comparison of modern lc- ms/ms techniques for analysis of
TRANSCRIPT
Comparison of Modern LC-MS/MS Techniques for
Analysis of TOrCs in Water
Tarun Anumol, Shane Snyder NEMC 2014
Introduction
Current Trends
Science Advisory Board
Current Trends
Automation
Traditional Extraction Techniques
Analysis of TOrCs in Water
Analysis of TOrCs by C-SPE
Sample collection and Transport
Surrogate addition
Extraction (SPE) by Autotrace
Evaporation
Analysis
Sample Transport
Sample Volume
Analysis of TOrCs by OSPE
Surrogate Addition into 5 mL of sample
Analysis (1700 µL injection volume)
Instrument Setup
Instrument Setup
Agilent Flexcube connected to 6460 MS/MS
Large Volume Direct Injection
Surrogate Addition into 1 mL of sample
Analysis (100 µL injection volume)
Trace Organic Chemicals
Atenolol (ß-blocker) Atrazine (Herbicide)
Bisphenol A (plasticizer) Caffeine (stimulant)
Benzophenone (UV-blocker)
Carbamazepine (Anti-seizure)
DEET (Insect-repellant) Dexamethasone (glucocorticoid) Trimethoprim (Antibiotic)
Estrone (Hormone) Fluoxetine (Anti-depressant) Gemfibrozil (Anti-cholesterol)
Trace Organic Chemicals
Ibuprofen (Analgesic) Meprobamate (Anti-anxiety)
PFBS (Fluoro-surfactant) PFOA (Fluoro-surfactant)
Naproxen (Pain-reliever)
PFOS (Fluoro-surfactant)
Primidone (Anticonvulsant) Simazine (Herbicide) Sulfamethoxazole (Antibiotic)
TCPP (Flame-retardant) Triclocarban (Anti-microbial) Triclosan (Anti-microbial)
Analytical Method
Ate
nolo
l
Caf
fein
e Tr
imet
hopr
im
Prim
idon
e
Mep
roba
mat
e
Diphenhydramine
Dilt
iaze
m
TCE
P D
EE
T Te
stos
tero
ne
Nap
roxe
n P
FOA TC
PP
Ben
zoph
enon
e D
iclo
fena
c Ib
upro
fen Gem
fibro
zil
PFO
S
Tric
loca
rban
Tric
losa
n
Sim
azin
e
Pre
dnis
one
Ben
zotri
azol
e
Atra
zine
True Recoveries in WW
7
Atenolol d
3C13
Caffein
e 3
Trimeth
oprim d 5
Primidone d
3
Mepro
bamate
d 6 C13
Sulfameth
oxazo
le 5
Diphenhyd
ramine d
3
Ditiaze
m d
10
Carbam
ezap
ine d 4
Dexam
ethas
one d5
Fluoxetin
e d
12
TCEP d5
Atrazin
e d 6
DEET d
10
Benzo
phenone d
4
Propylp
araben
d 3 d1C13
Napro
xen_
4C13
PFOA 3
Ibuprofen
d 4 C13
PFOS 6
Gemfib
rozil
d 12
C13
Triclosa
n
0
25
50
75
100
125
150 Conventional SPEOnline SPEDirect Injection
Reco
very
(%)
Method Detection Limit
8 replicates using Glaser et al. method
Atenolol
Atrazin
e
Benzo
phenone
Benzo
triaz
ole
Bisphen
ol A
Caffein
e
Carbam
ezap
ine
Clofibric
Acid
DEET
Diclofen
ac
Diphenhyd
ramine
Ditiaze
m
Fluoxetin
e
Gemfib
rozil
Hydrac
ortiso
ne
Hydro
chloro
thiazide
Ibuprofen
Mepro
bamate
Napro
xen
Norges
trel
PFHxAPFOA
PFOS
Primidone
Propran
olol
Propylp
araben
Simaz
ine
Sulfameth
oxazo
leTCEP
TCPP
Testoste
rone
Tricloca
rban
Triclosa
n
Trimeth
oprim
0.0625
0.125
0.25
0.5
1
2
4
8
16
MDL (ng/L)
Con
cent
ratio
n (n
g/L)
Matrix Effects
7
Atenolol d
5
Atrazin
e d
10
Benzo
phenone d
4
Benzo
triaz
ole d
12C13
Bisphen
ol A
3C13
Caffein
e
10
Carbam
ezap
ine d
6
DEET d6C13
Diclofen
ac
5
Diphenhyd
ramine d
3
Ditiaze
m d 5
Fluoxetin
e d
6
Gemfib
rozil
d
Ibuprofen
d3 3
Mepro
bamate
d 3 d1C13
Napro
xen
2 C13
PFHxA
4 C13
PFOA 4 C13
PFOS 5
Primidone d
4
Propylp
araben
d 6C13
Sulfameth
oxazo
le 12
TCEP d6 C13
Tricloca
rban
12C13
Triclosa
n 3
Trimeth
oprim d
Averag
e-30
-20
-10
0
10
20
30
40
50
60
70
80
90
100SW WWE (1:5 dil) WWE
Mat
rix E
ffect
(%)
Ion Suppression: Online SPE
Ultrapure water
Wastewater effluent (0.2 um filtered)
Carbamazepine_d10 Concentration: 100 ppt Injection Vol: 1.5 mL Mass: 150 pg
Ion Suppression: Conventional SPE
Ultrapure water
Wastewater effluent (0.2 um filtered)
Carbamazepine_d10 Concentration: 50 ppb Injection Vol: 3 µL Mass: 150 pg
Ion Suppression: Direct Injection
Ultrapure water
Wastewater effluent (0.2 um filtered)
Carbamazepine_d10 Concentration: 3 ppb Injection Vol: 50 µL Mass: 150 pg
Ion Suppression Effects
Comparison of 3 methods
Atenolol d
7
Sulfameth
oxazo
le 13
C3
Carbam
azep
ine d10
DEET d6
TCEP d12
Gemfib
rozil
d60
20
40
60
80
100
Conventional SPE (500 fold)Online SPEDirect Injection
Surr
ogat
e R
ecov
ery
(%)
Ion Suppression Effects
Atenolol
Mepro
bamate
Sulfameth
oxazo
le
Carbam
azep
ineDEET
TCEP
Gemfib
rozil
0.1
1
10
100
1000
CSPEOSPELVI
Met
hod
Det
ectio
n Li
mit
(ng/
L)
Ion Suppression Effects
Atenolol
Mepro
bamate
Sulfameth
oxazo
le
Carbam
azep
ineDEET
TCEP
Gemfib
rozil
0.1
1
10
100
1000
CSPE-MRL
OSPE-MRL
LVI-MRL
Met
hod
Rep
ortin
g Li
mit
(ng/
L)
Analysis of Emerging Contaminants in Water
Conventional SPE Method Online SPE Method Direct Injection Method
1 L sample 1.5 mL sample 0.1 mL sample
0.01-10 ng/L
36 CECs
5 hours
0.1-20 ng/L
33 CECs
30 min
10-100 ng/L
21 CECs
15 min
7
Atenolol d
3C13
Caffein
e 3
Trimeth
oprim d 5
Primidone d
3
Mepro
bamate
d 6 C13
Sulfameth
oxazo
le 5
Diphenhyd
ramine d
3
Ditiaze
m d
10
Carbam
ezap
ine d 4
Dexam
ethas
one d5
Fluoxetin
e d
12
TCEP d5
Atrazin
e d 6
DEET d
10
Benzo
phenone d
4
Propylp
araben
d 3 d1C13
Napro
xen_
4C13
PFOA 3
Ibuprofen
d 4 C13
PFOS 6
Gemfib
rozil
d 12
C13
Triclosa
n
0
25
50
75
100
125
150 Conventional SPEOnline SPEDirect Injection
Reco
very
(%)
Conclusions q Online SPE allows sensitive analysis of trace organics in water while
allowing significant time and labor savings.
q Method has been proven to be robust in several different water matrixes.
q Online SPE is significantly less affected by ion suppression compared with conventional offline extraction techniques.
q LVI is currently not sensitive enough to attain desired MRLs but offers promise with rapid increase in sensitivity of newer mass spectrometers.
q Use of online SPE with accurate mass detectors (ToF & Q-ToF) could allow for real-time analysis of trace unknowns in water.
Acknowledgements
Agilent Technologies Ø Joe Weitzel Ø Dr. Sheher Mohsin
Snyder Research Lab
