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Comparison of Analytical
Methods for Analysis of
Emerging Organic
Contaminants in Water
Tarun Anumol
Sheher Mohsin
Jerry Zweigenbaum
Agilent Technologies
Shane Snyder
University of Arizona
July 28, 2015 Confidentiality Label 1
E m e r g i n g O r g a n i c C o n t a m i n a n t sC a t e g o r i e s
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WERF (2008)
GC
Who Cares?Why we monitor
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• Public Perception
• Health & Safety Concerns
• Potential Government Regulations
Who Cares?Climate Change, Draught
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AnalysisWater Matrices
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Traditional Extraction TechniquesSample Preparation
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Conventional MethodSolid Phase Extraction
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Sample collection
Surrogate addition
(200 ng/sample)
Extraction (SPE)
Evaporation
Analysis
Filtering
Sample VolumesReduction in sample volume, cost of transport
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Sample Volume
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Automated Online SPEReduction in labor, faster analysis
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Agilent 1290 FlexcubeIntegrated online SPE system
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Solvents for LC
Only one LC pump
Triple quad
MS for
quantification
Solvents for
SPE
Configuration
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10
9
76
2
3
4
5
Binary
Pump
SPE
cartridge 1
Flex
cube
pump
Sample
Injection
Loop
Analytical
Column
SPE
cartridge 2
1
Mass
Spectrometer
Waste
Flexcube Pump Flow Path
Binary Pump Flow Path
Equilibrating
Loading
8
Configuration
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10
9
8
76
2
3
4
5
Binary
Pump
SPE
cartridge 1
Flex
cube
pump
Sample
Injection
Loop
Analytical
Column
SPE
cartridge 2
1
Mass
Spectrometer
Waste
Flexcube Pump Flow Path
Binary Pump Flow Path
Elution
Loading
Online SPE LC-MS/MSWorkflow
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Sample
Collection
(1-20 mL)
Surrogate
Addition (0.3
ng/sample)
Automated
Extraction
(Online)
Analysis
Evolution of Mass Spectrometers
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Agilent 6410 (50:1) Agilent 6430 (300:1)
Agilent 6460 (1,000:1)Agilent 6490/6495 (10,000:1)
() denotes minimum S/N for 1 pg reserpine on column
Large Volume Injection (LVI) LC-MS/MSWorkflow
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Sample
Collection
(0.1-5 mL)
Surrogate
Addition (0.1
ng/sample)
NO Extraction Analysis
Emerging Organic Chemicals
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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)
Emerging Organic Chemicals
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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)
LC ConditionsLinear Gradient
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LC Method
0 1 2 3 4 5 6 7 8 9 10 11 12 13 140
20
40
60
80
100A (%)
Time (min)
Gra
die
nt
(%)
A: Water + 0.1% Acetic Acid
B: ACN + 0.1% Acetic AcidAgilent 1290
Infinity LC
Poroshell EC 120
C-18, 2.1x50 mm
Method Detection Limits
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MDL
Method:
Glaser et
al. (1981)
7 replicates
Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Dex
amet
hasone
Dic
lofe
nac
Dip
henhyd
ram
ine
Diti
azem
Gem
fibro
zil
Ibupro
fen
Mep
robam
ate
Nap
roxe
n
PFO
A
PFO
S
Prim
idone
Sulfa
met
hoxazo
le
TCEP
Triclo
carb
an
Trimet
hoprim
0
5
10
1550
100
150
200
250400
600Conventional SPE
Online SPE
Direct Injection
Me
tho
d D
ete
cti
on
Lim
it (
ng
/L)
Ion Suppression Comparison of methods
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Conventional SPE Online SPE Direct Injection
Matrix Effects in Surface Water
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Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Dex
amet
hasone
Dic
lofe
nac
Dip
henhyd
ram
ine
Diti
azem
Gem
fibro
zil
Ibupro
fen
Mep
robam
ate
Nap
roxe
n
PFO
A
PFO
S
Prim
idone
TCEP
Triclo
carb
an
Trimet
hoprim
-50
-25
0
25
50
75
100
125
Conventional SPE
Online SPE
Direct Injection
Ma
trix
Eff
ec
ts (
%)
Matrix Effects in Wastewater Effluent
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Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Dex
amet
hasone
Dic
lofe
nac
Dip
henhyd
ram
ine
Diti
azem
Gem
fibro
zil
Ibupro
fen
Mep
robam
ate
Nap
roxe
n
PFO
A
PFO
S
Prim
idone
TCEP
Triclo
carb
an
Trimet
hoprim
-50
-25
0
25
50
75
100
125
Conventional SPE
Online SPE
Direct Injection
Ma
trix
Eff
ec
ts (
%)
Method Detection Limits
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Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Diti
azem
Ibupro
fen
Nap
roxe
n
PFO
A
Prim
idone
TCEP
Trimet
hoprim
0
10
20
30
40
50
60
70
80
90
100150
200
250
Conventional SPE
Online SPE
Direct Injection
Me
tho
d D
ete
cti
on
Lim
it (
ng
/L)
Method Reporting Limits in Wastewater EffluentMRL = MDL*100/Surrogate Recovery (%)
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Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Diti
azem
Ibupro
fen
Nap
roxe
n
PFO
A
Prim
idone
TCEP
Trimet
hoprim
0
10
20
30
40
50
60
70
80
90
100
200
Conventional SPE
Online SPE
Direct Injection
Me
tho
d R
ep
ort
ing
Lim
it (
ng
/L)
ReproducibilitySeven replicates of WW effluent samples
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Ate
nolol
Atraz
ine
Ben
zophen
one
Caf
fein
e
Car
bamez
apin
e
DEE
T
Dex
amet
hasone
Dic
lofe
nac
Dip
henhyd
ram
ine
Diti
azem
Gem
fibro
zil
Ibupro
fen
Mep
robam
ate
Nap
roxe
n
PFO
A
PFO
S
Prim
idone
TCEP
Triclo
carb
an
Trimet
hoprim
0
5
10
15
2030
40
50
60
Conventional SPE
Online SPE
Direct Injection
Rep
rod
ucib
ilit
y a
s R
SD
(%
)
Conclusions
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Online SPE allows sensitive analysis of trace organics in water
while allowing significant time, labor and reagent savings.
Conventional SPE can be significantly affected by ion
suppression compared with online SPE and LVI techniques
especially for multi-residue methods.
LVI may currently not be sensitive enough to attain desired MRLs
in finished drinking water but offers promise with rapid increase in
sensitivity of newer mass spectrometers.
Use of online SPE with accurate mass detectors (ToF & Q-ToF)
could allow for real-time analysis of trace unknowns in water.
References
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Conventional offline SPE method:• Anumol, T.; Merel, S.; Snyder, S., High Sensitivity HPLC Analysis of Contaminants of Emerging Concern in
Water using the Agilent 6460 Triple Quadrupole LC/MS System. Agilent Application Note, 2012, (5991-1412EN).
• Anumol, T.; Merel, S.; Clarke, B.; Snyder, S., Ultra high performance liquid chromatography tandem mass spectrometry for rapid analysis of trace organic contaminants in water. Chemistry Central Journal 2013, 7, (1), 104.
Automated online SPE method:• Anumol, T.; Mohsin, S.; Snyder, S., Sensitive LC/MS quantitation of trace organic contaminants in water with
online SPE enrichment. Agilent Application Note 2013, (5991-1849EN).
• Anumol, T.; Snyder, S. A., Rapid analysis of trace organic compounds in water by automated online solid-phase extraction coupled to liquid chromatography–tandem mass spectrometry. Talanta 2015, 132, (0), 77-86.
Direct injection method:• Anumol, T.; Wu, S.; Merel, S.; Mohsin, S.; Snyder, S., Analysis of Trace Organic Contaminants in Water by
Direct Injection Using Agilent 6490 LC/MS/MS with Pos/Neg Switching. Agilent Application Note 2013, (5991-2732EN).
• Anumol, T,; Wu, S.; DosSantos, M M.; Daniels, K D.; Snyder, S., Rapid direct injection LC-MS/MS method for analysis of prioritized indicator compounds in wastewater effluent. Environmental Science: Water Research & Technology 2015