New perspective on the determination of polybrominated diphenyl …€¦ · – thermal degradation...
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New perspective on the determination of polybrominated diphenyl ethers and other flame retardants in sewage sludge by UPLC/MS-MS using both APCI and APPI Giuseppe Mascolo , Vito Locaputo CNR – Istituto di Ricerca Sulle Acque Via F. de Blasio, 5 70132 Bari ITALY
Transcript of New perspective on the determination of polybrominated diphenyl …€¦ · – thermal degradation...
New perspective on the determination of polybrominated diphenyl ethers and other
flame retardants in sewage sludge by UPLC/MS-MS using both APCI and APPI
Giuseppe Mascolo, Vito Locaputo
CNR – Istituto di Ricerca Sulle AcqueVia F. de Blasio, 5 70132 BariITALY
Presentation outline
• Focusing the problem about brominated flame retardants (BFRs);
• Benefits of UPLC-MS/MS with respect to GC-MS for the determination of BFRs;
- Comparison of ESI, APPI and APCI;- Matrix effect (signal suppression and background);- Method validation (extraction, LOD, LOQ);- Application to municipal sewage sludge samples;
• Results obtained by UPLC-MS/MS on sewage sludge samples;
• Conclusions.
FOCUSING THE PROBLEM• Brominated flame retardants (BFRs) are ubiquitous in the
environment due to their widespread use in many industrial and consumer products as a consequence of fire prevention policies.
• Their usage is justified by the effective electron-scavenging action of bromine leading to chain scission and flame poisoning.
• More than 175 different types of flame retardants exist but BFRs are the largest market group (low cost and high efficiency for protection against flammability).
• More than 200,000 metric tons of BFRs are produced each year. Therefore, as a consequence of diffuse discharges to the environment, they have been detected in many area indicating persistence and bioaccumulation.
Investigated brominated flame retardants
OHHO
Cl
ClCl
Cl
Tetrachlorobisphenol- A (TCBP-A)
OH
Br
BrBr
Br
Tetrabromobisphenol- A (TBBP-A)
O
Brm Brn
PolyBrominated Diphenyl Ethers (PBDEs)
Br
BrO
Br
Br Br
Br
OBr
Br
Tetrabromobisphenol-A-Bis (TBBP-A- Bis)
Br
BrBr
BrBr
Br
1,2,5,6,9,10-Hexabromocyclododecane (HBCD)3 isomers: α-HBCD, β-HBCD, γ-HBCD
Environmental relevance of BFRs• BFrs are hydrophobic compounds → bioaccumulation.
• BFRs have been found in breast milk, animals, sediments, sewage sludge, etc.
• Several studies showed that BFRs lead to toxic effects or estrogenic action.
• If sewage sludge is disposed of to incineration PBDEs can be transformed into bromo-dibenzodioxins and bromo-dibenzofuranes.
• 2000/60/EC directive includes PBDEs in the priority substances list.
• Two out of three PBDE formulations (Octa-BDE and Deca-BDE) were banned in the European Union (directive CE 2003/11/EEC).
Current limitations about PBDEs determination
• GC-MS is commonly used (EI or electron capture negative ionization (ECNI). Main drawbacks are:
– thermal degradation problems (congeners with > 8 Br);
– EI: selective, [M-Br2]+ are monitored, poor sensitivity, large drop in sensitivity for congeners with > 6 Br;
– ECNI: good sensitivity, poor selectivity (Br- is monitored).
LC-MS for PBDEs determination
• However, up to now :– just APPI proved to be useful;– obtained LODs are much higher than those of GC-NICI/MS;
• Advantages:– proper selectivity can be obtained by MS-MS detection mode;– detecting metabolites of PBDEs, i.e. hydroxylated PBDEs and
glucuronic acid or glutathione conjugates;
• Present investigation:– to compare APCI vs APPI;– to obtain LODs comparable to those of GC-NICI/MS;
• Employed system: Acquity UPLC with API 5000.
TIC of UPLC-MS/MS chromatograms (10 µg L-1 each compound).
TIC: from Sample 1 (Std 10ppb ESI ) of Std 10ppb ESI .wiff (Turbo Spray) Max. 9.4e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e5
9.4e5 4.35.1
4.1
ESI (-)
TCBPA
TBBPA HBCDD
TIC: from Sample 1 (std 10 ppb APCI) of std 10 ppb APCI.wiff (Heated Nebulizer) Max. 6.0e4 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e5
4.34.1 5.03.0 5.04.03.7
APCI (-)
TIC: from Sample 2 (Std 10 ppb APPI) of Std 10 ppb APPI.wiff (Photospray) Max. 4.1e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e5 4.3
4.14.53.7 5.13.43.0 3.32.50.7 2.81.6 2.10.3 1.2 1.4 2.30.2 0.5 2.0
APPI (-)
Results: first group of compoundsTIC: from Sample 1 (Std 10ppb ESI ) of Std 10ppb ESI .wiff (Turbo Spray) Max. 9.4e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e5
9.4e5 4.35.1
4.1
ESI (-)
TCBPA
TBBPA HBCDD
TIC: from Sample 1 (std 10 ppb APCI) of std 10 ppb APCI.wiff (Heated Nebulizer) Max. 6.0e4 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e44.3
4.15.0
3.0 5.04.03.7 5.21.81.10.7 3.63.3 5.3 6.96.80.5 2.5 6.32.32.0 6.25.83.01.6 7.11.3 7.7 7.8 8.5 8.60.9 9.3 9.6 9.80.3 4.8 7.2 7.5 8.0 8.7 9.10.2
APCI (-)
TIC: from Sample 2 (Std 10 ppb APPI) of Std 10 ppb APPI.wiff (Photospray) Max. 4.1e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
2.0e5
4.0e5 4.3
4.1
4.53.7 5.13.43.0 3.32.50.7 2.81.6 2.10.3 1.2 1.4 2.30.2 0.5 2.01.1 4.6 5.2 7.96.15.7 8.45.7
APPI (-)
Br
BrBr
BrBr
Br
HO
Cl
Cl
Cl
ClOH
HO
Br
Br
Br
BrOH
Compound LOD, standard (pg)
LOD, sludge (pg)
LOQ, Sludge (ng/g)
HBCDD 0.029 0.080 0.011
0.005
0.011
TCBPA 0.020 0.041
TBBPA 0.059 0.082
Sensibilita e linearita .rdb (TClBPA): "Linear" Regression ("No" weighting): y = 1.11e+005 x + 151 (r = 0.9999)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0Concentration, ppb
0.00
5.00e4
1.00e5
1.50e5
2.00e5
2.50e5
3.00e5
3.50e5
4.00e5
4.50e5
5.00e5
5.50e5
6.00e5
6.50e5
7.00e5
7.50e5
8.00e5
8.50e5
9.00e5
9.50e5
1.00e6
1.05e6
1.10e6
1.14e6
Sensibilita e linearita .rdb (TBrBPA): "Linear" Regression ("No" weighting): y = 1.48e+005 x + 1.22e+003 (r = 0.9996)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0Concentration, ppb
0.0
1.0e5
2.0e5
3.0e5
4.0e5
5.0e5
6.0e5
7.0e5
8.0e5
9.0e5
1.0e6
1.1e6
1.2e6
1.3e6
1.4e6
1.5e6
Sensibilita e linearita .rdb (HBrCD): "Linear" Regression ("No" weighting): y = 2.9e+005 x + -643 (r = 0.9998)
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0Concentration, ppb
0.0
2.0e5
4.0e5
6.0e5
8.0e5
1.0e6
1.2e6
1.4e6
1.6e6
1.8e6
2.0e6
2.2e6
2.4e6
2.6e6
2.8e6
3.0e6
Calibration from 10 ppt10 pptto 10 ppb of TCBP-A:5uL injectR = 0.9999
Calibration from 10 ppt10 pptto 10 ppb of TBBP-A: 5uL injectR = 0.9999
Calibration from 1 ppt1 ppt to 10 ppb of HBrCD: 5uL injectR = 0.9998
Results: linearity
compound MW n. Br atoms
BDE-47 485.8 4
BDE-99 564.7 5
BDE-100 564.7 5
BDE-153 643.6 6
BDE-154 643.6 6
BDE-183 722.5 7
OBr
Br
Br
Br
OBr
Br
Br
BrBr
OBr
Br
Br
Br Br
OBr
Br BrBr
Br
Br
OBr
Br Br
Br
BrBr
OBr
Br Br
Br
Br
Br
Br
Second group of compounds: PBDEs and TBBPA-bis
compound MW n. Br atoms
BDE-196 801.4 8
BDE-197 801.4 8
BDE-203 801.4 8
BDE-205 801.4 8
BDE-209 959.2 10
TBBPA-bis 943.6 8
OBr
Br BrBr
BrBrBr
Br
O
Br Br
Br
Br
Br
Br Br
Br
OBr
Br BrBrBr
BrBr
Br
O
Br BrBrBr
BrBr
Br
Br
O
Br Br
Br
BrBrBr
Br
Br Br
Br
Br
BrO
Br
BrBr
Br
O
Br
Br
Product ion spectra of PBBPA-bis and selected PBDEs. CE value -40 and -45, APCI source.
-MS2 (748.80) CE (-45): 50 MCA scans from Sample 1 (Product 748.8) of Product 748.8.wiff (Heated Nebulizer) Max. 4.1e5 cps.
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800m/z, Da
0.0
5.0e4
1.0e5
1.5e5
2.0e5
2.5e5
3.0e5
3.5e5
4.0e5
Inte
nsity
, cps
81.0
530.8
332.9 545.8
748.9
161.7
292.6
81Br
81Br 81Br
81Br
O
O
81Br
81Br
81Br
Br
Br
O
Br
Br Br
Br
O
Br
Br
TBBPA-bis
Results: second group of compounds -MS2 (500.00) CE (-27): 1.474 to 1.541 min from Sample 1 (Ramp CE BDE-99) of Ramp CE BDE-99.wiff (Heated Nebulizer) Max. 2.9e4 cps.
50 100 150 200 250 300 350 400 450 500 550m/z, Da
0.0
2000.0
4000.0
6000.0
8000.0
1.0e4
1.2e4
1.4e4
1.6e4
1.8e4
2.0e4
2.2e4
2.4e4
2.6e4
2.8e4
Inte
nsity
, cps
159.5
81.0
500.7
265.7420.7340.7
268.0
O
BrBr
BrBr
BDE-99
Br
O
O-Br
BrBr
Br
MW = 564.7 [M-Br+O]-, MW = 500.8
-MS2 (488.80) CE (-40): 0.050 to 0.704 min from Sample 1 (Ms-Ms BDE 209) of Ms-Ms BDE 209.wiff (Heated Nebulizer) Max. 8.7e4 cps.
50 100 150 200 250 300 350 400 450 500 550m/z, Da
0.0
1.0e4
2.0e4
3.0e4
4.0e4
5.0e4
6.0e4
7.0e4
8.0e4
8.7e4
Inte
nsity
, cps
80.8
78.9
488.5
381.6 409.558.8 328.6
O
BrBr
Br
BDE-209Br
Br
BrBr
BrBr
Br
-Q1: 1.671 to 1.738 min from Sample 2 (spet to di massa del BDE 209 T 400 DP 150) of BDE209 infusione (0.5ppm).wiff (Heated Nebulizer) Max. 4.0e5 cps.
400 500 600 700 800 900 1000m/z, Da
0.0
1.0e5
2.0e5
3.0e5
4.0e5
Inte
nsity
, cps
896.5
486.7
446.4
[M-Br+O]-
[M-C6Br5]-
[M-C6Br5]-
Br
BrO
Br
BrBr
Br
O
[M-CH2CHBrCH2Br]-
-MS2 (736.00) CE (-40): 1.136 to 1.203 min from Sample 1 (Ramp CE BDE-197 bis) of Ramp CE BDE-197 bis.wiff (Heated Nebulizer) Max. 1.3e5 cps.
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800m/z, Da
0.00
1.00e4
2.00e4
3.00e4
4.00e4
5.00e4
6.00e4
7.00e4
8.00e4
9.00e4
1.00e5
1.10e5
1.20e5
Inte
nsity
, cps
78.9
576.6
736.8578.7
392.5
159.8 656.9423.4343.5267.2
O
BrBr
BrBr
BDE-197
BrBr
Br Br[M-Br+O]-
TIC of -MRM (60 pairs): from Sample 1 (std 25 ppb) of APCI std 25 ppb.wiff (Heated Nebulizer) Max. 2.1e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
2.0e4
4.0e4
6.0e4
8.0e4
1.0e5
1.2e5
1.4e5
1.6e5
1.8e5
2.0e5In
tens
ity, c
ps7.1
7.55.86.6
TIC of -MRM (60 pairs): from Sample 1 (std 25 ppb) of APPI std 25 ppb.wiff (Photospray) Max. 4.9e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e4
1.0e5
1.5e5
2.0e5
2.5e5
3.0e5
3.5e5
4.0e5
4.5e5
4.9e5
Inte
nsity
, cps
7.2
6.4
PBDEs: optimized separation by UPLC-MS/MS
BDE-47
BDE-100
BDE-99
BD
E-154
BDE-153BDE-183
BD
E-197
BDE-196
BDE-205
BDE-209
BDE-203
APPI
APCI
Experimental conditions:
•25 μg/L each congener
•Column: C18-BEH 2.1x150mm, 1.7μm, T= 40°C
•H2O/MeOH gradient from 50/50 to 0/100 in 5 min
•Flow = 250 μl/min
• toluene 75μl/min (APPI)
-Q1: 1.424 to 2.463 min from Sample 1 (std 1 ppm scan 600-1000) of scan 600-1000.wiff (Heated Nebulizer), Smoothed Max. 2.5e4 cps.
700 705 710 715 720 725 730 735 740 745 750 755 760m/z, Da
2000.0
4000.0
6000.0
8000.0
1.0e4
1.2e4
1.4e4
1.6e4
1.8e4
2.0e4
2.2e4
2.4e4
746.8
742.8
740.6 744.7
738.7
-Q1: 0.553 to 1.659 min from Sample 1 (Spettro di massa del BDE 203-205) of Spettro di massa del BDE 203-205.wiff (Heated Nebulizer), Smo... Max. 1.8e6 cps.
700 705 710 715 720 725 730 735 740 745 750 755 760m/z, Da
0.0
2.0e5
4.0e5
6.0e5
8.0e5
1.0e6
1.2e6
1.4e6
1.6e6
1.8e6
729.9
736.4738.2
734.4 740.3
732.4 742.5
743.8
-MS2 (736.00) CE (-50): 0.168 to 0.821 min from Sample 1 (Ms-Ms BDE 203-205) of Ms-Ms BDE 203-205.wiff (Heated Nebulizer) Max. 1.2e5 cps.
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800m/z, Da
1.00e4
2.00e4
3.00e4
4.00e4
5.00e4
6.00e4
7.00e4
8.00e4
9.00e4
1.00e5
1.10e51.17e5 736.8
78.9
423.5
575.9 654.7496.6
Br-
Product Ion Scan of 738.8
-MS2 (743.00) CE (-45): 0.084 to 1.139 min from Sample 1 (Ms-Ms del Bis) of Ms-Ms del Bis.wiff (Heated Nebulizer) Max. 4266.2 cps.
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750m/z, Da
500
1000
1500
2000
2500
3000
3500
40004266 743.1
80.7
526.8
541.7330.6
160.0 528.1
Product Ion Scan of 743.1
Br-
Br
BrO
Br
BrBr
Br
O
[M-CH2CHBrCH2Br]-
OBr
Br BrBrBr
BrBr
Br
OBr
Br OBrBr
BrBr
Br
[M-Br+O]-
BDE-203
Br
BrO
Br
BrBr
Br
O
Br
Br
Overlapping of TBBPA-bis and octa-BDE
Optimized separation of octa-BDEs and PBBPA-bis by UPLC-MS/MS
Experimental conditions:
•25 μg/L each congener
•100 μg/L TBBPA-bis
•Column: C18-BEH 2.1x150mm, 1.7μm, T= 40°C
•H2O/MeOH gradient from 50/50 to 0/100 in 5 min
•Flow = 250 μl/min
• toluene 75μl/min (APPI)
2 4 6 8Time, min
0.0
2.0e4
4.0e4
6.0e4
Inte
nsity
, cps
7.2
7.5
2 4 6 8 10Time, min
0
4
4
4
7.2
7.5BDE-205BDE-203
BDE-196
BDE-197TBBPA-bis
2 4 6 8Time, min
0.0
5000.0
1.0e4
1.5e4
2.0e4
2.3e4In
tens
ity, c
ps7.1
7.5
2 4 6 8 10Time, min
7.1
7.5BDE-205BDE-203
BDE-196
BDE-197
TBBPA-bis
APPI
APCI
0.E+00
2.E+05
4.E+05
6.E+05
8.E+05
1.E+06
BDE-47BDE-10
0BDE-99BDE-15
4BDE-15
3BDE-18
3BDE-19
7BDE-19
6BDE-20
3BDE-20
5BDE-20
9TBBPA-bis
Peak
are
a, c
ps
APCI APPI
Peak area and signal-to-noise ratio of investigated BFRs from a standard-mix solution (25 µg L-1 each congener and 100 µg L-1 for TBBPA-bis).
0
500
1000
1500
2000
BDE-47BDE-10
0BDE-99BDE-15
4BDE-15
3BDE-18
3BDE-19
7BDE-19
6BDE-20
3BDE-20
5BDE-20
9TBBPA-bis
sign
al-t
o-no
ise
ratio
APCI APPI
Which source is the best option ?
Take home: APCI allows lower LODs than APPI
What does it happen when BFRs are in the real matrix (sewage sludge) ?
0.E+00
2.E+05
4.E+05
6.E+05
8.E+05
1.E+06
0.E+00
2.E+05
4.E+05
6.E+05
BDE-47BDE-10
0BDE-15
4BDE-15
3BDE-18
3BDE-19
7BDE-19
6BDE-20
3BDE-20
5TBBPA-bis
Peak
are
a
APCI APPI
BDE-99B
Peak area and signal-to-noise ratio of BFRs obtained after PLE extraction (5 g to 0.5 mL) of municipal sludge (average of three replicates). BFRs not present in the sludge were spiked into the final extract at 10 µg L-1
(BDE-183, BDE-196, BDE-203, BDE-205) and 100 µg L-1 (TBBPA-bis), respectively.
0
500
1000
1500
2000
2500
0
100
200
300
BDE-47BDE-10
0BDE-15
4BDE-15
3BDE-18
3BDE-19
7BDE-19
6BDE-20
3BDE-20
5TBBPA-bis
Sign
al-to
-noi
se ra
tio
APCI APPI
BDE-99B
Take home: APCI allows lower LODs than APPI
0.0E+00
1.0E+05
2.0E+05
3.0E+05
BDE-183
BDE-196
BDE-203
BDE-205
TBBPA-bis
Peak
are
a
APCI, stdAPCI, sludgeAPPI, stdAPPI, sludge
BFRs (standard solution or spiked in the sludge extract) by APCI andAPPI. PBDE congeners spiked at 10 µg L-1 and TBBPA-bis at 100 µg L-1
into the final extract of sludge (PLE , 5 g to 0.5 mL).
Take home: negligible ion suppression for APCI
What about ion suppression due to the matrix ?
APCI APPI
Compound LOD, standard (pg)
LOD, sludge (pg)
LOQ, Sludge (ng/g)
LOD, standard (pg)
LOD, sludge (pg)
LOQ, Sludge (ng/g)
BDE-47 0.72 2.1 0.14 6.3 19.0 1.3BDE-99 0.16 0.34 0.023 0.33 1.8 0.12BDE-100 0.24 0.52 0.035 0.56 3.0 0.20BDE-153 0.19 0.27 0.018 0.26 0.43 0.029BDE-154 0.37 0.53 0.036 0.77 1.3 0.087BDE-183 0.10 0.15 0.010 0.11 0.19 0.012BDE-196 0.17 0.32 0.021 0.40 0.75 0.050BDE-197 0.48 0.92 0.062 1.1 2.0 0.13BDE-203 0.15 0.29 0.019 0.21 0.80 0.054BDE-205 0.14 0.27 0.018 0.21 0.75 0.052BDE-209 0.70 2.1 0.14 0.89 2.0 0.15
TBBPA-bis 6.0 9.9 0.66 7.0 9.3 0.55
Performance of the method
The method was succefully validated on a NIST sediment and applied to sludge samples → J. Chrom. A, 2010, 1217, 4601- 4611.
XIC of -MRM (60 pairs): 418.8/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer), Summed <XIC of -MRM (60 pairs): 420.9/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 420.9/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 422.9/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 422.9/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 424.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)> Max. 2.4e4 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
2000.0
4000.0
6000.0
8000.0
1.0e4
1.2e4
1.4e4
1.6e4
1.8e4
2.0e4
2.2e42.4e4
Intens
ity, c
ps
x 0.1
5.244.89
6.745.745.11 7.29
5.40 6.57
6.272.54
PBDEs occurrence in sewage sludge
BDE-47(tetra-BDE)
XIC of -MRM (60 pairs): 496.8/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer), Summed <XIC of -MRM (60 pairs): 498.9/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 498.9/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 500.9/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 500.9/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 502.9/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 502.9/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 504.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)> Max. 2.1e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
2.0e4
4.0e4
6.0e4
8.0e4
1.0e5
1.2e5
1.4e5
1.6e5
1.8e5
2.0e52.1e5
Intens
ity, c
ps
5.74
5.23
6.355.54
BDE-100BDE-99
(penta-BDE)
XIC of -MRM (60 pairs): 576.6/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer), Summed <XIC of -MRM (60 pairs): 578.6/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 578.6/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 580.8/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 580.8/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 582.5/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 582.5/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 584.5/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)> Max. 2.7e5 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
5.0e4
1.0e5
1.5e5
2.0e5
2.5e5
2.7e5
Intens
ity, c
ps
6.34
6.54
5.76
6.01
6.83
BDE-154
BDE-153(esa-BDE)
XIC of -MRM (60 pairs): 654.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer), Summed <XIC of -MRM (60 pairs): 654.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 656.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 656.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 658.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 658.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 660.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 660.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 662.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 662.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)> Max. 1.9e6 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.0
2.0e5
4.0e5
6.0e5
8.0e5
1.0e6
1.2e6
1.4e6
1.6e6
1.8e6
Intens
ity, c
ps
6.54
6.83
7.056.01
BDE-183(epta-BDE)
XIC of -MRM (60 pairs): 732.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer), Summed <XIC of -MRM (60 pairs): 734.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 734.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 736.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 736.7/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 738.7/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 738.8/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 738.8/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 740.6/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 740.6/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 740.8/79.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)>, Summed <XIC of -MRM (60 pairs): 740.8/81.0 Da from Sample 1 (RSM_1) of RSM_1.wiff (Heated Nebulizer)> Max. 1.3e6 cps.
1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0Time, min
0.00
1.00e5
2.00e5
3.00e5
4.00e5
5.00e5
6.00e5
7.00e5
8.00e5
9.00e5
1.00e6
1.10e6
1.20e61.29e6
Intens
ity, c
ps
7.05
7.15
6.71 BDE-205
BDE-203
BDE-196
BDE-197
(octa-BDE)
Conclusions• UPLC-MS/MS proved to be very effective for the determination
of PBDEs, TBBPA-bis, TCBPA, TBBPA and HBCDs.
• LODs are in the range of 0.020 - 6.0 pg.
• As for PBDEs, APCI gave better sensitivity than APPI (due to less background).
• Due to the high resolving power of UPLC, it is possible to detect and quantify a big number of PBDE congeners.
AcknowledgmentThis study was part of the EU Neptune project financed by the EU Commission.
http://www.eu-neptune.org
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