LC-MS Applications for Environmental Analysis

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5 Thermo Scientific Poster Note • PN63560_E 06/12S
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Sample
100ppbQC
Spiked Water
Sample Area Calc Amount
100ppbQC 878 117
Spiked Water 2489 332
pentaBromoEthylBenzene
435 440 445
m/z
436.60
34.64 438.42
440.73
441.64 444.93
436.70
34.70 438.70
440.70
441.78 443.86
NL:
2.01E6
PentaBromoEthylBenzene#
433-475 RT: 7.45-8.18
AV: 43T: -pNSIQ1MS
[249.700-749.630]
NL:
8.08E3
C 8H 5Br4 O:
C 8H 5Br4 O1
p(gss, s/p:40)Chrg-1
R:
o bisphenol A
540 545 550 555
m/z
542.65
540.69 544.54
8.66 546.64
547.69 558.82 556.65
542.75
540.73 544.75
546.76
547.84
NL:
2.31E5
TetraBromoBisPhenolA#80-
140 RT: 1.37-2.41 AV: 61
T: - pNSIQ1MS
[293.870-793.800]
NL:
7.53E3
C 15H 11Br4O2:
C 15H 11Br4O2
p(gss, s/p:40)Chrg-1
R:
us theoretical
ization
lower spectrum is
s.
FIGURE 4. Calibration curves and r
1,2,5,6,9,10-hexabromocyclododec
the TSQ MS from
from low to high and
n ions (Table 1).
mission experiments
e to its highly efficient
was acquired in the
was chosen to
re 3) and avoid
.
peak represents the
tal of ten peaks from
ach spot in a
eated twice for a
d as low as 50 ppb,
odecane, and
ility at this level was
y. Thus, it was not
ound. Poor
and could easily
ds. However, even
obtain some
exported to Excel.
A San Francisco (SF) water sample w
described, and drying at 60 ºC for ten
(Figure 3). It is interesting to note that
SF water sample the compound resp
enhancement of tetrabromophthalic a
tetrabromobisphenol A, 1,2,5,6,9,10-h
dibromopropyl)isocyanurate (Figure 3
applying the standards in the same m
while sample variation was observed,
method of detecting and quantitating
the effect of labeled standards and m
Conclusions
 The linear ion trap MS with the D
excellent method of detecting BF
ion information.
 The Quantum Access MAX MS
generated full scan spectra for B
match to theoretical spectra confi
linear ion trap and 2) facilitated t
transition fragments, and collisio
 BFR and OC quantitative experi
be as low as 50 ppb for several c
 Further work to minimize sample
matrix on sample response will b
 DART-SVP provides a quick sim
the need for sample preparation
References
1. Emerging Brominated Flame R
Amelie Kierkegaard, Niklas Ric
Barcelo´ (eds.), Brominated Fla
Heidelberg 2010, Published onl
Acknowledgement
We would like to thank IonSense Cor
depicts linear ion
a was acquired with
as generated with
500 550
527.67
542.83
515.17 498.08 92
FIGURE 3. TSQ MS data for calibrators and unknowns. Each panel depicts the
compounds in the following order from top to bottom:
1) kepone 6) hexabromobenzene
2) allyl 2,4,6-tribromophenyl ether 7) tetrabromobisphenol A
3) 2-bromo-1,3-bis(dibromomethyl)benzene 8) 1,2,5,6,9,10-hexabromocyclododecane
4) tetrabromophthalic anhydride 9) tris(2,3-dibromopropyl)isocyanurate
5) 2,3,4,5,6-pentabromoethylbenzene
C:\Blackburn\...\50ppb_AC 5/3/20127:45:48PM 50ppb
5uL line2X,10uL total
RT:0.00 -4.10 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
0
50
100 RT: 2.91
RT: 3.22 RT: 2.31 RT: 2.61
RT: 0.49 RT: 2.00 RT: 1.09 RT: 0.79 RT: 1.40 RT: 1.70
RT: 3.94 RT: 3.73 RT: 0.24
RT: 2.54
RT: 2.09
RT: 3.17 RT: 1.71
RT: 0.61 RT: 3.76 RT: 1.27 RT: 0.99 RT: 0.21
RT: 0.87 RT: 1.46 RT: 2.01
RT: 1.77 RT: 3.85 RT: 3.40 RT: 2.69 RT: 2.45 RT: 0.25
RT: 1.39 RT: 3.23
RT: 2.92 RT: 2.24
RT: 1.03 RT: 3.72 RT: 2.43
RT: 2.05 RT: 0.23
RT: 3.23 RT: 2.93
RT: 1.94
NL: 1.24E4
TICF: -c NSISRMms2 506.690
[424.802-424.804, 426.759-426.761] MS ICIS
50ppb_AC
NL: 2.56E1
TICF: -c NSISRMms2 306.855
[265.826-265.828] MS ICIS 50ppb_AC
NL: 2.12E1
TICF: -c NSISRMms2 370.757 [79.200-79.202,
81.098-81.100, 326.725-326.727] MS ICIS
50ppb_AC
NL: 1.96E1
TICF: -c NSISRMms2 398.711
[326.725-326.727, 354.834-354.836] MS ICIS
50ppb_AC
NL: 1.85E1
TICF: -c NSISRMms2 436.716 [81.055-81.057,
247.648-247.650, 356.593-356.595] MS
Genesis 50ppb_AC
RT:0.00 -4.02 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
RT: 2.91
RT: 1.40
RT: 0.77 RT: 1.09
RT: 2.00 RT: 3.22 RT: 0.47 RT: 2.33
RT: 1.74 RT: 2.65
RT: 2.59 RT: 2.94
RT: 0.79 RT: 2.29 RT: 1.10 RT: 3.24
RT: 1.70 RT: 1.38 RT: 2.01 RT: 0.49
RT: 2.92
RT: 2.60
RT: 3.18
RT: 1.06 RT: 2.01 RT: 1.38 RT: 1.67
RT: 0.81 RT: 2.31
NL: 7.17
TICF: - cNSISRMms2 486.588
[377.999-378.001, 379.727-379.729] MS
50ppb_AC
NL: 1.40E3
TICF: - cNSISRMms2 542.707
[290.795-290.797, 417.949-417.951,
419.722-419.724] MS Genesis
50ppb_AC
NL: 1.71E2
TICF: - cNSISRMms2 640.651
[79.095-79.097, 81.055-81.057] MS
Genesis 50ppb_AC
NL: 1.02E2
TICF: - cNSISRMms2 727.605
[79.298-79.300, 81.030-81.032] MS
Genesis 50ppb_AC
50 ppb
C:\Blackburn\...\1ppm_AC 5/3/20128:08:56PM 1 ppm
5uL line 2X,10uL total
RT:0.00 - 4.10 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
0
50
100 RT: 3.08
RT: 2.78
RT: 1.88 RT: 2.49
RT: 2.19
RT: 0.96 RT: 1.58
RT: 1.26 RT: 3.38
RT: 0.67 RT: 3.55 RT: 4.05
RT: 3.18
RT: 1.36 RT: 1.65 RT: 1.95 RT: 2.56 RT: 2.25 RT: 2.86 RT: 3.47 RT: 1.04
RT: 0.74 RT: 4.07 RT: 3.62
RT: 2.18
RT: 2.80 RT: 1.82 RT: 4.00 RT: 3.68 RT: 3.35
RT: 2.98 RT: 1.38 RT: 1.08
RT: 0.64 RT: 0.49 RT: 0.15
RT: 1.29 RT: 3.09 RT: 3.39
RT: 1.58
RT: 2.20 RT: 2.49
RT: 0.97 RT: 2.81
RT: 0.65 RT: 3.81
RT: 3.58
RT: 0.15
RT: 3.11
RT: 1.90 RT: 2.81
RT: 2.20 RT: 1.60
RT: 1.25
RT: 0.97 RT: 0.67 RT: 2.51 RT: 3.42
NL: 6.54E3
TICF: - c NSISRMms2 506.690
[424.802-424.804, 426.759-426.761] MS ICIS
1ppm_AC
NL: 5.51E3
TICF: - c NSISRMms2 306.855
[265.826-265.828] MS ICIS 1ppm_AC
NL: 2.42E1
TICF: - c NSISRMms2 370.757
[79.200-79.202, 81.098-81.100,
326.725-326.727] MS ICIS 1ppm_AC
NL: 4.56E3
TICF: - c NSISRMms2 398.711
[326.725-326.727, 354.834-354.836] MS ICIS
1ppm_AC
NL: 8.04E2
TICF: - c NSISRMms2 436.716
[81.055-81.057, 247.648-247.650,
356.593-356.595] MS Genesis 1ppm_AC
RT:0.00 - 4.32 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100 RT: 3.42
RT: 2.79 RT: 0.97
RT: 2.19 RT: 3.11
RT: 1.90
RT: 1.26 RT: 2.51
RT: 1.60
RT: 1.26 RT: 3.10
RT: 2.78 RT: 2.19 RT: 2.49
RT: 1.60 RT: 3.40
RT: 0.98 RT: 1.91
RT: 0.69
RT: 3.10
RT: 2.78
RT: 1.89 RT: 1.26 RT: 2.48 RT: 0.96 RT: 2.17 RT: 3.41
RT: 1.59
RT: 0.68
RT: 3.10
RT: 2.48 RT: 2.78
RT: 1.26 RT: 3.41 RT: 0.96 RT: 1.89 RT: 2.19 RT: 1.57
RT: 0.68
NL: 1.78E2
TIC F: - cNSISRMms2486.588
[377.999-378.001, 379.727-379.729] MS
Genesis 1ppm_AC
NL: 5.96E4
TIC F: - cNSISRMms2542.707
[290.795-290.797, 417.949-417.951,
419.722-419.724] MS Genesis
1ppm_AC
NL: 9.59E3
TIC F: - cNSISRMms2640.651
[79.095-79.097, 81.055-81.057] MS
Genesis 1ppm_AC
NL: 4.99E3
TIC F: - cNSISRMms2727.605
[79.298-79.300, 81.030-81.032] MS
Genesis 1ppm_AC
1 ppm
C:\Blackburn\...\SF_Water_AC 5/3/20128:59:14PM SFWater
5uL line2X,10uL total
RT:0.00 -4.10 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
0
50
100 RT: 2.82
RT: 3.96 RT: 3.26 RT: 2.18
RT: 1.95 RT: 1.48 RT: 0.72 RT: 0.45 RT: 0.28
RT: 1.94
RT: 1.22
RT: 3.88
RT: 3.61 RT: 3.42 RT: 3.19 RT: 2.55
RT: 2.26 RT: 2.04 RT: 1.75 RT: 1.58 RT: 0.86 RT: 0.56 RT: 0.12
RT: 3.35
RT: 2.72 RT: 2.13 RT: 2.44 RT: 3.88
RT: 1.40
NL: 9.83
TICF: - cNSISRMms2 506.690
[424.802-424.804, 426.759-426.761] MS ICIS
SF_Water_AC
NL: 9.02
TICF: - cNSISRMms2 306.855
[265.826-265.828] MS ICIS SF_Water_AC
NL: 1.94E1
TICF: - cNSISRMms2 370.757 [79.200-79.202,
81.098-81.100, 326.725-326.727] MS ICIS
SF_Water_AC
NL: 7.29E1
TICF: - cNSISRMms2 398.711
[326.725-326.727, 354.834-354.836] MS ICIS
SF_Water_AC
NL: 1.82E1
TICF: - cNSISRMms2 436.716 [81.055-81.057,
247.648-247.650, 356.593-356.595] MS Genesis
SF_Water_AC
RT:0.00 -4.23 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
RT: 0.97
RT: 3.19 RT: 2.14 RT: 1.84
NL: 7.05
TICF: - cNSISRMms2 486.588
[377.999-378.001, 379.727-379.729]
MS SF_Water_AC
NL: 1.07E1
TICF: - cNSISRMms2 542.707
[290.795-290.797, 417.949-417.951,
419.722-419.724] MS SF_Water_AC
NL: 1.16E1
TICF: - cNSISRMms2 640.651
[79.095-79.097, 81.055-81.057] MS
GenesisSF_Water_AC
NL: 7.02
TICF: - cNSISRMms2 727.605
[79.298-79.300, 81.030-81.032] MS
SF_Water_AC
SF Water
C:\Blackburn\...\SF_Water_SpikedI_AC 5/3/20129:16:41PM SFWaterspikedw/500ppb
5uL line2X,10uL total
RT:0.00 -4.10 SM:7G
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
0
50
100 RT: 1.01
RT: 1.66 RT: 3.19
RT: 2.57
RT: 2.25 RT: 0.73 RT: 3.67
RT: 2.85 RT: 1.92 RT: 0.25
RT: 3.18
RT: 0.78
RT: 2.24
RT: 1.88
RT: 1.36 RT: 2.86 RT: 1.59 RT: 4.08 RT: 3.68 RT: 3.39 RT: 0.47 RT: 0.26
RT: 1.35
RT: 0.68
RT: 3.49 RT: 1.08 RT: 3.13 RT: 3.68 RT: 2.81 RT: 2.56 RT: 2.18 RT: 1.93 RT: 1.78
RT: 3.51 RT: 2.58 RT: 3.21
RT: 1.94 RT: 2.85
RT: 2.24
RT: 1.67
RT: 1.37
RT: 1.04
RT: 0.72
RT: 3.97 RT: 0.50 RT: 0.23
RT: 1.44 RT: 3.47
RT: 1.92
RT: 2.89 RT: 2.54
RT: 2.34 RT: 1.12 RT: 1.62
NL: 3.42E1
TICF: -cNSISRMms2 506.690 [424.802-424.804,
426.759-426.761] MS ICIS SF_Water_SpikedI_AC
NL: 7.46E1
TICF: -cNSISRMms2 306.855 [265.826-265.828]
MS ICISSF_Water_SpikedI_AC
NL: 2.23E1
TICF: - cNSISRMms2 370.757 [79.200-79.202,
81.098-81.100, 326.725-326.727] MS ICIS
SF_Water_SpikedI_AC
NL: 8.66E3
TICF: -cNSISRMms2 398.711 [326.725-326.727,
354.834-354.836] MS ICIS SF_Water_SpikedI_AC
NL: 8.35E1
TICF: - cNSISRMms2 436.716 [81.055-81.057,
247.648-247.650, 356.593-356.595] MS Genesis
SF_Water_SpikedI_AC
RT:0.00 -4.49 SM:7G
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100 RT: 1.90 RT: 1.64
RT: 0.73 RT: 1.05
RT: 2.26 RT: 2.64
RT: 3.48
RT: 3.18
RT: 2.57
RT: 1.96 RT: 1.68 RT: 2.27 RT: 2.85 RT: 1.36
RT: 1.05
RT: 0.75
RT: 1.04
RT: 2.53
RT: 1.95 RT: 1.62 RT: 2.23 RT: 3.44 RT: 0.71 RT: 2.84 RT: 3.14
RT: 1.32
RT: 1.04 RT: 1.95 RT: 2.54 RT: 3.12 RT: 3.47
RT: 1.64 RT: 2.23 RT: 2.84
RT: 1.34 RT: 0.72
NL: 1.50E1
TICF: - cNSISRMms2 486.588
[377.999-378.001, 379.727-379.729] MS
Genesis SF_Water_SpikedI_AC
NL: 1.89E4
TICF: - cNSISRMms2 542.707
[290.795-290.797, 417.949-417.951,
419.722-419.724] MS Genesis
SF_Water_SpikedI_AC
NL: 3.81E3
TICF: - cNSISRMms2 640.651
[79.095-79.097, 81.055-81.057] MS Genesis
SF_Water_SpikedI_AC
NL: 7.31E2
TICF: - cNSISRMms2 727.605
[79.298-79.300, 81.030-81.032] MS Genesis
SF_Water_SpikedI_AC
SF Water spiked w/ 500 ppb
C:\Blackburn\...\100ppbQC 5/3/20127:03:19PM 100ppbsampleasQC
5uL line spotted2X, total10uL
RT:0.00 -4.00 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100
0
50
100 RT: 3.62
RT: 3.33 RT: 1.51 RT: 2.14
RT: 1.82 RT: 3.01
RT: 2.73 RT: 2.42
RT: 1.21
RT: 0.91
RT: 0.53
RT: 1.86 RT: 1.29 RT: 2.51
RT: 1.60 RT: 2.20 RT: 2.79 RT: 3.10 RT: 3.40
RT: 1.01 RT: 3.91 RT: 3.74 RT: 0.54
RT: 2.98
RT: 2.76 RT: 1.56 RT: 3.48 RT: 2.32 RT: 2.02
RT: 1.07 RT: 0.76 RT: 0.35
RT: 3.27
RT: 3.59
RT: 2.72
RT: 0.88 RT: 1.51 RT: 2.45 RT: 1.77 RT: 2.09 RT: 3.95
RT: 0.54
RT: 1.02 RT: 1.51 RT: 1.93
RT: 2.82 RT: 3.12
RT: 2.53
NL: 7.06E3
TICF: - cNSISRMms2 506.690
[424.802-424.804, 426.759-426.761] MS ICIS
100ppbQC
NL: 1.35E2
TICF: - cNSISRMms2 306.855
[265.826-265.828] MS ICIS 100ppbQC
NL: 1.48E1
TICF: -cNSISRMms2 370.757 [79.200-79.202,
81.098-81.100, 326.725-326.727] MS ICIS
100ppbQC
NL: 3.80E2
TICF: - cNSISRMms2 398.711
[326.725-326.727, 354.834-354.836] MS ICIS
100ppbQC
NL: 8.81E1
TICF: -cNSISRMms2 436.716 [81.055-81.057,
247.648-247.650, 356.593-356.595] MS
Genesis 100ppbQC
RT:0.00 -4.01 SM:7G
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0
Time (min)
0
50
100
0
50
100
0
50
100
Relative Abundance
0
50
100 RT: 3.29
RT: 2.76
RT: 2.14
RT: 1.02
RT: 2.73
RT: 1.51 RT: 3.03 RT: 1.84
RT: 1.21 RT: 2.43 RT: 3.62 RT: 2.14
RT: 0.93 RT: 3.32
RT: 3.36
RT: 1.84 RT: 3.66 RT: 2.14
RT: 1.50 RT: 2.73 RT: 3.02
RT: 2.43
RT: 1.23
RT: 0.93
RT: 3.62
RT: 3.34
RT: 1.50 RT: 3.02 RT: 0.87 RT: 1.82 RT: 2.75
RT: 2.43
RT: 1.22 RT: 2.09
NL: 1.73E1
TICF: - cNSISRMms2 486.588
[377.999-378.001, 379.727-379.729] MS
Genesis 100ppbQC
NL: 5.97E3
TICF: - cNSISRMms2 542.707
[290.795-290.797, 417.949-417.951,
419.722-419.724] MS Genesis
100ppbQC
NL: 4.32E2
TICF: - cNSISRMms2 640.651
[79.095-79.097, 81.055-81.057] MS
Genesis 100ppbQC
NL: 4.45E2
TICF: - cNSISRMms2 727.605
[79.298-79.300, 81.030-81.032] MS
Genesis 100ppbQC
100 ppb QC
All compound peaks corresponding to
data point at each level. A minimum o
included in a curve. Chromatograms
in Figure 4.