Analysis of Dioxins and dl-PCBs with High Resolution and Triple ...

The world leader in serving science
Analysis of Dioxins and dl-PCBs with
High Resolution and Triple Quadrupole
GC/MS
Using the TargetQuan Software Suite
Hans-Joachim Huebschmann
GC/MS Technology Manager, Thermo Fisher Scientific
Frank Theobald
Environmental Consulting, Cologne

Target Compound Analysis with Highest Selectivity
2
Selectivity for Trace Analysis
High Resolution or MS/MS?
The New DFS Analyzer Concept
TSQ Triple Quad Technology
Solutions for Food Safety and
Environmental Analysis
• Pesticides
• Dioxins and dl-PCBs
• Brominated Flame Retardants
TargetQuan

Parathion-Ethyl – Structure Specific Selectivity
100
50
MS/MS
Product Ion
m/z 109
C 2 H 6 OPS +
29
65
81
97
109
125
139
39
15
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
(mainlib) Parathion
45 75
150
218
172
201
246
275
155
3
186
O
O
N
S
P
O
O
O
235
263
291
M + m/z 291
MS/MS
Precursor
Nominal
Mass Axis

Parathion – Accurate Mass Selectivity
C10H14NO5PS: C10 H14 N1 O5 P1 S1 p(gss, s/p:40) Chrg...
Relative Abundance
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
0
291.03248
C 10 H 14 NO 5 PS
M + Accurate Mass
m/z 291.03248
HRMS MID
measurement only on
m/z 291.03248
Resolution Power
R = 10,000
292.03544
291.0 291.2 291.4 291.6 291.8 292.0 292.2 292.4 292.6 292.8 293.0 293.2 293.4
m/z
4
100
50
29
65
81
97
109
39
15
0
10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300
(mainlib) Parathion
45 75
150
218
172
201
246
275
293.03080
125
139
155
186
O
O
N
S
P
O
O
O
235
263
291
Accurate
Mass Axis

Why High Selectivity with “High Resolution” ?
Low Resolution
Yet another
chlorinated
compound
TCDD
High Resolution
Analytical Arguments
• Get ultimate selectivity for “high res MID”
• Get rid of isobaric background
• Get ultimate specificity for “accurate mass”
• Target compound confirmation
• Structure elucidation
Legal Aspects Require …
… target compound confirmation
… positive assay of the target molecule
… results withstanding any legal interrogation
5

HRMS Confirmation in Sports Doping
Mass Selective
m/z:335
m/z:336
3:10 3:15 3:20 3:25 3:30 3:35
Accurate Mass
High Resolution
Low Resolution (Quadrupole) High Selectivity
High Specificity
m/z:335.069
m/z:336.058
Separation of the Metandienone
metabolite 18-nor-EMD from
Stearic Acid at a trace level of

Quinoxyfen in Hops using SIM and MS/MS
RT: 17.13 - 27.39
Relative Abundance
Relative Abundance
Relative Abundance
Relative Abundance
Relative Abundance
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
DSQ II
SIM Mode
19.61
RT: 23.76
NL: 6.37E4
m/z= 236.50-237.50 F: + c SIM
24.01
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
20.27 20.40 21.09 21.30
21.67
22.17
22.52 22.97
23.28
23.55 24.11 24.55 25.35
25.52
25.65
25.87
26.45 26.78
MS probe20f_sim
19.65 20.15
18 19 20 21 22 23 24 25 26 27
Time (min)
22.93
7
23.53
RT: 23.76
20.19 23.43 24.55
20.57 21.25 22.17 22.41 24.02 24.67 25.48 26.26
20.57
TSQ Quantum GC
MS/MS (SRM Mode)
RT: 23.76
23.13 24.17
22.93 25.18 25.34 26.31 27.09
23.37
26.46
21.67
21.89 22.52
21.15
RT: 23.77
RT: 23.77
24.59
25.37
26.62
27.35
NL: 2.67E4
m/z= 271.50-272.50 F: + c SIM
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
MS probe20f_sim
NL: 9.94E3
m/z= 306.50-307.50 F: + c SIM
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
MS probe20f_sim
NL: 6.10E5
m/z= 207.50-208.50 F: + c EI
SRM ms2 237.000
[207.999-208.001] MS
Genesis Probe20F
Superior Selectivity
Free from sample matrix
NL: 1.06E6
m/z= 236.50-237.50 F: + c EI
SRM ms2 272.000
[236.999-237.001] MS
Genesis Probe20F

The world leader in serving science
DFS
High Resolution GC/MS
DFS Product Details
The New Analyzer Concept

New DFS Ion Optics – Clear and Concise
9

DFS Analyzer - New Radially Lamelated Magnet
• Smaller, less weight
• Allows for compact instrument
• All analyzer components stay
on instrument during
shipment
• Field probe for unique calibration
• Fastest scanning speeds
10

DFS Common Instrument Control Software
Makes the DFS as easy to operate as a Benchtop MS
11
• Common User Interface
• known from
• DSQ, PolarisQ or
• LCQ, LTQ series
• Auto Tune
• Auto Resolution

The world leader in serving science
TSQ Quantum GC
Triple Quadrupole GC/MS
TSQ Product Details
The Quantum Analyzer Concept

TSQ Quantum GC: Selected Reaction Monitoring
Purpose: Quantitation
on a single product ion, no spectrum
“Monitor a Transition”
from Precursor to Product Ion
Park Q1 on precursor ion
e.g. Parathion m/z 291
13
Park Q3 on product ion
SRM on m/z 109

Inside the TSQ Quantum GC
Conversion Dynode + Multiplier
Q3
Collision
Cell (Q2)
Q1
14
Turbo
DuraBrite
Ion Source

Why Hyperbolic Quadrupoles ?
TSQ 7000
1993 to 2000
r 0 = 4 mm
L = 250 mm
Hyperbolic Quadrupoles
* Patented HyperQuad Advantage available with TSQ Discovery
15
TSQ Quantum*
2001 to …
r 0 = 4/6 mm
L = 250 mm
• Same basic design as predecessor TSQ 7000.
• True hyperbolic pole face with high-precision
• Improved Ion Transmission and Sensitivity
• Extended field radius - TSQ Quantum GC 4 mm
• Improved Selectivity – Uniquely increased resolution
• Improved Mass Peak Shape - With quads of 250 mm length

TSQ Quantum GC – Standard Resolution at 0.7 FWHM
0.7 u
Only TSQ Quantum GC
1.0 u
16
2.0 u
3.0 u
m/z 300/ 0.7 = R 428
m/z 500/ 0.7 = R 714
m/z 1000/ 0.7 = R 1428
Other manufacturers open up
Q1 resolution to a multiple
of unit resolution to increase
ion transmission
but severely sacrifice selectivity.

Highly Resolved Q1 SRM – Increased Selectivity
0.4 u !
0.7 u
H-SRM Mode
Only TSQ Quantum GC
17
Increased Q1 resolution
Increases SRM selectivity
without loss
in ion transmission
due to hyperbolic
quadrupoles

TSQ Quantum GC - The Innovative Collision Cell
Square Quad Collision Cell
High Speed + High Sensitivity:
Improved SRM Efficiency
• 5 x higher than former octapole cells
• 185 mm long ion path
No Neutral Noise
• 90 Degree
Memory Eliminated
• Active “cleaning”
• No false positives at low LOQ
Entrance lens
assembly,
controls collision
energy
18
Collision cell housing,
Argon, ca. 4 mTorr
Exit lens
assembly
Square quadrupole
collision cell

Quinoxyfen in Hops using SIM and MS/MS
RT: 17.13 - 27.39
Relative Abundance
Relative Abundance
Relative Abundance
Relative Abundance
Relative Abundance
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
DSQII
SIM Mode
19.61
RT: 23.76
NL: 6.37E4
m/z= 236.50-237.50 F: + c SIM
24.01
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
20.27 20.40 21.09 21.30
21.67
22.17
22.52 22.97
23.28
23.55 24.11 24.55 25.35
25.52
25.65
25.87
26.45 26.78
MS probe20f_sim
19.65 20.15
18 19 20 21 22 23 24 25 26 27
Time (min)
22.93
19
23.53
RT: 23.76
20.19 23.43 24.55
20.57 21.25 22.17 22.41 24.02 24.67 25.48 26.26
20.57
TSQ Quantum GC
MS/MS (SRM Mode)
RT: 23.76
23.13 24.17
22.93 25.18 25.34 26.31 27.09
23.37
26.46
21.67
21.89 22.52
21.15
RT: 23.77
RT: 23.77
24.59
25.37
26.62
27.35
NL: 2.67E4
m/z= 271.50-272.50 F: + c SIM
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
MS probe20f_sim
NL: 9.94E3
m/z= 306.50-307.50 F: + c SIM
ms [236.50-237.50,
271.50-272.50, 306.50-307.50]
MS probe20f_sim
NL: 6.10E5
m/z= 207.50-208.50 F: + c EI
SRM ms2 237.000
[207.999-208.001] MS
Genesis Probe20F
Superior Selectivity
Free from sample matrix
NL: 1.06E6
m/z= 236.50-237.50 F: + c EI
SRM ms2 272.000
[236.999-237.001] MS
Genesis Probe20F

QED MS/MS for Structural Confirmation
100
Set level close
50 to MRL
concentration
Relative Abundance
90
80
70
60
40
30
20
10
0
SRM chromatogram
RT:10.0
9.8 10.0 10.2 10.4 10.6
min
20
Intensity
SRM data point
MS/MS spectrum
m/z

Triple Quadrupole: QED - SRM Switched to MSMS
Purpose: Confirmation of a positive result
Park Q1 on precursor ion
e.g. Quinalphos m/z 274
Library Search for Identification
21
SRM: QED: Scan Monitor Q3 in for Q3 the the
target product product ion spectrum ion

RER – Information Rich Product Ion Spectra
RER
Reverse Energy Ramp
17Oct04 #204-214 RT: 1.78-1.85 AV: 5 NL: 1.06E6
F: + c ESI sid=7.00 Full ms2 184.000@cid10.00 [30.000-190.000]
143.0
100
Relative Abundance
80
60
40
20
0
147.9 166.2
40 60 80 100 120 140 160 180
m/z
17Oct04 #203-213 RT: 1.77-1.84 AV: 5 NL: 5.12E4
F: + c ESI sid=7.00 Full ms2 184.000@cid30.00 [30.000-190.000]
95.1
100
Relative Abundance
80
60
40
20
0
Colligion Energy
10 eV
94.2
Colligion Energy
30 eV
125.0
148.0
49.5
98.3
55.6 92.1 110.5 143.0
78.9 165.5
40 60 80 100 120 140 160 180
m/z
184.1
17Oct02 #104-111 RT: 1.75-1.87 AV: 8 NL: 8.07E4
T: + c ESI sid=7.00 Full ms2 184.000@cid15.00 [30.000-190.000]
143.0
100
Relative Abundance
RER spectrum
80
60
40
20
0
22
94.1
95.1
124.9
111.1
148.3
49.5 64.3 79.1
129.3 167.4
40 60 80 100 120 140 160 180
m/z
40
30
20
184.1
10
コリジョンエネルギー(eV)

The world leader in serving science
Multi-Residue Analysis of
Pesticides in Food
using H-SRM
on the TSQ Quantum GC
by Kuniyo Sugitate
Application Specialist
Thermo Fisher Scientific, Yokohama, Japan

GC-MS/MS Method: EI H-SRM
GC TRACE GC ultra
Column : 30 m x 0.25 mm I.D. x 0.25 µm 5% Phenyl Phase
Injection mode : Splitless with Surge (200 kPa,1 min)
Injection Temp : 240 ℃
Oven Temp : 80℃(1 min)→20 ℃/min→180 ℃→5℃/min→280 ℃(10 min)
Flow : constant flow 1.2 mL/min
Transferline Temp : 280 ℃
AS TriPlus
Injection Volume : 1 μL
Injection mode : Hot Needle
Syringe : 80 mm Needle
MS TSQ Quantum GC
Ion Source Temp : 220 ℃
Emission Current : 25 μA
Ionization mode : EI
Ion volume : Closed EI
Analytical mode: SRM (Selected Reaction Monitoring)
Scan width : 0.002 m/z
Scan Time : 0.002 sec, 0.005 sec, 0.01 sec
Peak Width for H-SRM: Q1: 0.4 Da, Q3: 0.7 Da
Collision Gas Pressure : 1.2 mTorr (Ar)
24

Variable Segments with > 300 Transitions/s
Dwell time ≥ 2 ms
>300 Transitions/s
=
>300 Targets/s
25
Segments are
adjusted by using a
standard
chromatogram

Sensitivity at 1/10 MRL - 1 ppb in Green Pepper
green-paprika_spiked_1ppb 2007/03/29 15:57:47 green-paprika_spiked_1ppb
Rti-5MS scan time 0.010 SETTIME=0.001
RT: 15.32 - 18.40 SM: 5G
100
15.82
50
0
100
50
0
100
50
0
100
50
0
100
50
0
100
50
0
15.84
16.25
16.43
16.76
Pyriminobac
-methyl
Bupirimate
Thifluzamide
Fenoxanil
Chlorbenzilate
16.86
-Z
16 17 18
Time (min)
NL: 2.71E4
TIC F: + c CI SRM ms2
316.050@cid10.00
[207.999-208.001] MS
green-paprika_spiked_1ppb
NL: 9.50E4
TIC F: + c CI SRM ms2
448.730@cid10.00
[428.999-429.001] MS
green-paprika_spiked_1ppb
NL: 3.54E4
TIC F: + c CI SRM ms2
293.010@cid20.00
[154.999-155.001] MS
green-paprika_spiked_1ppb
NL: 2.09E5
TIC F: + c CI SRM ms2
250.940@cid15.00
[138.999-139.001] MS
green-paprika_spiked_1ppb
NL: 2.12E5
18.19 TIC F: + c CI SRM ms2
302.020@cid15.00
[255.799-255.801] MS
green-paprika_spiked_1ppb
-E
Oxadixyl
NL: 6.54E4
TIC F: + c CI SRM ms2
163.030@cid10.00
[131.999-132.001] MS
green-paprika_spiked_1ppb
RT: 16.60 - 18.66 SM: 5G
100
17.30
50
0
100
50
0
100
50
0
100
50
0
100
50
0
100
50
0
17.38
Edifenphos
Quinoxyfen
Lenacil
Triazophos
17.72
17.74
17.78
Trifloxystrobin
Fluacrypyrim
18.01
17.0 17.5
Time (min)
18.0 18.5
26
NL: 3.32E4
TIC F: + c CI SRM ms2
256.940@cid10.00
[161.999-162.001] MS
green-paprika_spiked_1ppb
NL: 4.61E4
TIC F: + c CI SRM ms2
188.970@cid10.00
[128.899-128.901] MS
green-paprika_spiked_1ppb
NL: 4.48E4
TIC F: + c CI SRM ms2
309.910@cid10.00
[172.999-173.001] MS
green-paprika_spiked_1ppb
NL: 1.59E5
TIC F: + c CI SRM ms2
271.950@cid10.00
[236.999-237.001] MS
green-paprika_spiked_1ppb
NL: 7.33E4
TIC F: + c CI SRM ms2
152.960@cid15.00
[135.999-136.001] MS
green-paprika_spiked_1ppb
NL: 2.06E4
TIC F: + c CI SRM ms2
222.030@cid10.00
[161.899-161.901] MS
green-paprika_spiked_1ppb
RT: 17.64 - 20.09 SM: 5G
100
18.19
50
0
100
50
0
100
50
0
100
50
0
100
50
0
100
50
0
18.39
Pyriminobac
-methyl-E
18.51
Mefenpyr
-diethyl
Pyributicarb
Tebuconazole
19.15
19.24
Pyridafenthion
Diclofop-methyl
19.46
18 19
Time (min)
20
NL: 1.93E5
TIC F: + c CI SRM ms2
302.020@cid15.00
[255.799-255.801] MS
green-paprika_spiked_1ppb
NL: 5.74E4
TIC F: + c CI SRM ms2
250.030@cid20.00
[124.999-125.001] MS
green-paprika_spiked_1ppb
NL: 7.13E4
TIC F: + c CI SRM ms2
252.930@cid15.00
[161.999-162.001] MS
green-paprika_spiked_1ppb
NL: 1.06E5
TIC F: + c CI SRM ms2
252.950@cid20.00
[188.999-189.001] MS
green-paprika_spiked_1ppb
NL: 2.04E5
TIC F: + c CI SRM ms2
164.970@cid10.00
[107.999-108.001] MS
green-paprika_spiked_1ppb
NL: 5.00E4
TIC F: + c CI SRM ms2
339.940@cid10.00
[198.999-199.001] MS
green-paprika_spiked_1ppb

Specificity: Enhanced Resolution (H-SRM)
RT:8.00 - 12.00
100
Relative Abundance
95
90
85
80
75
70
65
60
55
50
45
40 8.02
35
30
25
20
15
10
5
0.7Da
RT: 9.90
9.95
10.60
9.97
10.32
10.74
8.688.75 10.02
11.35
10.43 11.83
8.39 9.78 10.99 11.46
8.33 8.53 9.51 10.16
11.11 11.64
9.15
8.20 9.13 9.17 9.68
11.27
0
8.0 8.5 9.0 9.5 10.0
Time (min)
10.5 11.0 11.5 12.0
RT:11.00 - 14.00
100
Relative Abundance
95
90
85
80
75
70
65
60
55
50
45
40
35
30
11.35
11.42
0.7Da
11.97
RT: 12.60
12.53
12.83
12.90
25
20
15
12.50
13.01
13.54 13.96
10
5
11.15
0
11.0 11.2
12.68
11.53 11.95
12.30
11.8311.93 12.19 12.38
11.4 11.6 11.8 12.0 12.2 12.4 12.6 12.8
Time (min)
13.2413.34 13.04
13.62 13.84
13.16
13.42
13.0 13.2 13.4 13.6 13.8 14.0
1 ppb samples
Pyroquilon
in Carrot
Parathion in
Green Pepper
O
N
O P
O
O
S
N O
27
O
RT:8.00 - 12.00
100
Relative Abundance
95
90
85
80
75
70
65
60
55
50
45
40
35
RT: 9.90
H-SRM 0.4Da
30
25
10.5810.61
11.69
20
10.44
10.86
15 8.25 8.51 9.279.32 10
9.43
8.03 8.54
8.999.17
5 8.43 8.79 9.66
8.94
10.00 10.40
10.68
11.44
11.1211.3811.46 11.75
11.80
0
8.0 8.5 9.0 9.5 10.0
Time (min)
10.5 11.0 11.5 12.0
RT:11.00 - 14.00
100
RT: 12.60
Relative Abundance
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
H-SRM 0.4Da
5
0
11.1811.35 11.6611.7911.9912.0612.1912.30
12.67 12.9813.1213.28
13.5213.6513.75
11.0 11.2 11.4 11.6 11.8 12.0 12.2 12.4 12.6 12.8
Time (min)
13.0 13.2 13.4 13.6 13.8 14.0

Area
TSQ Quantum GC - Tetradifon
5000000
4800000
4600000
4400000
4200000
4000000
3800000
3600000
3400000
3200000
3000000
2800000
2600000
2400000
2200000
2000000
1800000
1600000
1400000
1200000
1000000
800000
600000
400000
4.1 % RSD at 5 PPB
Tetradifon
Y = 761.05+45923.1*X R^2 = 0.9992 W: Equal
200000
0
19.0 19.5 20.0 20.5 21.0 21.5
0
Time (min)
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110
28
RT: 18.9758 - 21.5239 SM: 3B
Relative Abundance
100
95
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
10
5
RT: 20.5244 NL: 2.00E4
TIC F: + c CI SRM
ms2
355.750@cid10.00
1 ppb
[228.999-229.001]
MS ICIS std_04

The world leader in serving science
DFS
High Resolution GC/MS
Analytical Performance
for Dioxin and dl-PCB Analysis

DFS Sensitivity for 100 fg Dioxin S/N > 1000:1 !
30

DFS Sensitivity - 2 fg native tcdd (TargetQuan Software)
31

DFS - TCDD in Biological Matrix Samples
Ion ratio confirmation
mass trace
Quan ion mass trace
15 fg/µL 2378-TCDD (2 µL inj. ) from complex matrix sample (blood)
32

Robust Performance with Real Samples (Blood)
Isotope ratio confirmation, ratio % for m/z 320/322
At lowest LOQs, here at the 15 fg/µL level
Robust performance over > 38 samples + 9 std runs
Demonstrates compliance with EU and EPA 1613 regulations
33

The world leader in serving science
Dioxins/Furans and dl-PCBs
by EI SRM
on TSQ Quantum GC
Dirk Krumwiede
Thermo Fisher, Bremen, Germany

TSQ Quantum GC PCDD/Fs EPA1613 CS1, 1/10 diluted
C:\XCalibur\Data\dk_test\dio122 9/20/2007 4:31:46 PM 2 ul DF CS1 (1/10), 5 win, SRM
SRM (pw 0.7), coll en 22, gas pressure 2.0, 40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), 120(2)-10-220(2)-3-260, scan width 0.002, ists 250, xline 290
RT: 12.56 - 27.47
13.65
100
Relative Abundance
50
0
100
50
0
100
50
0
100
50
0
100
50
0
100
50
0
100
50
0
13.87
13.76 14.72
13.99
14.15 14.66
15.77
16.46
13.66 13.99
15.66
15.61
16.61
16.70
15.76 16.46
16.83
18.74 18.85
19.43 20.14
17.57 18.49
17.63
20.27
19.73 19.95
19.63
19.20
20.57
18.73 19.72 26.44
20.13 21.75 23.05
14.10 17.09 20.30 21.98 23.65 26.23
14 16 18 20 22 24 26
Time (min)
35
NL: 1.28E4
TIC F: + c EI SRM ms2
305.900
[242.899-242.901] MS
dio122
NL: 1.33E4
TIC F: + c EI SRM ms2
321.900
[258.899-258.901] MS
dio122
NL: 5.30E4
TIC F: + c EI SRM ms2
339.900
[276.800-277.000] MS
dio122
NL: 4.53E4
TIC F: + c EI SRM ms2
355.900
[292.800-293.000] MS
dio122
NL: 3.75E4
TIC F: + c EI SRM ms2
373.800
[310.700-310.900] MS
dio122
NL: 3.74E4
TIC F: + c EI SRM ms2
389.800
[326.700-326.900] MS
dio122
NL: 1.77E6
TIC MS dio122
tcdf
tcdd
pcdf
pcdd
hcdf
hcdf
TIC
(concentrations of natives: tcdd/tcdf: 50 fg/µL; penta to hepta dioxins/furans: 250 fg/µL; octas: 500 fg/µL)

TSQ Quantum GC: Screenshot from a Fish Extract
C:\XCalibur\...\dio220 9/21/2007 4:22:52 PM 1 ul dioxins fish extract 1
SRM (pw 0.7), coll en 22, gas pressure 2.0, 40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), 120(2)-10-220(2)-3-260 sample 4278: Blue Swimmer Crab
RT: 12.78 - 14.48
Relative Abundance
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
100
80
60
40
20
0
RT: 12.96
AA: 77093
RT: 13.46
AA: 118203
RT: 13.99
AA: 147134
12.8 13.0 13.2 13.4 13.6 13.8 14.0 14.2 14.4
Time (min)
36
RT: 14.09
AA: 75177
RT: 13.04
AA: 42016
RT: 13.09
AA: 1119
RT: 13.38
AA: 1325
RT: 13.53
AA: 24861 RT: 13.71
AA: 4143
RT: 14.22
AA: 21444
RT: 12.96
RT: 13.46
AA: 107459
RT: 13.99
AA: 129040
AA: 81402 RT: 14.09
RT: 13.04
AA: 75512
AA: 40518
RT: 13.38
AA: 1490
RT: 13.50
AA: 27461 RT: 13.72
AA: 4918
RT: 13.82
AA: 10033891
RT: 14.22
AA: 18253
RT: 13.36
AA: 1116
RT: 13.83
AA: 9604228
RT: 13.94
AA: 20934
RT: 13.98
AA: 11505
RT: 14.09
AA: 5193487
RT: 14.09
AA: 4897430
RT: 14.22
AA: 43397
RT: 14.23
AA: 36225
NL: 4.95E4
TIC F: + c EI SRM
ms2 319.900
[256.899-256.901]
MS ICIS dio220
NL: 4.64E4
TIC F: + c EI SRM
ms2 321.900
[258.899-258.901]
MS ICIS dio220
NL: 3.83E6
TIC F: + c EI SRM
ms2 331.900
[267.899-267.901]
MS ICIS dio220
NL: 3.65E6
TIC F: + c EI SRM
ms2 333.900
[269.899-269.901]
MS ICIS dio220
Native tcdd
Quan mass
Native tcdd
Ratio mass
13 C12 TCDD
Quan mass
13 C12 TCDD
Ratio mass

Penta-PCBs EPA 1668 Standard – CS1 1 pg/µL
C:\XCalibur\...\pcb408 9/27/2007 11:26:37 AM 1 ul PCB (68A-CS1, 1 pg/ul) SRM, 6 win, en 22
40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), ists 250, xline 290, asamp an com 1, same cable
RT: 18.13 - 21.24 SM: 3G
Relative Abundance
100
80
60
40
20
100
80
60
40
20
100
80
60
40
20
100
80
60
40
20
RT: 19.80
RT: 19.65 RT: 20.15
RT: 19.65
RT: 19.80
RT: 20.15
RT: 18.39 RT: 19.64 RT: 20.14
RT: 20.01
RT: 18.70 RT: 18.91
RT: 18.39 RT: 19.64 RT: 20.14
RT: 20.25
18.5 19.0 19.5 20.0 20.5 21.0
Time (min)
37
RT: 20.25
RT: 20.24
RT: 20.54
RT: 18.61 RT: 18.89 RT: 19.09
RT: 20.24
RT: 20.54
RT: 20.73
RT: 20.73
RT: 20.73
RT: 20.73
RT: 20.88
RT: 20.88
NL: 2.87E5
TIC F: + c EI SRM
ms2 323.900
[253.949-253.951]
MS ICIS pcb408
NL: 2.82E5
TIC F: + c EI SRM
ms2 325.900
[255.949-255.951]
MS ICIS pcb408
NL: 2.75E7
TIC F: + c EI SRM
ms2 335.920
[265.989-265.991]
MS ICIS pcb408
NL: 2.65E7
TIC F: + c EI SRM
ms2 337.920
[267.989-267.991]
MS ICIS pcb408
penta PCB
Quan mass
penta PCB
Ratio mass
penta 13 C 12 -PCB
Quan mass
penta 13 C 12 -PCB
Ratio mass

Mono-ortho PCB from Egg Extract, conc. ≥ 100 fg
C:\XCalibur\...\pcb417 9/27/2007 4:34:44 PM 1 ul Egg, mono-ortho PCBs (Nr. 6), nonane (2d syrg)
rediluted to 500 ul nonae in vial 6, 40eV, 100 uA, closed EI vol., 30 m DB5MS (0.1), ists 250, xline 290, asamp an com 1, same cable
RT: 14.30 - 22.69 SM: 3G
Relative Abundance
100
80
60
40
20
100
80
60
40
20
100
80
60
40
20
100
80
60
40
20
RT: 14.47
RT: 17.09
RT: 18.72
RT: 18.72
RT: 19.61
RT: 19.81
RT: 19.81
15 16 17 18 19 20 21 22
Time (min)
38
RT: 20.75
RT: 20.74
RT: 17.10 RT: 22.43
RT: 19.80
RT: 20.14
RT: 20.72
RT: 19.64
RT: 17.46 RT: 18.18
RT: 20.97 RT: 21.80
RT: 19.80 RT: 20.73
RT: 20.14
RT: 19.63
RT: 16.59 RT: 17.44 RT: 18.17
RT: 21.23 RT: 22.09
NL: 1.02E5
TIC F: + c EI SRM
ms2 323.900
[253.949-253.951]
MS ICIS pcb417
NL: 9.92E4
TIC F: + c EI SRM
ms2 325.900
[255.949-255.951]
MS ICIS pcb417
NL: 1.78E6
TIC F: + c EI SRM
ms2 335.920
[265.989-265.991]
MS ICIS pcb417
NL: 1.64E6
TIC F: + c EI SRM
ms2 337.920
[267.989-267.991]
MS ICIS pcb417
penta PCB
Quan mass
penta PCB
Ratio mass
penta 13 C 12 -PCB
Quan mass
penta 13 C 12 -PCB
Ratio mass

The world leader in serving science
DFS
High Resolution GC/MS
DFS Product Details
Productivity and Economics

DFS – The Unique Concept for Dual GC Configuration
40
2 TRACE GC Ultra GCs
1 TriPlus Autosampler
1 High Resolution MS
Inject from one vial tray into two
different GCs or columns
Analyses on columns with different
polarity within one sequence
Simultaneous dual GC operation
For confirmatory analysis according
to EPA 1613
Analytical flexibility with different
columns installed
Dioxins, PCBs, BFRs, POPs …

Why 2 TRACE GC Ultra GCs ? Some Examples
Using columns of different polarities
• e.g. for dioxins:
• TR-5MS with 360 dgs C max.
• a polar column of e.g. 2330 type with 275 dgs C max
Different length - Brominated flame retartands (BFRs)
• Standard 30 m column
• DecaPDE needs a very short column (5-6 m), cut in 1 datafile
Increased sample throughput
• While cooling off the 1 st GC the 2 nd GC is ready for injection
• Simultaneous runs with staggered injections
Upgradeable to max of 4 columns at any time to fit individual
needs.
41

Dual GC – Sequential Operation
AS inject
START GC-1
START DFS
GC runtime 20 min
Time savings
AS inject
Heat off/Cooldown/Equilibration 5
min
START GC-2
START DFS
• Heat off + cooldown +
equilibration
• > 20% for a 20 min run
GC runtime 20 min
42
AS inject
Heat off/Cooldown/Equilibration 5
min
START GC
START DFS
GC runtime 20 min
Heat off/Cooldown
Equilibration 5 min
further analyses

Dual GC – Simultaneous Dual Data Acquisition
AS inject
START GC-1
START DFS
GC runtime 60 min
Time savings
AS inject
START GC-2
START DFS
GC runtime 60 min
• Only peak window acquired
• 100% Duty cycle of DFS
Double sample throughput
Heat off/Cooldown/Equilibration 5 min
AS inject
43
START GC-1
START DFS
GC runtime 60 min
Heat off/Cooldown/Equilibration 5 min
further analyses

Integrity of Chromatography - WHO PCBs - Marker PCBs
Courtesy Wessling Labs, Germany
44

Integrity of Chromatography – PCDD and PCDF Analysis
Courtesy Wessling Labs, Germany
45

Power Consumption – Save 100 000 € !
DFS
MS 1.9 kW
GC 1.0 kW
Data system 0.3 kW
Water chiller 1.5 kW
----------
Sum 4.7 kW
Power consumption per year
41 MWh
(= ca. 3,300 EUR * )
46
Competitor (diffusion pumps)
MS 14.0 kW
GC 1.0 kW
Data system 0.3 kW
Water chiller 11.0 kW
----------
Sum 26.3 kW
Power consumption per year
230 MWh
(= ca. 18,400 EUR * )
* calculations based on 0.08 EUR/kWh

The world leader in serving science
TargetQuan
Software Suite for Isotope Dilution
Quantitation
Specially designed for
EPA 1613, EPA 1668

TargetQuan – Spreadsheet
48

TargetQuan – Retention Time Picker
49

TargetQuan – Quan and Ratio Masses
50

TargetQuan – Qualifiers and Limits
51

TargetQuan – Structure of the Quantitation Method
52

TargetQuan – Screen Views Organize Appearance
53

TargetQuan – Screen View – Integration
54

TargetQuan – Options for Integration
55

TargetQuan – Screen View During Integration
56

TargetQuan – Screen View with Integration Done
57

TargetQuan – Multiple Targets with ISTD
58

TargetQuan – Peak Display Options
59

TargetQuan – Results in Spreadsheet View
60

TargetQuan – Results Calculated Area and Height
61

TargetQuan – Result QA/QC Status Report
62

TargetQuan – Results with Failed Component
63

TargetQuan – Manual Check and Integration
64

TargetQuan – Result After Manual Integration
65

TargetQuan – Compound with Response Curve
66

TargetQuan – Report as pdf File
67

TargetQuan – Report as Spreadsheet
68

TargetQuan – Report with Graphics
69

TargetQuan – Report Export to Excel
70

TSQ Quantum GC – Proof Statements
Unique Target Compound Selectivity
• Hyperbolic quads and H-SRM
Superior Results with Complex Matrix Samples
• Shorten sample clean-up
• Reliable quantitation – peak integration
Superior Sensitivity
• Trace levels at your syringe tip
Unique High Speed Data Acquisition
• Especially multi-component trace analysis
• For Fast GC applications
High Productivity
• Increased throughput – get results faster
• Most cost efficient analysis
Confirmation of Positive Compounds
• In only one run
Ease-of-Use
• TargetQuan and QuanLab Workflow SW
71

DFS GC/HRMS – Target Compound Confirmation
Analytical Flexibility
• Up to 4 columns stay permanently installed
• Columns of different film type
• Columns of different length
• Injectors SSL, PTV, OC, Large Volume inj.
• Manual or by common autosampler injection
Highest Productivity
• Sequential Analyses
• Simultaneous Dual GC Analyses
Unparalleled Economics
• Immediate results
• 24/7 system availability
• Cost per analysis cut down
72

Thank you
for your attention
73