comparison of analytical methods for analysis of emerging ... · agilent 1290 flexcube integrated...

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

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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

QUESTIONS ???

tarun.anumol@agilent.com

Ph (O): 302-636-1517

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