.3 3625.3 
% RSD 6.7 6.1 3.6 2.5 3.2 1.5
13 
DETERMINATION OF DIOXINS IN SAMPLE EXTRACTS
14 Quantification of Dioxins in the Sample Extracts 
•The egg, animal fat and fish meal samples were analyzed for their dioxin content. 
•The calculated concentration of each individual dioxin congener (pg TEQ/g fat or ng/kg %dw) was compared with the values obtained from the GC-HRMS.
15 
Chromatography & Selectivity 2378-TCDD in Sample Extracts 
95 fg 28 fg 
98 fg fish meal 
mixed animal fat egg
16 
Egg Samples - Comparison with GC-HRMS 
0.00 
0.10 
0.20 
0.30 
0.40 
0.50 
0.60 
0.70 
0.80 
0.90 
1.00 
WHO pg TEQ/g fat 
GC-HRMS 
GC-MS/MS egg 0.52g 
GC-MS/MS egg 0.51 g
17 Fish Meal - Comparison with GC-HRMS
18 
Ion Ratio Stability: IR Egg Sample vs. Theoretical IR
19 Ion Ratio Stability: IR Egg Sample vs. IR CS3
20 
Precision of Measurements: Sample Extracts 
•Obtaining valid estimates of PCDD/Fs concentration in sample extracts is critical. 
•Precision measurement of the total dioxin content (as WHO TEQ pg/g or ng/kg) for a sequence of n=13 repeat injections of the mixed animal fat and the fish meal samples
21 Fish Meal: Precision of Total Dioxin Content (n=13)
22 
Mixed Animal Fat: Precision of Total Dioxin Content (n=13)
23 
Comparison with GC-HRMS 
Total dioxin content of sample extracts 
•Average values of replicate injections (n) with corresponding standard deviations (in brackets) are given. 
Sample type 
WHO-PCDD/F-TEQ-ub 
GC-HRMS 
GC-MS/MS 
Deviation % 
egg (n=2) 
3.39 pg/g 
3.27 (0.03) 
-3.5 
fish meal (n=13) 
0.26 ng/kg % dw 
0.25 (0.01) 
-2.2 
mixed animal fat (n=13) 
0.83 pg/g 
0.85 (0.04) 
2.8
24 
Conclusions 
•Excellent selectivity and sensitivity was achieved (ex: 28 fg 2378-TCDD absolute amount on column) 
•Precision measurements of the total dioxin content (WHO-PCDD/F-TEQ-ub) were obtained for two low level contaminated samples (fish meal and mixed animal fat) with %RSD values <6% (n=13). 
•Deviation of the total dioxin content (WHO-PCDD/F-TEQ-ub) from the GC-HRMS data was analyzed within the ±20% for all the samples. 
•The data shows excellent agreement between the results obtained using the TSQ 8000 Evo GC-MS/MS and those obtained using GC-HRMS. 
•TSQ 8000 Evo triple quadrupole system is a sensitive and robust system suitable for the quantification and confirmation of low level dioxins and furans in food and feed matrices.
25 
Acknowledgements
26 Thank You for Your Attention! Stay connected with us Twitter @ChromSolutions Chromatography Solutions Blog http://chromblog.thermoscientific.com/blog YouTube http://www.youtube.com/ChromSolutions Facebook http://www.facebook.com/ChromatographySolutions Pinterest http://pinterest.com/chromsolutions/
Economic POPs 
Dave Hope, Patrick Pond, Wasana Mudalige, Jose del Pozo, Matt Wright 
Pacific Rim Laboratories Inc. 
Presented at Thermo Scientific Vendor Seminar 
Madrid, Spain September 2,2014
Outline 
• 
Cost of Analysis 
• 
Saving time on extraction - Accelerated Solvent Extraction (ASE) 
• 
Saving time and money on clean-up - Cape Technologies Clean-up Kits 
• 
Is GC-MS/MS technology ready for POPs – Thermo Scientific™ TSQ™ 8000 system
Economic Costs – POPs Lab 
• 
Laboratory 
– 
$1-3M or higher if budget allows 
• 
Instrument 
– 
$150-400k up to $250-600k depending on options 
• 
Staffing (2-10) 
– 
$20-50 per hour ($40-100k per annum) 
• 
Soft costs 
– 
Chemicals 7-10% revenue 
– 
Consumables 5-10% revenue 
– 
Service contracts/R&M 5-7% revenue or 5-10% instrument cost 
– 
Staff Training 6 weeks to 6 months or $5-35k
Cost of Analysis 
• 
Sample Extraction (batch of 10 samples) 
– 
Water: liquid/liquid sep funnel 6-8 h 
– 
Soil/tissue: soxhlet 6-8 h 
– 
Tissue: acid digestion 12 h 
– 
@ $20 per hour with 10 sample batch $16-24 
– 
@ $20 per hour with 6 sample batch $25-40 
– 
@ $20 per hour with 2 sample batch $50-75
Sample clean-up 
• 
Clean-up steps (4-8 h each) 
– 
Acid or base washes 
– 
Acid/base silica gel 
– 
Basic Alumina 
– 
Florisil (separate dioxins and PCBs) 
– 
Carbon 
• 
Soft costs 
– 
Preparing reagents 
– 
Cleaning reusable glassware – 2 h per day 
– 
Re-analyzing cross contaminated samples
Simplified Clean-up for Food and Environmental Sample 
• 
Cape Technologies tandem acid silica gel / carbon columns 
– 
Originally designed as clean-up kit for EPA Method 4025 (Screening for PCDD/F by Immunoassay) 
– 
quick and cheap – 4-6 h to complete 12 samples, <$20/sample disposable columns, $500 hardware 
– 
Columns are disposable, therefore reduces PCB carryover from improper washing of reusable columns (not to mention the labor savings) 
– 
Separates dioxins from PCBs 
– 
Separates dl PCBs from interfering PCBs with high LOC 
– 
Yang et al (MOE Ontario) developed method to separate PCB, PBDE and PCDD/F (Dioxin 2010)
Cape Technologies Clean-up Kit 
• 
Glass column, 15 mm x 27 cm, loaded with 5 g acid (30%) silica gel (63-200 μm) 
• 
25 mm column available with 14 or 28 g acid (50%) silica (32-63 μm) 
• 
Each column individually sealed, wrapped in boxes of 12 
• 
Carbon soxhlet extracted with Toluene prior to packing in Teflon column (one end flat and the other end bevelled for easy identification of flow direction) 
• 
150 mg of 2% carbon in FEP Teflon
Columning Procedure 
• 
Pre-rinse carbon column 
– 
10 mL toluene 
– 
10 mL DCM 
– 
30 mL hexane 
• 
Attached carbon column to acid silica gel – bevelled side down 
• 
Load sample in 1-2 mL hexane 
• 
Elute 30 mL hexane (F1) – pressurize to 10 psi (1-2 mL/min) 
• 
Remove carbon and attach to empty glass column 
• 
Elute 6 mL 1:1 toluene/hexane (F2) 
• 
Reverse carbon column flow 
• 
Elute 30 mL toluene (F3)
F3 – PCDD/F 
• 
All 17 congeners found in F3 
• 
Spike recoveries for TeCDD/F- HpCDD/F were 93-107% with RSD<12% 
• 
Recovery of OCDD was 85% and OCDF 49% 
• 
There may be some loss of non-2,3,7,8 congeners (especially TeCDD/F) 
• 
Cut point between F2/F3 tight for TeCDD/F (F2 max volume 6 mL of 50:50 toluene/hexane)
Accelerated Solvent Extraction (ASE) 
• 
Has been widely used for soils and tissues in conventional analyses (ppm/ppb) 
• 
Cells and lines subject to trace contamination and carry over at ultra-trace levels 
• 
Recently given an Thermo Scientific™ Dionex™ ASE™ 350 Accelerated Solvent Extractor to play with complete with 100 mL Thermo Scientific™ Dionium™ cells 
• 
Thermo Fisher Scientific has application notes for tissue samples using max 1 g lipid 
• 
PRL methodology requires 5-10 g lipid for lowest DLs 
• 
Initial problems with packing cells – critical not to 
– 
over pack them – SOLVENT LEAKAGE WARNING 
– 
under pack them – VAPOUR PRESSURE WARNING 
• 
Instrument lines and cells required thorough cleaning after installation
ASE 350 System 
Extraction Conditions 
Extraction Solvent: Hexane/Acetone 3:1 
Temperature: 100 °C 
Pressure: 1600 psi 
Heat Time: 5 min 
Static Time: 5 min 
Flush Volume: 70% 
Purge Time: 120 s 
Static Cycles: 3 
Total Prep Time: 15 min per sample 
Total Extraction Time: 25 min per sample
Butter (n=5) 
Units: ng/kg (pg/g) 
Control 
Average 
Spike 
Recovery 
RSD 
2378-TCDD 
<0.03 
<0.03 
20 
91% 
15% 
12378-PeCDD 
<0.033 
<0.033 
100 
94% 
5% 
123478-HxCDD 
0.15 
0.20 
100 
82% 
14% 
123678-HxCDD 
0.56 
0.60 
100 
87% 
8% 
123789-HxCDD 
0.18 
0.25 
100 
90% 
3% 
1234678-HpCDD 
1.21 
1.69 
100 
96% 
7% 
OCDD 
0.88 
1.83 
200 
95% 
2% 
2378-TCDF 
<0.03 
<0.03 
100 
94% 
11% 
12378-PeCDF 
<0.039 
0.07 
100 
92% 
5% 
23478-PeCDF 
<0.039 
<0.039 
100 
90% 
8% 
123478-HxCDF 
0.16 
0.24 
100 
82% 
14% 
123678-HxCDF 
0.12 
0.12 
100 
86% 
9% 
123789-HxCDF 
<0.056 
<0.056 
100 
93% 
5% 
234678-HxCDF 
0.11 
0.20 
100 
80% 
16% 
1234678-HpCDF 
<0.052 
<0.052 
100 
88% 
12% 
1234789-HpCDF 
<0.085 
<0.085 
100 
87% 
9% 
OCDF 
<0.13 
0.20 
200 
66% 
6% 
Use 6.25 g of butter (80% lipid) mixed with 10 g diatomaceous earth 
Add internal standards 
Pack 100 mL Dionium cell with 
• 
30 mm cellulose filter 
• 
10 g Dionex ASE Prep CR Na+ form (sulphonated divinyl benzene/styrene copolymer) 
• 
Add sample mix 
• 
Top with diatomaceous earth to 10 mm from top of cell 
Cape Technologies column clean-up
Butter PCB data 
ng/kg 
Control 
Average (n=3) 
Spike Recovery 
PCB 28 
<2 
12.8 
73% 
PCB 52 
5.1 
19.1 
92% 
PCB 101 
<2 
<2 
116% 
PCB 153 
61.7 
58.4 
112% 
PCB 138 
39.6 
48.7 
109% 
PCB 180 
25.6 
22.0 
99% 
PCB 81 
<1 
<1 
103% 
PCB 77 
<1 
<1 
97% 
PCB 123 
<1 
<1 
88% 
PCB 118 
51.1 
41.7 
86% 
PCB 114 
<1 
<1 
103% 
PCB 105 
<1 
<1 
99% 
PCB 126 
<1 
<1 
96% 
PCB 167 
<1 
<1 
103% 
PCB 156 
5.8 
4.1 
110% 
PCB 157 
<1 
<1 
105% 
PCB 169 
<1 
<1 
95% 
PCB 189 
<1 
<1 
82%
Horse Meat 
Control (n=1) 
Average (n=5) 
RSD 
2,3,7,8-TCDD 
0.27 
0.18 
21% 
1,2,3,7,8-PeCDD 
1.0 
0.94 
22% 
1,2,3,4,7,8-HxCDD 
1.8 
1.7 
22% 
1,2,3,6,7,8-HxCDD 
3.8 
4.2 
9% 
1,2,3,7,8,9-HxCDD 
0.57 
0.42 
31% 
1,2,3,4,6,7,8-HpCDD 
33 
30 
4% 
OCDD 
58 
54 
8% 
2,3,7,8-TCDF 
0.075 
0.11 
65% 
1,2,3,7,8-PeCDF 
0.087 
0.093 
90% 
2,3,4,7,8-PeCDF 
0.36 
0.32 
38% 
1,2,3,4,7,8-HxCDF 
0.29 
0.27 
25% 
1,2,3,6,7,8-HxCDF 
0.46 
0.49 
20% 
1,2,3,7,8,9-HxCDF 
0.091 
0.085 
133% 
2,3,4,6,7,8-HxCDF 
0.20 
0.24 
53% 
1,2,3,4,6,7,8-HpCDF 
1.97 
1.92 
9% 
1,2,3,4,7,8,9-HpCDF 
0.076 
0.11 
69% 
OCDF 
0.39 
0.30 
55% 
TEQ 
2.47 
2.29 
PCB 81 
<0.5 
<0.5 
PCB 77 
<0.5 
<0.5 
PCB 123 
21 
8.8 
22% 
PCB 118 
714 
401 
5% 
PCB 114 
21 
11 
30% 
PCB 105_127 
265 
150 
3% 
PCB 126 
16 
9.2 
30% 
PCB 167 
61 
55 
3% 
PCB 156 
91 
97 
3% 
PCB 157 
24 
22 
11% 
PCB 169 
<0.5 
<0.5 
PCB 189 
14 
21 
12% 
Total TEQ 
4.15 
3.24 
5 g fat processed through ASE and Cape Technologies clean-up and analyzed on Thermo Scientific™ DFS™ High Resolution GC/MS System. 
Control sample processed through our standard 3N HCl digestion
Can economy model TSQ 8000 GC/MS run PCDD/F 
• 
Benchtop instrument 
• 
More affordable 
• 
Increased uptime 
• 
Easier maintenance 
• 
Lower electrical usage
So easy anyone can learn??? 
• 
It helps if you know how to type! 
• 
Monitor M-COCl 
– 
No chlorinated diphenylether interference 
• 
EPA 1613b calibration, with CS- Lo and 0.2 x CS-Lo
TSQ 8000 GC/MS Calibration 20 fg – 200 pg
20 fg/uL to 200 pg/uL TCDD
Data Comparison ASE – Cape Tech – TSQ 8000 MS 
• 
Ten vials of CARP-2 (ground whole carp reference material) from NRC Canada 
• 
Reference concentrations for PCDD/F and select PCBs (several congeners in excess of 100 ug/kg) 
• 
Entire contents of vial (approx 10 g) extracted using ASE 350 
• 
Cape Technologies tandem acid silica gel / carbon clean-up 
• 
Analysis by DFS HRMS System 
• 
Analysis by TSQ 8000 Triple Quadrupole GC-MS
CARP-2 results 
DFS (n=10) 
TSQ 8000 (n=7) 
Reference Values 
Average 
RSD 
Average 
RSD 
ng/kg 
ng/kg 
ng/kg 
2378-TCDD 
6.7-8.1 
7.74 
5% 
8.18 
6% 
12378-PeCDD 
4.0-6.6 
4.65 
13% 
5.09 
14% 
123478-HxCDD 
1.3-1.9 
1.56 
12% 
1.56 
11% 
123678-HxCDD 
5.0-6.6 
5.66 
10% 
5.23 
13% 
123789-HxCDD 
0.66-0.90 
0.71 
32% 
0.60 
13% 
1234678-HpCDD 
5.5-7.3 
6.77 
7% 
5.75 
14% 
OCDD 
7.7-11.1 
8.71 
10% 
8.80 
9% 
2378-TCDF 
16.6-19.8 
18.5 
6% 
18.3 
8% 
12378-PeCDF 
5.3-5.9 
5.97 
14% 
6.13 
8% 
23478-PeCDF 
15.2 
8% 
15.4 
14% 
123478-HxCDF 
4.04 
17% 
3.88 
18% 
123678-HxCDF 
2.56 
19% 
2.48 
15% 
234678-HxCDF 
1.27 
32% 
1.37 
34% 
123789-HxCDF 
0.27 
38% 
0.22 
69% 
1234678-HpCDF 
4.42 
11% 
3.96 
17% 
1234789-HpCDF 
<1 
0.74 
17% 
OCDF 
<1 
1.29 
17%
7.7 
11.1 
0 
2 
4 
6 
8 
10 
12 
ng/kg 
CARP-2 Comparison – TSQ 8000 GC-MS vs DFS HRMS
Conclusions 
• 
Cape Technologies provides a simple, inexpensive clean-up for dioxins and PCBs 
• 
ASE can be made clean and effective for food samples at ppq levels 
• 
TSQ 8000 GC-MS system has the sensitivity and specificity to analyze PCDD/F from food extracts.

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Chromatography: Meeting the Challenges of EU regulations with up-to-date Confirmatory Solutions

  • 1. Meeting the challenges of EU regulations with up-to-date confirmatory solutions Lunch Seminar at the 34th International Symposium on Halogenated Persistent Organic Pollutants (Dioxin 2014)
  • 2. Validation of a triple quadrupole GC-MS/MS technology for detection, quantification and confirmation of low level dioxins in feed and food samples Cristian Cojocariu, PhD ThermoFisher Scientific, Runcorn, UK
  • 3. 3 Overview •Thermo Scientific™ TSQ 8000™ Evo triple quadrupole GC-MS was used to detect and confirm low level of PCDD/Fs in sample extracts, taking into account the EU Commission Regulation 589/2014 and the new Regulation No. 709/2014 •A thorough validation of the TSQ 8000 Evo GC-MS/MS for dioxin confirmation was performed. •Instrument sensitivity, linearity, chromatography, LOD/LOQs and precision of measurements were assessed. •Data acquired using the GC-MS/MS was compared with the GC-HRMS data acquired for the same samples and measurements uncertainties were assessed.
  • 5. 5 TSQ 8000 Evo GC-MS System •State of the art triple quadrupole GC-MS system introduced at ASMS 2014 •Fast collision cell instrument with enhanced velocity optics with EvoCell technology to provide high SRM transition speeds, precision and sensitivity •ExtractaBrite™ ion source is heated throughout ensuring high matrix tolerance •Ion source fully removable, hot, under vacuum when cleaning is necessary or swapping with a spare; no vent to clean your instrument
  • 6. 6 GC & MS Conditions Thermo Scientific™ TRACE™ 1310 GC Parameters Column TG-5 SIL MS, 60 m x 0.25 x 0.25 Injection Volume (mL): 2 Liner SSL single taper 4mm ID 78.5mm Inlet (°C): 260 Inlet Module and Mode: splitless Carrier Gas, (mL/min): He, 1.2 Oven Temperature Program time (min): 33 TSQ 8000 Evo Mass Spectrometer Parameters Transfer line (°C): 280 Ionization type: EI Ion source(°C): 300 Electron energy (eV): 40 Acquisition Mode: SRM Q1 Peak Width (AMU): 0.7 Q3 Peak Width (AMU): 0.7 GC MS
  • 7. 7 Samples •Wellington Lab standards used in the experiments described below: EPA1613 calibration set TF-TCDD-MXD Compound Concentration (fg/μL) 1368-TCDD 10 1379-TCDD 25 1378-TCDD 100 1478-TCDD 250 1234-TCDD 500 2378-TCDD 1000
  • 8. 8 Samples •Matrix samples (previously analysed on a GC-HRMS instrument) provided by EU-RL, Freiburg •Samples chosen were naturally contaminated with low level of PCDD/Fs. •Used to assess and validate the LOQs in matrix samples as well as to check precision of total dioxin content at low level. •Extraction and clean-up was carried out in accordance with the existing methods for food and feed either automatically (PowerPrep™ SPE) or partly manual/partly automated (GPC, multi-layer silica, Florisil®, carbon). Mixed animal fat Fish meal Egg fat 11 Egg fat 2 Weighted sample: 10.0 g fat 60.2 g sample (= 10.0 g fat) 0.52 g fat 0.51 g fat Lipid content [%]: n/a 16.6 n/a n/a Moisture content [%]: n/a 5.3 n/a n/a Final volume: 40 μl 40 μl 10 μl 10 μl 13C Internal standard 13C Internal standard 13C Internal standard 13C Internal standard 2378 TCDF 50 50 10 10 12378 PCDF 50 50 10 10 23478-PCDF 200 200 40 40 123478 HxCDF 100 100 20 20 123678 HxCDF 100 100 20 20 234678 HxCDF 50 50 10 10 123789 HxCDF 50 50 10 10 1234678 HpCDF 100 100 20 20 1234789 HpCDF 50 50 10 10 OCDF 100 100 20 20 2378 TCDD 50 50 10 10 12378 PCDD 100 100 20 20 123478 HxCDD 100 100 20 20 123678 HxCDD 200 200 40 40 123789 HxCDD 50 50 10 10 1234678 HpCDD 200 200 40 40 OCDD 600 600 120 120 13C Recovery standard 13C Recovery standard 13C Recovery standard 13C Recovery standard 1234-TCDD 50 50 10 10
  • 9. 9 Data Acquisition and Data Processing •Data were acquired using timed-Selected Reaction Monitoring (timed-SRM). •A minimum of 12 points/chromatographic peak were acquired. •Data processing was performed with Thermo Scientific™ TargetQuan 3.1 software.
  • 10. 10 Linearity of Response •Linearity assessed by determining the average RF %RSD values from a six point calibration curve measured at the beginning and at the end of the sample batch. •Values represent duplicate measurements of each calibration point, measured at the beginning and end of a batch. Compound Concentration range (pg/μL) Average RF stdev RF %RSD 2378-TCDF 0.1 - 40 1.0 0.04 3.7 2378-TCDD 0.1 - 40 1.4 0.02 1.4 12378-PeCDF 0.5 - 200 1.0 0.01 0.9 23478-PeCDF 0.5 - 200 1.0 0.02 1.8 12378-PeCDD 0.5 - 200 1.2 0.03 2.5 123478-HxCDF 0.5 - 200 1.0 0.01 0.8 123678-HxCDF 0.5 - 200 1.0 0.01 1.3 234678-HxCDF 0.5 - 200 1.0 0.01 1.3 123478-HxCDD 0.5 - 200 0.9 0.01 0.7 123678-HxCDD 0.5 - 200 1.1 0.01 1.3 123789-HxCDD 0.5 - 200 1.0 0.01 0.7 123789-HxCDF 0.5 - 200 1.0 0.05 4.5 1234678-HpCDF 0.5 - 200 1.1 0.01 0.9 1234678-HpCDD 0.5 - 200 1.1 0.01 1.0 1234789-HpCDF 0.5 - 200 1.1 0.02 1.4 OCDD 1.0 - 400 1.5 0.02 1.6 OCDF 1.0 - 400 1.1 0.02 1.4
  • 11. 11 Determination of Limit of Quantification •LOQ calculated from CSL x5 and CSL x10 dilution and taking into account the ion ratio, response factors and precision limits. •LOQ for each native compound was calculated taking into account the student’s-t critical values for the corresponding degrees of freedom (99% confidence). Compound pg/μL 2378-TCDF 0.01 2378-TCDD 0.01 12378-PeCDF 0.02 23478-PeCDF 0.02 12378-PeCDD 0.02 123478-HxCDF 0.04 123678-HxCDF 0.04 234678-HxCDF 0.03 123478-HxCDD 0.06 123678-HxCDD 0.03 123789-HxCDD 0.04 123789-HxCDF 0.04 1234678-HpCDF 0.02 1234678-HpCDD 0.05 1234789-HpCDF 0.02 OCDD 0.05 OCDF 0.03
  • 12. 12 Sensitivity test: stepped standard • Overlayed SRM chromatograms (quan ion) of six TCDD congeners in the stepped standard. • Concentrations represents ‘on column’ amount. RT: 13.37 - 14.94 SM: 3B 13.4 13.5 13.6 13.7 13.8 13.9 14.0 14.1 14.2 14.3 14.4 14.5 14.6 14.7 14.8 14.9 Time (min) 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 14.78 14.57 14.30 14.15 13.65 13.52 14.86 13.53 13.76 14.38 14.41 14.67 14.56 NL: 8.47E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_11 NL: 8.33E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_03 NL: 8.49E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_05 NL: 8.25E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_06 NL: 8.35E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_07 NL: 8.38E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_08 NL: 8.53E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_09 NL: 8.48E4 TIC F: + c EI SRM ms2 321.890@cid20.00 [258.925-258.935] MS 19May2014_10 1368-TCDD 10 fg IR % = 9 1379-TCDD 25 fg IR % = 6 1378-TCDD 100 fg IR % = 7 1478-TCDD 250 fg IR % = 6 2378-TCDD 1000 fg IR % = 4 1234-TCDD 500 fg IR % = 11 Inj. No. Concentration 10 fg 25 fg 100 fg 250 fg 500 fg 1000 fg 1 3129 7011 25940 60219 87635 239216 2 3045 6209 25998 59108 85789 240162 3 3047 7055 27425 58262 87578 237274 4 2637 7440 25734 59335 87079 233655 5 2678 6376 27805 58583 83897 234470 6 2964 6513 27097 58902 85373 238554 7 2828 6931 26347 59936 86844 242740 8 2699 6579 25033 55519 79471 232038 mean 2878.4 6764.3 26422.4 58733.0 85458.3 237263.6 STDEV 192.5 411.7 940.7 1452.1 2730.3 3625.3 % RSD 6.7 6.1 3.6 2.5 3.2 1.5
  • 13. 13 DETERMINATION OF DIOXINS IN SAMPLE EXTRACTS
  • 14. 14 Quantification of Dioxins in the Sample Extracts •The egg, animal fat and fish meal samples were analyzed for their dioxin content. •The calculated concentration of each individual dioxin congener (pg TEQ/g fat or ng/kg %dw) was compared with the values obtained from the GC-HRMS.
  • 15. 15 Chromatography & Selectivity 2378-TCDD in Sample Extracts 95 fg 28 fg 98 fg fish meal mixed animal fat egg
  • 16. 16 Egg Samples - Comparison with GC-HRMS 0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00 WHO pg TEQ/g fat GC-HRMS GC-MS/MS egg 0.52g GC-MS/MS egg 0.51 g
  • 17. 17 Fish Meal - Comparison with GC-HRMS
  • 18. 18 Ion Ratio Stability: IR Egg Sample vs. Theoretical IR
  • 19. 19 Ion Ratio Stability: IR Egg Sample vs. IR CS3
  • 20. 20 Precision of Measurements: Sample Extracts •Obtaining valid estimates of PCDD/Fs concentration in sample extracts is critical. •Precision measurement of the total dioxin content (as WHO TEQ pg/g or ng/kg) for a sequence of n=13 repeat injections of the mixed animal fat and the fish meal samples
  • 21. 21 Fish Meal: Precision of Total Dioxin Content (n=13)
  • 22. 22 Mixed Animal Fat: Precision of Total Dioxin Content (n=13)
  • 23. 23 Comparison with GC-HRMS Total dioxin content of sample extracts •Average values of replicate injections (n) with corresponding standard deviations (in brackets) are given. Sample type WHO-PCDD/F-TEQ-ub GC-HRMS GC-MS/MS Deviation % egg (n=2) 3.39 pg/g 3.27 (0.03) -3.5 fish meal (n=13) 0.26 ng/kg % dw 0.25 (0.01) -2.2 mixed animal fat (n=13) 0.83 pg/g 0.85 (0.04) 2.8
  • 24. 24 Conclusions •Excellent selectivity and sensitivity was achieved (ex: 28 fg 2378-TCDD absolute amount on column) •Precision measurements of the total dioxin content (WHO-PCDD/F-TEQ-ub) were obtained for two low level contaminated samples (fish meal and mixed animal fat) with %RSD values <6% (n=13). •Deviation of the total dioxin content (WHO-PCDD/F-TEQ-ub) from the GC-HRMS data was analyzed within the ±20% for all the samples. •The data shows excellent agreement between the results obtained using the TSQ 8000 Evo GC-MS/MS and those obtained using GC-HRMS. •TSQ 8000 Evo triple quadrupole system is a sensitive and robust system suitable for the quantification and confirmation of low level dioxins and furans in food and feed matrices.
  • 26. 26 Thank You for Your Attention! Stay connected with us Twitter @ChromSolutions Chromatography Solutions Blog http://chromblog.thermoscientific.com/blog YouTube http://www.youtube.com/ChromSolutions Facebook http://www.facebook.com/ChromatographySolutions Pinterest http://pinterest.com/chromsolutions/
  • 27. Economic POPs Dave Hope, Patrick Pond, Wasana Mudalige, Jose del Pozo, Matt Wright Pacific Rim Laboratories Inc. Presented at Thermo Scientific Vendor Seminar Madrid, Spain September 2,2014
  • 28. Outline • Cost of Analysis • Saving time on extraction - Accelerated Solvent Extraction (ASE) • Saving time and money on clean-up - Cape Technologies Clean-up Kits • Is GC-MS/MS technology ready for POPs – Thermo Scientific™ TSQ™ 8000 system
  • 29. Economic Costs – POPs Lab • Laboratory – $1-3M or higher if budget allows • Instrument – $150-400k up to $250-600k depending on options • Staffing (2-10) – $20-50 per hour ($40-100k per annum) • Soft costs – Chemicals 7-10% revenue – Consumables 5-10% revenue – Service contracts/R&M 5-7% revenue or 5-10% instrument cost – Staff Training 6 weeks to 6 months or $5-35k
  • 30. Cost of Analysis • Sample Extraction (batch of 10 samples) – Water: liquid/liquid sep funnel 6-8 h – Soil/tissue: soxhlet 6-8 h – Tissue: acid digestion 12 h – @ $20 per hour with 10 sample batch $16-24 – @ $20 per hour with 6 sample batch $25-40 – @ $20 per hour with 2 sample batch $50-75
  • 31. Sample clean-up • Clean-up steps (4-8 h each) – Acid or base washes – Acid/base silica gel – Basic Alumina – Florisil (separate dioxins and PCBs) – Carbon • Soft costs – Preparing reagents – Cleaning reusable glassware – 2 h per day – Re-analyzing cross contaminated samples
  • 32. Simplified Clean-up for Food and Environmental Sample • Cape Technologies tandem acid silica gel / carbon columns – Originally designed as clean-up kit for EPA Method 4025 (Screening for PCDD/F by Immunoassay) – quick and cheap – 4-6 h to complete 12 samples, <$20/sample disposable columns, $500 hardware – Columns are disposable, therefore reduces PCB carryover from improper washing of reusable columns (not to mention the labor savings) – Separates dioxins from PCBs – Separates dl PCBs from interfering PCBs with high LOC – Yang et al (MOE Ontario) developed method to separate PCB, PBDE and PCDD/F (Dioxin 2010)
  • 33. Cape Technologies Clean-up Kit • Glass column, 15 mm x 27 cm, loaded with 5 g acid (30%) silica gel (63-200 μm) • 25 mm column available with 14 or 28 g acid (50%) silica (32-63 μm) • Each column individually sealed, wrapped in boxes of 12 • Carbon soxhlet extracted with Toluene prior to packing in Teflon column (one end flat and the other end bevelled for easy identification of flow direction) • 150 mg of 2% carbon in FEP Teflon
  • 34. Columning Procedure • Pre-rinse carbon column – 10 mL toluene – 10 mL DCM – 30 mL hexane • Attached carbon column to acid silica gel – bevelled side down • Load sample in 1-2 mL hexane • Elute 30 mL hexane (F1) – pressurize to 10 psi (1-2 mL/min) • Remove carbon and attach to empty glass column • Elute 6 mL 1:1 toluene/hexane (F2) • Reverse carbon column flow • Elute 30 mL toluene (F3)
  • 35. F3 – PCDD/F • All 17 congeners found in F3 • Spike recoveries for TeCDD/F- HpCDD/F were 93-107% with RSD<12% • Recovery of OCDD was 85% and OCDF 49% • There may be some loss of non-2,3,7,8 congeners (especially TeCDD/F) • Cut point between F2/F3 tight for TeCDD/F (F2 max volume 6 mL of 50:50 toluene/hexane)
  • 36. Accelerated Solvent Extraction (ASE) • Has been widely used for soils and tissues in conventional analyses (ppm/ppb) • Cells and lines subject to trace contamination and carry over at ultra-trace levels • Recently given an Thermo Scientific™ Dionex™ ASE™ 350 Accelerated Solvent Extractor to play with complete with 100 mL Thermo Scientific™ Dionium™ cells • Thermo Fisher Scientific has application notes for tissue samples using max 1 g lipid • PRL methodology requires 5-10 g lipid for lowest DLs • Initial problems with packing cells – critical not to – over pack them – SOLVENT LEAKAGE WARNING – under pack them – VAPOUR PRESSURE WARNING • Instrument lines and cells required thorough cleaning after installation
  • 37. ASE 350 System Extraction Conditions Extraction Solvent: Hexane/Acetone 3:1 Temperature: 100 °C Pressure: 1600 psi Heat Time: 5 min Static Time: 5 min Flush Volume: 70% Purge Time: 120 s Static Cycles: 3 Total Prep Time: 15 min per sample Total Extraction Time: 25 min per sample
  • 38. Butter (n=5) Units: ng/kg (pg/g) Control Average Spike Recovery RSD 2378-TCDD <0.03 <0.03 20 91% 15% 12378-PeCDD <0.033 <0.033 100 94% 5% 123478-HxCDD 0.15 0.20 100 82% 14% 123678-HxCDD 0.56 0.60 100 87% 8% 123789-HxCDD 0.18 0.25 100 90% 3% 1234678-HpCDD 1.21 1.69 100 96% 7% OCDD 0.88 1.83 200 95% 2% 2378-TCDF <0.03 <0.03 100 94% 11% 12378-PeCDF <0.039 0.07 100 92% 5% 23478-PeCDF <0.039 <0.039 100 90% 8% 123478-HxCDF 0.16 0.24 100 82% 14% 123678-HxCDF 0.12 0.12 100 86% 9% 123789-HxCDF <0.056 <0.056 100 93% 5% 234678-HxCDF 0.11 0.20 100 80% 16% 1234678-HpCDF <0.052 <0.052 100 88% 12% 1234789-HpCDF <0.085 <0.085 100 87% 9% OCDF <0.13 0.20 200 66% 6% Use 6.25 g of butter (80% lipid) mixed with 10 g diatomaceous earth Add internal standards Pack 100 mL Dionium cell with • 30 mm cellulose filter • 10 g Dionex ASE Prep CR Na+ form (sulphonated divinyl benzene/styrene copolymer) • Add sample mix • Top with diatomaceous earth to 10 mm from top of cell Cape Technologies column clean-up
  • 39. Butter PCB data ng/kg Control Average (n=3) Spike Recovery PCB 28 <2 12.8 73% PCB 52 5.1 19.1 92% PCB 101 <2 <2 116% PCB 153 61.7 58.4 112% PCB 138 39.6 48.7 109% PCB 180 25.6 22.0 99% PCB 81 <1 <1 103% PCB 77 <1 <1 97% PCB 123 <1 <1 88% PCB 118 51.1 41.7 86% PCB 114 <1 <1 103% PCB 105 <1 <1 99% PCB 126 <1 <1 96% PCB 167 <1 <1 103% PCB 156 5.8 4.1 110% PCB 157 <1 <1 105% PCB 169 <1 <1 95% PCB 189 <1 <1 82%
  • 40. Horse Meat Control (n=1) Average (n=5) RSD 2,3,7,8-TCDD 0.27 0.18 21% 1,2,3,7,8-PeCDD 1.0 0.94 22% 1,2,3,4,7,8-HxCDD 1.8 1.7 22% 1,2,3,6,7,8-HxCDD 3.8 4.2 9% 1,2,3,7,8,9-HxCDD 0.57 0.42 31% 1,2,3,4,6,7,8-HpCDD 33 30 4% OCDD 58 54 8% 2,3,7,8-TCDF 0.075 0.11 65% 1,2,3,7,8-PeCDF 0.087 0.093 90% 2,3,4,7,8-PeCDF 0.36 0.32 38% 1,2,3,4,7,8-HxCDF 0.29 0.27 25% 1,2,3,6,7,8-HxCDF 0.46 0.49 20% 1,2,3,7,8,9-HxCDF 0.091 0.085 133% 2,3,4,6,7,8-HxCDF 0.20 0.24 53% 1,2,3,4,6,7,8-HpCDF 1.97 1.92 9% 1,2,3,4,7,8,9-HpCDF 0.076 0.11 69% OCDF 0.39 0.30 55% TEQ 2.47 2.29 PCB 81 <0.5 <0.5 PCB 77 <0.5 <0.5 PCB 123 21 8.8 22% PCB 118 714 401 5% PCB 114 21 11 30% PCB 105_127 265 150 3% PCB 126 16 9.2 30% PCB 167 61 55 3% PCB 156 91 97 3% PCB 157 24 22 11% PCB 169 <0.5 <0.5 PCB 189 14 21 12% Total TEQ 4.15 3.24 5 g fat processed through ASE and Cape Technologies clean-up and analyzed on Thermo Scientific™ DFS™ High Resolution GC/MS System. Control sample processed through our standard 3N HCl digestion
  • 41. Can economy model TSQ 8000 GC/MS run PCDD/F • Benchtop instrument • More affordable • Increased uptime • Easier maintenance • Lower electrical usage
  • 42. So easy anyone can learn??? • It helps if you know how to type! • Monitor M-COCl – No chlorinated diphenylether interference • EPA 1613b calibration, with CS- Lo and 0.2 x CS-Lo
  • 43. TSQ 8000 GC/MS Calibration 20 fg – 200 pg
  • 44. 20 fg/uL to 200 pg/uL TCDD
  • 45. Data Comparison ASE – Cape Tech – TSQ 8000 MS • Ten vials of CARP-2 (ground whole carp reference material) from NRC Canada • Reference concentrations for PCDD/F and select PCBs (several congeners in excess of 100 ug/kg) • Entire contents of vial (approx 10 g) extracted using ASE 350 • Cape Technologies tandem acid silica gel / carbon clean-up • Analysis by DFS HRMS System • Analysis by TSQ 8000 Triple Quadrupole GC-MS
  • 46. CARP-2 results DFS (n=10) TSQ 8000 (n=7) Reference Values Average RSD Average RSD ng/kg ng/kg ng/kg 2378-TCDD 6.7-8.1 7.74 5% 8.18 6% 12378-PeCDD 4.0-6.6 4.65 13% 5.09 14% 123478-HxCDD 1.3-1.9 1.56 12% 1.56 11% 123678-HxCDD 5.0-6.6 5.66 10% 5.23 13% 123789-HxCDD 0.66-0.90 0.71 32% 0.60 13% 1234678-HpCDD 5.5-7.3 6.77 7% 5.75 14% OCDD 7.7-11.1 8.71 10% 8.80 9% 2378-TCDF 16.6-19.8 18.5 6% 18.3 8% 12378-PeCDF 5.3-5.9 5.97 14% 6.13 8% 23478-PeCDF 15.2 8% 15.4 14% 123478-HxCDF 4.04 17% 3.88 18% 123678-HxCDF 2.56 19% 2.48 15% 234678-HxCDF 1.27 32% 1.37 34% 123789-HxCDF 0.27 38% 0.22 69% 1234678-HpCDF 4.42 11% 3.96 17% 1234789-HpCDF <1 0.74 17% OCDF <1 1.29 17%
  • 47. 7.7 11.1 0 2 4 6 8 10 12 ng/kg CARP-2 Comparison – TSQ 8000 GC-MS vs DFS HRMS
  • 48. Conclusions • Cape Technologies provides a simple, inexpensive clean-up for dioxins and PCBs • ASE can be made clean and effective for food samples at ppq levels • TSQ 8000 GC-MS system has the sensitivity and specificity to analyze PCDD/F from food extracts.