using triple quadrupole gc-ms in full scan, sim, srm, and ... … · srm, and srm/full scan modes....
TRANSCRIPT
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger,1 Dwain Cardona,1 Cristian Cojocariu,2 Paul Silcock,2 Alexander Semyonov,1 Jason Cole1 1Thermo Fisher Scientific, Austin, TX; 2Thermo Fisher Scientific, Runcorn, UK
2 Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger1, Dwain Cardona1, Cristian Cojocariu2, Paul Silcock2, Alexander Semyonov1, Jason Cole1 1Thermo Fisher Scientific, Austin, TX, 2Thermo Fisher Scientific, Runcorn, UK
Overview This work describes how triple quadrupole gas chromatography-mass spectrometry (GC-MS) systems can be used in single quadrupole modes to satisfy current regulations as well as be able to easily switch to powerful SRM methods when needed, especially in preparation for future updates to regulations. Also included are some potential applications of mixed MS modes, such as simultaneous FS/SRM.
Introduction Many laboratories are adopting triple quadrupole GC-MS systems to access the widely accepted advantages brought by high-selectivity detection of target analytes. However, while the advantages of MS/MS scan modes, particularly SRM, are well documented, some regulated methods such as EPA 8270 do not permit use of triple quadrupole GC-MS systems. Laboratories that are accredited for these “prescriptive” regulated methods are then compelled to continue with current technology such as single quadrupole GC-MS instruments. These regulated methods prevent users becoming familiar with the latest technology so they are not able to use triple quadrupole technology unregulated sample analysis or special projects.
The versatility of the Thermo Scientific™ GC-MS/MS systems will be demonstrated in the various operational modes offered. Methods were developed for semi-volatile organic compounds (SVOCs) and pesticides, and data is presented in full scan, SIM, SRM, and SRM/full scan modes. Figure 1 provides an overview of triple quadrupole method development.
The Thermo Scientific™ TSQ™ Duo GC-MS/MS coupled to a Thermo Scientific™ TRACE™ 1310 GC, enables truly simple operation whether you choose to use it in single or triple quadrupole mode. It also bridges the gap between single and triple quadrupole mode use within the same instrument to allow easy adoption of powerful MS/MS workflows when required. Using the instrument in single quadrupole GC-MS mode allows you to continue running your current instrument configuration and established methods. The integrated software walks you through a step-by-step process to manage the transition to powerful, triple quadrupole methods.
FIGURE 1. Overview of triple quadrupole method development.
Full Scan Data SVOC calibration curves were generated from 1 to 200 ppm in methylene chloride and analyzed on the TSQ Duo GC-MS/MS and ISQ GC-MS instruments. A comparison of the %RSDs of the curves is shown in Figure 2. A comparison of 10 replicate injections at 1 ppm is displayed in Figure 3.
SIM Data SIM was used for the analysis of THC in urine samples. THC, THC-OH, and THC-COOH were extracted and derivatized for this study. Concentrations used were the cutoff value (15 ng/mL), 125% of the cutoff value (18.75 ng/mL), and 40% of the cutoff value (6 ng/mL). Table 1 shows the %RSDs of 10 replicate analyses of these three concentrations.
FIGURE 2. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of the curve for 100+ compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
FIGURE 3. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of 10 replicates at 1 ppm.
0
2
4
6
8
10
12
14
16
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
SRM Data SVOC calibration standards were prepared in methylene chloride from 1 to 1000 ppb. Transitions and collision energies for SRM were determined and optimized using the AutoSRM function of the software. Curves using internal standards were generated. Figure 4 displays the linearity of the curves. Figure 5 is a comparison of the curve %RSDs for the TSQ Duo GC-MS/MS and the ISQ GC-MS.
FIGURE 4. r2 values for a curve 1 ppb to 1000 ppb.
TSQDuo ISQ Classic TSQDuo ISQ Classic TSQDuo ISQ ClassicCutoff Cutoff 125% Cutoff 125% Cutoff 40% Cutoff 40% Cutoff
15 ng/mL 15 ng/mL 18.75 ng/mL 18.75 ng/mL 6 ng/mL 6 ng/mLTHC 2.8 5.8 4.6 3.9 9.4 2.4THC-OH 2.3 2.8 4.4 4.0 8.2 1.9THC-COOH 2.0 3.2 2.8 3.5 9.5 1.9
TABLE 1. %RSD of 10 replicates THC samples – TSQ Duo vs ISQ.
0.9400
0.9500
0.9600
0.9700
0.9800
0.9900
1.0000
1.0100
N-N
itros
odim
ethy
lam
ine
2-Fl
uoro
phen
ol (S
urr)
Phe
nol
Bis
(2-c
hlor
oeth
yl)e
ther
1,
3-D
ichl
orob
enze
ne
Ben
zyl a
lcoh
ol
2-M
ethy
lphe
nol (
o-cr
esol
) 4-
Met
hylp
heno
l (p-
cres
ol)
Hex
achl
oroe
than
e N
itrob
enze
ne
2-N
itrop
heno
l B
is(2
-chl
oroe
thox
y)m
etha
ne
1,2,
4-Tr
ichl
orob
enze
ne
4-C
hlor
oani
line
4-C
hlor
o-3-
met
hylp
heno
l 1-
Met
hyln
apht
hale
ne
2,4,
6-Tr
ichl
orop
heno
l 2-
Fluo
robi
phen
yl (S
urr)
2-N
itroa
nilin
e D
imet
hylp
htha
late
2,
6-D
initr
otol
uene
A
cena
phth
ene
Ace
naph
thyl
ene
4-N
itrop
heno
l (S
PC
C)
Dib
enzo
fura
n 2,
3,5,
6-Te
trach
loro
phen
ol
4-C
hlor
ophe
nyl p
heny
l eth
er
4-N
itroa
nilin
e D
iphe
nyla
min
e 2,
4,6-
Trib
rom
ophe
nol (
Sur
r) H
exac
hlor
oben
zene
P
hena
nthr
ene
Car
bazo
le
Fluo
rant
hene
B
enzy
l but
yl p
htha
late
B
enz(
a)an
thra
cene
C
hrys
ene
Ben
zo(b
)fluo
rant
hene
B
enzo
(a)p
yren
e D
iben
z(a,
h)an
thra
cene
r2 V
alue
FIGURE 6. Comparison of MDLs from SRM vs. SRM/FS analysis (ppb).
SRM/FS Data A sample of fruit drink was extracted using the QuEChERS method of extraction and cleanup. The extract was concentrated 5x, and then 147 pesticides were spiked into the extract to produce calibration curves from 1 ppb to 200 ppb. The calibration curves were constructed for both methods: SRM and alternating SRM/full scan for 147 pesticides. The linearity for most of the compounds was R2 > 0.98 for both methods of analysis. Ten replicates of a 1 ppb and 10 ppb standard in fruit juice extract were analyzed to determine the MDLs for the two instrument methods. A comparison of the MDLs of both methods are shown in Figure 6. MDLs are slightly higher with the full scan added to the instrument method, but very comparable.
Fruit drink was spiked at 100 ppb and analyzed using the SRM/full scan instrument mode. This extract was also spiked with two phthalates at a 1 ppm level. The full scan chromatogram shows several peaks above the 100 ppb pesticide spike. Peaks are at retention times of 9.29, 9.73, 10.39, 10.91, and a very large saturated peak at 31.00 minutes. A close-up view of the first four compounds is shown in Figure 7. Figure 8 displays the NIST library matches for those non-targeted compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 5. %RSDs for the calibration curve – TSQ Duo and ISQ.
Conclusion As can be seen from this data, the TSQ Duo GC/MS-MS system can be used as a single quadrupole instrument that provides additional triple quadrupole capabilities to any laboratory. Whether the application is full scan, SIM, SRM, or a combination of SRM and full scan, the TSQ Duo system produces sensitive, accurate results.
All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
FIGURE 7. Close-up view of four unknown peaks in 100 ppb spiked fruit drink.
Dimethyl phthalate at 9.29 min Phenol, 2,4-bis (1,1-dimethylethyl) at 9.72 min used as a UV stabilizer in plastics
Diethyl phthalate at10.39 min Triethyl citrate at 0.91 min used as a plasticizer and food additive
FIGURE 8. NIST Library match for four unknown peaks.
PO10436
3Thermo Scienti� c Poster Note • PITTCON • PN10436-EN 0215S
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger1, Dwain Cardona1, Cristian Cojocariu2, Paul Silcock2, Alexander Semyonov1, Jason Cole1 1Thermo Fisher Scientific, Austin, TX, 2Thermo Fisher Scientific, Runcorn, UK
Overview This work describes how triple quadrupole gas chromatography-mass spectrometry (GC-MS) systems can be used in single quadrupole modes to satisfy current regulations as well as be able to easily switch to powerful SRM methods when needed, especially in preparation for future updates to regulations. Also included are some potential applications of mixed MS modes, such as simultaneous FS/SRM.
Introduction Many laboratories are adopting triple quadrupole GC-MS systems to access the widely accepted advantages brought by high-selectivity detection of target analytes. However, while the advantages of MS/MS scan modes, particularly SRM, are well documented, some regulated methods such as EPA 8270 do not permit use of triple quadrupole GC-MS systems. Laboratories that are accredited for these “prescriptive” regulated methods are then compelled to continue with current technology such as single quadrupole GC-MS instruments. These regulated methods prevent users becoming familiar with the latest technology so they are not able to use triple quadrupole technology unregulated sample analysis or special projects.
The versatility of the Thermo Scientific™ GC-MS/MS systems will be demonstrated in the various operational modes offered. Methods were developed for semi-volatile organic compounds (SVOCs) and pesticides, and data is presented in full scan, SIM, SRM, and SRM/full scan modes. Figure 1 provides an overview of triple quadrupole method development.
The Thermo Scientific™ TSQ™ Duo GC-MS/MS coupled to a Thermo Scientific™ TRACE™ 1310 GC, enables truly simple operation whether you choose to use it in single or triple quadrupole mode. It also bridges the gap between single and triple quadrupole mode use within the same instrument to allow easy adoption of powerful MS/MS workflows when required. Using the instrument in single quadrupole GC-MS mode allows you to continue running your current instrument configuration and established methods. The integrated software walks you through a step-by-step process to manage the transition to powerful, triple quadrupole methods.
FIGURE 1. Overview of triple quadrupole method development.
Full Scan Data SVOC calibration curves were generated from 1 to 200 ppm in methylene chloride and analyzed on the TSQ Duo GC-MS/MS and ISQ GC-MS instruments. A comparison of the %RSDs of the curves is shown in Figure 2. A comparison of 10 replicate injections at 1 ppm is displayed in Figure 3.
SIM Data SIM was used for the analysis of THC in urine samples. THC, THC-OH, and THC-COOH were extracted and derivatized for this study. Concentrations used were the cutoff value (15 ng/mL), 125% of the cutoff value (18.75 ng/mL), and 40% of the cutoff value (6 ng/mL). Table 1 shows the %RSDs of 10 replicate analyses of these three concentrations.
FIGURE 2. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of the curve for 100+ compounds.
0
5
10
15
20
25 N
-Nitr
osod
imet
hyla
min
e E
than
amin
e, N
-met
hyl-N
-nitr
oso-
M
etha
nesu
lfoni
c ac
id, e
thyl
est
er
Ani
line
Phe
nol,
2-ch
loro
- B
enze
ne, 1
,4-d
ichl
oro-
P
heno
l, 2-
met
hyl-
(O C
reso
l) o-
Tolu
idin
e N
itrob
enze
ne-D
5(su
rrog
ate)
is
opho
rone
M
etha
ne, b
is(2
-chl
oroe
thox
y)-
Nap
htha
lene
-D8
1-P
rope
ne, 1
,1,2
,3,3
,3-h
exac
hlor
o-
Phe
nol,
4-ch
loro
-3-m
ethy
l- B
enze
ne, 1
,2,3
,5-te
trach
loro
- 2-
fluor
obip
heny
l,(su
rrog
ate)
2-
Nitr
oani
line
Ben
zene
, 2-m
ethy
l-1,3
-din
itro-
A
cena
phth
ene-
d10
Phe
nol,
4-ni
tro-
Dib
enzo
fura
n 2-
Nap
htha
lena
min
e P
heno
l, 2-
met
hyl,
4,6-
dini
tro-
2,4,
6-tri
brom
ophe
nol (
surr
ogat
e)
Phe
nace
tin
Ben
zene
, pen
tach
loro
nitro
- P
hena
nthr
ene
Dib
utyl
pht
hala
te
Ben
zidi
ne
Ben
zena
min
e, N
,N-d
imet
hyl-4
-(phe
nyla
zo)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 3. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of 10 replicates at 1 ppm.
0
2
4
6
8
10
12
14
16
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
SRM Data SVOC calibration standards were prepared in methylene chloride from 1 to 1000 ppb. Transitions and collision energies for SRM were determined and optimized using the AutoSRM function of the software. Curves using internal standards were generated. Figure 4 displays the linearity of the curves. Figure 5 is a comparison of the curve %RSDs for the TSQ Duo GC-MS/MS and the ISQ GC-MS.
FIGURE 4. r2 values for a curve 1 ppb to 1000 ppb.
TSQDuo ISQ Classic TSQDuo ISQ Classic TSQDuo ISQ ClassicCutoff Cutoff 125% Cutoff 125% Cutoff 40% Cutoff 40% Cutoff
15 ng/mL 15 ng/mL 18.75 ng/mL 18.75 ng/mL 6 ng/mL 6 ng/mLTHC 2.8 5.8 4.6 3.9 9.4 2.4THC-OH 2.3 2.8 4.4 4.0 8.2 1.9THC-COOH 2.0 3.2 2.8 3.5 9.5 1.9
TABLE 1. %RSD of 10 replicates THC samples – TSQ Duo vs ISQ.
0.9400
0.9500
0.9600
0.9700
0.9800
0.9900
1.0000
1.0100
N-N
itros
odim
ethy
lam
ine
2-Fl
uoro
phen
ol (S
urr)
Phe
nol
Bis
(2-c
hlor
oeth
yl)e
ther
1,
3-D
ichl
orob
enze
ne
Ben
zyl a
lcoh
ol
2-M
ethy
lphe
nol (
o-cr
esol
) 4-
Met
hylp
heno
l (p-
cres
ol)
Hex
achl
oroe
than
e N
itrob
enze
ne
2-N
itrop
heno
l B
is(2
-chl
oroe
thox
y)m
etha
ne
1,2,
4-Tr
ichl
orob
enze
ne
4-C
hlor
oani
line
4-C
hlor
o-3-
met
hylp
heno
l 1-
Met
hyln
apht
hale
ne
2,4,
6-Tr
ichl
orop
heno
l 2-
Fluo
robi
phen
yl (S
urr)
2-N
itroa
nilin
e D
imet
hylp
htha
late
2,
6-D
initr
otol
uene
A
cena
phth
ene
Ace
naph
thyl
ene
4-N
itrop
heno
l (S
PC
C)
Dib
enzo
fura
n 2,
3,5,
6-Te
trach
loro
phen
ol
4-C
hlor
ophe
nyl p
heny
l eth
er
4-N
itroa
nilin
e D
iphe
nyla
min
e 2,
4,6-
Trib
rom
ophe
nol (
Sur
r) H
exac
hlor
oben
zene
P
hena
nthr
ene
Car
bazo
le
Fluo
rant
hene
B
enzy
l but
yl p
htha
late
B
enz(
a)an
thra
cene
C
hrys
ene
Ben
zo(b
)fluo
rant
hene
B
enzo
(a)p
yren
e D
iben
z(a,
h)an
thra
cene
r2 V
alue
FIGURE 6. Comparison of MDLs from SRM vs. SRM/FS analysis (ppb).
SRM/FS Data A sample of fruit drink was extracted using the QuEChERS method of extraction and cleanup. The extract was concentrated 5x, and then 147 pesticides were spiked into the extract to produce calibration curves from 1 ppb to 200 ppb. The calibration curves were constructed for both methods: SRM and alternating SRM/full scan for 147 pesticides. The linearity for most of the compounds was R2 > 0.98 for both methods of analysis. Ten replicates of a 1 ppb and 10 ppb standard in fruit juice extract were analyzed to determine the MDLs for the two instrument methods. A comparison of the MDLs of both methods are shown in Figure 6. MDLs are slightly higher with the full scan added to the instrument method, but very comparable.
Fruit drink was spiked at 100 ppb and analyzed using the SRM/full scan instrument mode. This extract was also spiked with two phthalates at a 1 ppm level. The full scan chromatogram shows several peaks above the 100 ppb pesticide spike. Peaks are at retention times of 9.29, 9.73, 10.39, 10.91, and a very large saturated peak at 31.00 minutes. A close-up view of the first four compounds is shown in Figure 7. Figure 8 displays the NIST library matches for those non-targeted compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 5. %RSDs for the calibration curve – TSQ Duo and ISQ.
Conclusion As can be seen from this data, the TSQ Duo GC/MS-MS system can be used as a single quadrupole instrument that provides additional triple quadrupole capabilities to any laboratory. Whether the application is full scan, SIM, SRM, or a combination of SRM and full scan, the TSQ Duo system produces sensitive, accurate results.
All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
FIGURE 7. Close-up view of four unknown peaks in 100 ppb spiked fruit drink.
Dimethyl phthalate at 9.29 min Phenol, 2,4-bis (1,1-dimethylethyl) at 9.72 min used as a UV stabilizer in plastics
Diethyl phthalate at10.39 min Triethyl citrate at 0.91 min used as a plasticizer and food additive
FIGURE 8. NIST Library match for four unknown peaks.
PO10436
4 Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger1, Dwain Cardona1, Cristian Cojocariu2, Paul Silcock2, Alexander Semyonov1, Jason Cole1 1Thermo Fisher Scientific, Austin, TX, 2Thermo Fisher Scientific, Runcorn, UK
Overview This work describes how triple quadrupole gas chromatography-mass spectrometry (GC-MS) systems can be used in single quadrupole modes to satisfy current regulations as well as be able to easily switch to powerful SRM methods when needed, especially in preparation for future updates to regulations. Also included are some potential applications of mixed MS modes, such as simultaneous FS/SRM.
Introduction Many laboratories are adopting triple quadrupole GC-MS systems to access the widely accepted advantages brought by high-selectivity detection of target analytes. However, while the advantages of MS/MS scan modes, particularly SRM, are well documented, some regulated methods such as EPA 8270 do not permit use of triple quadrupole GC-MS systems. Laboratories that are accredited for these “prescriptive” regulated methods are then compelled to continue with current technology such as single quadrupole GC-MS instruments. These regulated methods prevent users becoming familiar with the latest technology so they are not able to use triple quadrupole technology unregulated sample analysis or special projects.
The versatility of the Thermo Scientific™ GC-MS/MS systems will be demonstrated in the various operational modes offered. Methods were developed for semi-volatile organic compounds (SVOCs) and pesticides, and data is presented in full scan, SIM, SRM, and SRM/full scan modes. Figure 1 provides an overview of triple quadrupole method development.
The Thermo Scientific™ TSQ™ Duo GC-MS/MS coupled to a Thermo Scientific™ TRACE™ 1310 GC, enables truly simple operation whether you choose to use it in single or triple quadrupole mode. It also bridges the gap between single and triple quadrupole mode use within the same instrument to allow easy adoption of powerful MS/MS workflows when required. Using the instrument in single quadrupole GC-MS mode allows you to continue running your current instrument configuration and established methods. The integrated software walks you through a step-by-step process to manage the transition to powerful, triple quadrupole methods.
FIGURE 1. Overview of triple quadrupole method development.
Full Scan Data SVOC calibration curves were generated from 1 to 200 ppm in methylene chloride and analyzed on the TSQ Duo GC-MS/MS and ISQ GC-MS instruments. A comparison of the %RSDs of the curves is shown in Figure 2. A comparison of 10 replicate injections at 1 ppm is displayed in Figure 3.
SIM Data SIM was used for the analysis of THC in urine samples. THC, THC-OH, and THC-COOH were extracted and derivatized for this study. Concentrations used were the cutoff value (15 ng/mL), 125% of the cutoff value (18.75 ng/mL), and 40% of the cutoff value (6 ng/mL). Table 1 shows the %RSDs of 10 replicate analyses of these three concentrations.
FIGURE 2. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of the curve for 100+ compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
FIGURE 3. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of 10 replicates at 1 ppm.
0
2
4
6
8
10
12
14
16
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
SRM Data SVOC calibration standards were prepared in methylene chloride from 1 to 1000 ppb. Transitions and collision energies for SRM were determined and optimized using the AutoSRM function of the software. Curves using internal standards were generated. Figure 4 displays the linearity of the curves. Figure 5 is a comparison of the curve %RSDs for the TSQ Duo GC-MS/MS and the ISQ GC-MS.
FIGURE 4. r2 values for a curve 1 ppb to 1000 ppb.
TSQDuo ISQ Classic TSQDuo ISQ Classic TSQDuo ISQ ClassicCutoff Cutoff 125% Cutoff 125% Cutoff 40% Cutoff 40% Cutoff
15 ng/mL 15 ng/mL 18.75 ng/mL 18.75 ng/mL 6 ng/mL 6 ng/mLTHC 2.8 5.8 4.6 3.9 9.4 2.4THC-OH 2.3 2.8 4.4 4.0 8.2 1.9THC-COOH 2.0 3.2 2.8 3.5 9.5 1.9
TABLE 1. %RSD of 10 replicates THC samples – TSQ Duo vs ISQ.
0.9400
0.9500
0.9600
0.9700
0.9800
0.9900
1.0000
1.0100
N-N
itros
odim
ethy
lam
ine
2-Fl
uoro
phen
ol (S
urr)
Phe
nol
Bis
(2-c
hlor
oeth
yl)e
ther
1,
3-D
ichl
orob
enze
ne
Ben
zyl a
lcoh
ol
2-M
ethy
lphe
nol (
o-cr
esol
) 4-
Met
hylp
heno
l (p-
cres
ol)
Hex
achl
oroe
than
e N
itrob
enze
ne
2-N
itrop
heno
l B
is(2
-chl
oroe
thox
y)m
etha
ne
1,2,
4-Tr
ichl
orob
enze
ne
4-C
hlor
oani
line
4-C
hlor
o-3-
met
hylp
heno
l 1-
Met
hyln
apht
hale
ne
2,4,
6-Tr
ichl
orop
heno
l 2-
Fluo
robi
phen
yl (S
urr)
2-N
itroa
nilin
e D
imet
hylp
htha
late
2,
6-D
initr
otol
uene
A
cena
phth
ene
Ace
naph
thyl
ene
4-N
itrop
heno
l (S
PC
C)
Dib
enzo
fura
n 2,
3,5,
6-Te
trach
loro
phen
ol
4-C
hlor
ophe
nyl p
heny
l eth
er
4-N
itroa
nilin
e D
iphe
nyla
min
e 2,
4,6-
Trib
rom
ophe
nol (
Sur
r) H
exac
hlor
oben
zene
P
hena
nthr
ene
Car
bazo
le
Fluo
rant
hene
B
enzy
l but
yl p
htha
late
B
enz(
a)an
thra
cene
C
hrys
ene
Ben
zo(b
)fluo
rant
hene
B
enzo
(a)p
yren
e D
iben
z(a,
h)an
thra
cene
r2 V
alue
FIGURE 6. Comparison of MDLs from SRM vs. SRM/FS analysis (ppb).
SRM/FS Data A sample of fruit drink was extracted using the QuEChERS method of extraction and cleanup. The extract was concentrated 5x, and then 147 pesticides were spiked into the extract to produce calibration curves from 1 ppb to 200 ppb. The calibration curves were constructed for both methods: SRM and alternating SRM/full scan for 147 pesticides. The linearity for most of the compounds was R2 > 0.98 for both methods of analysis. Ten replicates of a 1 ppb and 10 ppb standard in fruit juice extract were analyzed to determine the MDLs for the two instrument methods. A comparison of the MDLs of both methods are shown in Figure 6. MDLs are slightly higher with the full scan added to the instrument method, but very comparable.
Fruit drink was spiked at 100 ppb and analyzed using the SRM/full scan instrument mode. This extract was also spiked with two phthalates at a 1 ppm level. The full scan chromatogram shows several peaks above the 100 ppb pesticide spike. Peaks are at retention times of 9.29, 9.73, 10.39, 10.91, and a very large saturated peak at 31.00 minutes. A close-up view of the first four compounds is shown in Figure 7. Figure 8 displays the NIST library matches for those non-targeted compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 5. %RSDs for the calibration curve – TSQ Duo and ISQ.
Conclusion As can be seen from this data, the TSQ Duo GC/MS-MS system can be used as a single quadrupole instrument that provides additional triple quadrupole capabilities to any laboratory. Whether the application is full scan, SIM, SRM, or a combination of SRM and full scan, the TSQ Duo system produces sensitive, accurate results.
All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
FIGURE 7. Close-up view of four unknown peaks in 100 ppb spiked fruit drink.
Dimethyl phthalate at 9.29 min Phenol, 2,4-bis (1,1-dimethylethyl) at 9.72 min used as a UV stabilizer in plastics
Diethyl phthalate at10.39 min Triethyl citrate at 0.91 min used as a plasticizer and food additive
FIGURE 8. NIST Library match for four unknown peaks.
PO10436
5Thermo Scienti� c Poster Note • PITTCON • PN10436-EN 0215S
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger1, Dwain Cardona1, Cristian Cojocariu2, Paul Silcock2, Alexander Semyonov1, Jason Cole1 1Thermo Fisher Scientific, Austin, TX, 2Thermo Fisher Scientific, Runcorn, UK
Overview This work describes how triple quadrupole gas chromatography-mass spectrometry (GC-MS) systems can be used in single quadrupole modes to satisfy current regulations as well as be able to easily switch to powerful SRM methods when needed, especially in preparation for future updates to regulations. Also included are some potential applications of mixed MS modes, such as simultaneous FS/SRM.
Introduction Many laboratories are adopting triple quadrupole GC-MS systems to access the widely accepted advantages brought by high-selectivity detection of target analytes. However, while the advantages of MS/MS scan modes, particularly SRM, are well documented, some regulated methods such as EPA 8270 do not permit use of triple quadrupole GC-MS systems. Laboratories that are accredited for these “prescriptive” regulated methods are then compelled to continue with current technology such as single quadrupole GC-MS instruments. These regulated methods prevent users becoming familiar with the latest technology so they are not able to use triple quadrupole technology unregulated sample analysis or special projects.
The versatility of the Thermo Scientific™ GC-MS/MS systems will be demonstrated in the various operational modes offered. Methods were developed for semi-volatile organic compounds (SVOCs) and pesticides, and data is presented in full scan, SIM, SRM, and SRM/full scan modes. Figure 1 provides an overview of triple quadrupole method development.
The Thermo Scientific™ TSQ™ Duo GC-MS/MS coupled to a Thermo Scientific™ TRACE™ 1310 GC, enables truly simple operation whether you choose to use it in single or triple quadrupole mode. It also bridges the gap between single and triple quadrupole mode use within the same instrument to allow easy adoption of powerful MS/MS workflows when required. Using the instrument in single quadrupole GC-MS mode allows you to continue running your current instrument configuration and established methods. The integrated software walks you through a step-by-step process to manage the transition to powerful, triple quadrupole methods.
FIGURE 1. Overview of triple quadrupole method development.
Full Scan Data SVOC calibration curves were generated from 1 to 200 ppm in methylene chloride and analyzed on the TSQ Duo GC-MS/MS and ISQ GC-MS instruments. A comparison of the %RSDs of the curves is shown in Figure 2. A comparison of 10 replicate injections at 1 ppm is displayed in Figure 3.
SIM Data SIM was used for the analysis of THC in urine samples. THC, THC-OH, and THC-COOH were extracted and derivatized for this study. Concentrations used were the cutoff value (15 ng/mL), 125% of the cutoff value (18.75 ng/mL), and 40% of the cutoff value (6 ng/mL). Table 1 shows the %RSDs of 10 replicate analyses of these three concentrations.
FIGURE 2. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of the curve for 100+ compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
FIGURE 3. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of 10 replicates at 1 ppm.
0
2
4
6
8
10
12
14
16
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
SRM Data SVOC calibration standards were prepared in methylene chloride from 1 to 1000 ppb. Transitions and collision energies for SRM were determined and optimized using the AutoSRM function of the software. Curves using internal standards were generated. Figure 4 displays the linearity of the curves. Figure 5 is a comparison of the curve %RSDs for the TSQ Duo GC-MS/MS and the ISQ GC-MS.
FIGURE 4. r2 values for a curve 1 ppb to 1000 ppb.
TSQDuo ISQ Classic TSQDuo ISQ Classic TSQDuo ISQ ClassicCutoff Cutoff 125% Cutoff 125% Cutoff 40% Cutoff 40% Cutoff
15 ng/mL 15 ng/mL 18.75 ng/mL 18.75 ng/mL 6 ng/mL 6 ng/mLTHC 2.8 5.8 4.6 3.9 9.4 2.4THC-OH 2.3 2.8 4.4 4.0 8.2 1.9THC-COOH 2.0 3.2 2.8 3.5 9.5 1.9
TABLE 1. %RSD of 10 replicates THC samples – TSQ Duo vs ISQ.
0.9400
0.9500
0.9600
0.9700
0.9800
0.9900
1.0000
1.0100
N-N
itros
odim
ethy
lam
ine
2-Fl
uoro
phen
ol (S
urr)
Phe
nol
Bis
(2-c
hlor
oeth
yl)e
ther
1,
3-D
ichl
orob
enze
ne
Ben
zyl a
lcoh
ol
2-M
ethy
lphe
nol (
o-cr
esol
) 4-
Met
hylp
heno
l (p-
cres
ol)
Hex
achl
oroe
than
e N
itrob
enze
ne
2-N
itrop
heno
l B
is(2
-chl
oroe
thox
y)m
etha
ne
1,2,
4-Tr
ichl
orob
enze
ne
4-C
hlor
oani
line
4-C
hlor
o-3-
met
hylp
heno
l 1-
Met
hyln
apht
hale
ne
2,4,
6-Tr
ichl
orop
heno
l 2-
Fluo
robi
phen
yl (S
urr)
2-N
itroa
nilin
e D
imet
hylp
htha
late
2,
6-D
initr
otol
uene
A
cena
phth
ene
Ace
naph
thyl
ene
4-N
itrop
heno
l (S
PC
C)
Dib
enzo
fura
n 2,
3,5,
6-Te
trach
loro
phen
ol
4-C
hlor
ophe
nyl p
heny
l eth
er
4-N
itroa
nilin
e D
iphe
nyla
min
e 2,
4,6-
Trib
rom
ophe
nol (
Sur
r) H
exac
hlor
oben
zene
P
hena
nthr
ene
Car
bazo
le
Fluo
rant
hene
B
enzy
l but
yl p
htha
late
B
enz(
a)an
thra
cene
C
hrys
ene
Ben
zo(b
)fluo
rant
hene
B
enzo
(a)p
yren
e D
iben
z(a,
h)an
thra
cene
r2 V
alue
FIGURE 6. Comparison of MDLs from SRM vs. SRM/FS analysis (ppb).
SRM/FS Data A sample of fruit drink was extracted using the QuEChERS method of extraction and cleanup. The extract was concentrated 5x, and then 147 pesticides were spiked into the extract to produce calibration curves from 1 ppb to 200 ppb. The calibration curves were constructed for both methods: SRM and alternating SRM/full scan for 147 pesticides. The linearity for most of the compounds was R2 > 0.98 for both methods of analysis. Ten replicates of a 1 ppb and 10 ppb standard in fruit juice extract were analyzed to determine the MDLs for the two instrument methods. A comparison of the MDLs of both methods are shown in Figure 6. MDLs are slightly higher with the full scan added to the instrument method, but very comparable.
Fruit drink was spiked at 100 ppb and analyzed using the SRM/full scan instrument mode. This extract was also spiked with two phthalates at a 1 ppm level. The full scan chromatogram shows several peaks above the 100 ppb pesticide spike. Peaks are at retention times of 9.29, 9.73, 10.39, 10.91, and a very large saturated peak at 31.00 minutes. A close-up view of the first four compounds is shown in Figure 7. Figure 8 displays the NIST library matches for those non-targeted compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 5. %RSDs for the calibration curve – TSQ Duo and ISQ.
Conclusion As can be seen from this data, the TSQ Duo GC/MS-MS system can be used as a single quadrupole instrument that provides additional triple quadrupole capabilities to any laboratory. Whether the application is full scan, SIM, SRM, or a combination of SRM and full scan, the TSQ Duo system produces sensitive, accurate results.
All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
FIGURE 7. Close-up view of four unknown peaks in 100 ppb spiked fruit drink.
Dimethyl phthalate at 9.29 min Phenol, 2,4-bis (1,1-dimethylethyl) at 9.72 min used as a UV stabilizer in plastics
Diethyl phthalate at10.39 min Triethyl citrate at 0.91 min used as a plasticizer and food additive
FIGURE 8. NIST Library match for four unknown peaks.
PO10436
PN10436-EN 0215S
Using Triple Quadrupole GC-MS in Full Scan, SIM, SRM, and Mixed Scan Modes to Provide the Highest Coverage for Target and Non-target Analysis of Contaminants David Steiniger1, Dwain Cardona1, Cristian Cojocariu2, Paul Silcock2, Alexander Semyonov1, Jason Cole1 1Thermo Fisher Scientific, Austin, TX, 2Thermo Fisher Scientific, Runcorn, UK
Overview This work describes how triple quadrupole gas chromatography-mass spectrometry (GC-MS) systems can be used in single quadrupole modes to satisfy current regulations as well as be able to easily switch to powerful SRM methods when needed, especially in preparation for future updates to regulations. Also included are some potential applications of mixed MS modes, such as simultaneous FS/SRM.
Introduction Many laboratories are adopting triple quadrupole GC-MS systems to access the widely accepted advantages brought by high-selectivity detection of target analytes. However, while the advantages of MS/MS scan modes, particularly SRM, are well documented, some regulated methods such as EPA 8270 do not permit use of triple quadrupole GC-MS systems. Laboratories that are accredited for these “prescriptive” regulated methods are then compelled to continue with current technology such as single quadrupole GC-MS instruments. These regulated methods prevent users becoming familiar with the latest technology so they are not able to use triple quadrupole technology unregulated sample analysis or special projects.
The versatility of the Thermo Scientific™ GC-MS/MS systems will be demonstrated in the various operational modes offered. Methods were developed for semi-volatile organic compounds (SVOCs) and pesticides, and data is presented in full scan, SIM, SRM, and SRM/full scan modes. Figure 1 provides an overview of triple quadrupole method development.
The Thermo Scientific™ TSQ™ Duo GC-MS/MS coupled to a Thermo Scientific™ TRACE™ 1310 GC, enables truly simple operation whether you choose to use it in single or triple quadrupole mode. It also bridges the gap between single and triple quadrupole mode use within the same instrument to allow easy adoption of powerful MS/MS workflows when required. Using the instrument in single quadrupole GC-MS mode allows you to continue running your current instrument configuration and established methods. The integrated software walks you through a step-by-step process to manage the transition to powerful, triple quadrupole methods.
FIGURE 1. Overview of triple quadrupole method development.
Full Scan Data SVOC calibration curves were generated from 1 to 200 ppm in methylene chloride and analyzed on the TSQ Duo GC-MS/MS and ISQ GC-MS instruments. A comparison of the %RSDs of the curves is shown in Figure 2. A comparison of 10 replicate injections at 1 ppm is displayed in Figure 3.
SIM Data SIM was used for the analysis of THC in urine samples. THC, THC-OH, and THC-COOH were extracted and derivatized for this study. Concentrations used were the cutoff value (15 ng/mL), 125% of the cutoff value (18.75 ng/mL), and 40% of the cutoff value (6 ng/mL). Table 1 shows the %RSDs of 10 replicate analyses of these three concentrations.
FIGURE 2. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of the curve for 100+ compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
FIGURE 3. Comparison between the TSQ Duo GC-MS/MS and the ISQ GC-MS %RSDs of 10 replicates at 1 ppm.
0
2
4
6
8
10
12
14
16
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)- K
epon
e C
hrys
ene-
D12
bi
s(2-
ethy
lhex
yl)p
htha
late
B
enzo
[(k]fl
uora
nthe
ne
benz
o(a)
pyre
ne
Ben
zo[g
hi]p
eryl
ene
Duo
ISQ
SRM Data SVOC calibration standards were prepared in methylene chloride from 1 to 1000 ppb. Transitions and collision energies for SRM were determined and optimized using the AutoSRM function of the software. Curves using internal standards were generated. Figure 4 displays the linearity of the curves. Figure 5 is a comparison of the curve %RSDs for the TSQ Duo GC-MS/MS and the ISQ GC-MS.
FIGURE 4. r2 values for a curve 1 ppb to 1000 ppb.
TSQDuo ISQ Classic TSQDuo ISQ Classic TSQDuo ISQ ClassicCutoff Cutoff 125% Cutoff 125% Cutoff 40% Cutoff 40% Cutoff
15 ng/mL 15 ng/mL 18.75 ng/mL 18.75 ng/mL 6 ng/mL 6 ng/mLTHC 2.8 5.8 4.6 3.9 9.4 2.4THC-OH 2.3 2.8 4.4 4.0 8.2 1.9THC-COOH 2.0 3.2 2.8 3.5 9.5 1.9
TABLE 1. %RSD of 10 replicates THC samples – TSQ Duo vs ISQ.
0.9400
0.9500
0.9600
0.9700
0.9800
0.9900
1.0000
1.0100
N-N
itros
odim
ethy
lam
ine
2-Fl
uoro
phen
ol (S
urr)
Phe
nol
Bis
(2-c
hlor
oeth
yl)e
ther
1,
3-D
ichl
orob
enze
ne
Ben
zyl a
lcoh
ol
2-M
ethy
lphe
nol (
o-cr
esol
) 4-
Met
hylp
heno
l (p-
cres
ol)
Hex
achl
oroe
than
e N
itrob
enze
ne
2-N
itrop
heno
l B
is(2
-chl
oroe
thox
y)m
etha
ne
1,2,
4-Tr
ichl
orob
enze
ne
4-C
hlor
oani
line
4-C
hlor
o-3-
met
hylp
heno
l 1-
Met
hyln
apht
hale
ne
2,4,
6-Tr
ichl
orop
heno
l 2-
Fluo
robi
phen
yl (S
urr)
2-N
itroa
nilin
e D
imet
hylp
htha
late
2,
6-D
initr
otol
uene
A
cena
phth
ene
Ace
naph
thyl
ene
4-N
itrop
heno
l (S
PC
C)
Dib
enzo
fura
n 2,
3,5,
6-Te
trach
loro
phen
ol
4-C
hlor
ophe
nyl p
heny
l eth
er
4-N
itroa
nilin
e D
iphe
nyla
min
e 2,
4,6-
Trib
rom
ophe
nol (
Sur
r) H
exac
hlor
oben
zene
P
hena
nthr
ene
Car
bazo
le
Fluo
rant
hene
B
enzy
l but
yl p
htha
late
B
enz(
a)an
thra
cene
C
hrys
ene
Ben
zo(b
)fluo
rant
hene
B
enzo
(a)p
yren
e D
iben
z(a,
h)an
thra
cene
r2 V
alue
FIGURE 6. Comparison of MDLs from SRM vs. SRM/FS analysis (ppb).
SRM/FS Data A sample of fruit drink was extracted using the QuEChERS method of extraction and cleanup. The extract was concentrated 5x, and then 147 pesticides were spiked into the extract to produce calibration curves from 1 ppb to 200 ppb. The calibration curves were constructed for both methods: SRM and alternating SRM/full scan for 147 pesticides. The linearity for most of the compounds was R2 > 0.98 for both methods of analysis. Ten replicates of a 1 ppb and 10 ppb standard in fruit juice extract were analyzed to determine the MDLs for the two instrument methods. A comparison of the MDLs of both methods are shown in Figure 6. MDLs are slightly higher with the full scan added to the instrument method, but very comparable.
Fruit drink was spiked at 100 ppb and analyzed using the SRM/full scan instrument mode. This extract was also spiked with two phthalates at a 1 ppm level. The full scan chromatogram shows several peaks above the 100 ppb pesticide spike. Peaks are at retention times of 9.29, 9.73, 10.39, 10.91, and a very large saturated peak at 31.00 minutes. A close-up view of the first four compounds is shown in Figure 7. Figure 8 displays the NIST library matches for those non-targeted compounds.
0
5
10
15
20
25
N-N
itros
odim
ethy
lam
ine
Eth
anam
ine,
N-m
ethy
l-N-n
itros
o-
Met
hane
sulfo
nic
acid
, eth
yl e
ster
A
nilin
e P
heno
l, 2-
chlo
ro-
Ben
zene
, 1,4
-dic
hlor
o-
Phe
nol,
2-m
ethy
l- (O
Cre
sol)
o-To
luid
ine
Nitr
oben
zene
-D5(
surr
ogat
e)
isop
horo
ne
Met
hane
, bis
(2-c
hlor
oeth
oxy)
- N
apht
hale
ne-D
8 1-
Pro
pene
, 1,1
,2,3
,3,3
-hex
achl
oro-
P
heno
l, 4-
chlo
ro-3
-met
hyl-
Ben
zene
, 1,2
,3,5
-tetra
chlo
ro-
2-flu
orob
iphe
nyl,(
surr
ogat
e)
2-N
itroa
nilin
e B
enze
ne, 2
-met
hyl-1
,3-d
initr
o-
Ace
naph
then
e-d1
0 P
heno
l, 4-
nitro
- D
iben
zofu
ran
2-N
apht
hale
nam
ine
Phe
nol,
2-m
ethy
l, 4,
6-di
nitro
- 2,
4,6-
tribr
omop
heno
l (su
rrog
ate)
P
hena
cetin
B
enze
ne, p
enta
chlo
roni
tro-
Phe
nant
hren
e D
ibut
yl p
htha
late
B
enzi
dine
B
enze
nam
ine,
N,N
-dim
ethy
l-4-(p
heny
lazo
)-
Kep
one
Chr
ysen
e-D
12
bis(
2-et
hylh
exyl
)pht
hala
te
Ben
zo[(k
]fluo
rant
hene
be
nzo(
a)py
rene
B
enzo
[ghi
]per
ylen
e
Duo
ISQ
FIGURE 5. %RSDs for the calibration curve – TSQ Duo and ISQ.
Conclusion As can be seen from this data, the TSQ Duo GC/MS-MS system can be used as a single quadrupole instrument that provides additional triple quadrupole capabilities to any laboratory. Whether the application is full scan, SIM, SRM, or a combination of SRM and full scan, the TSQ Duo system produces sensitive, accurate results.
All trademarks are the property of Thermo Fisher Scientific and its subsidiaries.
This information is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others.
FIGURE 7. Close-up view of four unknown peaks in 100 ppb spiked fruit drink.
Dimethyl phthalate at 9.29 min Phenol, 2,4-bis (1,1-dimethylethyl) at 9.72 min used as a UV stabilizer in plastics
Diethyl phthalate at10.39 min Triethyl citrate at 0.91 min used as a plasticizer and food additive
FIGURE 8. NIST Library match for four unknown peaks.
PO10436
Africa +43 1 333 50 34 0Australia +61 3 9757 4300Austria +43 810 282 206Belgium +32 53 73 42 41Brazil +55 11 3731 5140Canada +1 800 530 8447China 800 810 5118 (free call domestic)
400 650 5118
Denmark +45 70 23 62 60Europe-Other +43 1 333 50 34 0Finland +358 9 3291 0200France +33 1 60 92 48 00Germany +49 6103 408 1014India +91 22 6742 9494Italy +39 02 950 591
Japan +81 6 6885 1213Korea +82 2 3420 8600Latin America +1 561 688 8700Middle East +43 1 333 50 34 0Netherlands +31 76 579 55 55 New Zealand +64 9 980 6700 Norway +46 8 556 468 00
Russia/CIS +43 1 333 50 34 0Singapore +65 6289 1190Sweden +46 8 556 468 00 Switzerland +41 61 716 77 00Taiwan +886 2 8751 6655UK/Ireland +44 1442 233555USA +1 800 532 4752
www.thermoscientific.com/chromatography©2015 Thermo Fisher Scienti� c Inc. All rights reserved. ISO is a trademark of the International Standards Organization. All other trademarks are the property of Thermo Fisher Scienti� c and its subsidiaries. This information is presented as an example of the capabilities of Thermo Fisher Scienti� c products. It is not intended to encourage use of these products in any manners that might infringe the intellectual property rights of others. Speci� cations, terms and pricing are subject to change. Not all products are available in all countries. Please consult your local sales representative for details.
Thermo Fisher Scienti� c,Sunnyvale, CA USA is ISO 9001 Certi� ed.