Target and non-target water testing - claim and reality · Zweckverband Landeswasserversorgung W....

Zweckverband Landeswasserversorgung

W. Schulz, T. Lucke, K. Wenger and R. Winzenbacher

Zweckverband Landeswasserversorgung Betriebs- und Forschungslaboratorium

Langenau

[email protected]

Target and non-target water testing - claim and reality -

analytica 2016 „Sciex Innovation Day“ Wednesday, May 11th


River water abstracted from the Danube

Danube

Raw water pump station Leipheim

Commissioning: 1973 Legal abstraction: 2300 l/s

Treatment capacity Waterworks Langenau: 1300 l/s


Neu-Ulm

Ulm

Langenau

Günzburg

Leipheim

Wiblingen

Erbach

Dellmensingen

Abstraction point

To waterworks Langenau

Central sewage treatment plant

Direct abstraction of Danube water in the downstream of the Cities of Ulm and Neu-Ulm


Pharmaceuticals

Iodinated X-ray contrast media

Metabolites

Pesticides Industrial chemicals

?

Organic micropollutants in the river water


Danube Features

Drinking water Features

Question

● removable

● ● not or partial removable

● transformation product

Removal and formation of organic trace substances during water treatment

Danube surface water

Drinking water

mass - RT scatterplots


0 100 200 300 400 500 600 700 800 900

Concentration (ng/L)

0e0

1e5

2e5

3e5

4e5

5e5

6e5

7e5

8e5A

rea

Calibration for Valsartansäure_2: y = 840.70071 x + 489.99720 (r = 0.99991) (weighting: None)

Standard

Excl. Standard

OHO

NN

NN

Valsartan acid

10 ng/L 50 ng/L 100 ng/L

AB Sciex QTRAP 6500

1300 cps 7000 cps 15000 cps

Concentration [ng/L]

Are

a


1 2 3 4 5 6 7 8 9

Visible Row Index

0

5

10

15

20

25

30

35

Cal

cula

ted

Con

cent

ratio

n

Mischprobe Donau 24.07.2014



Mischprobe Donau 30.07.2014Mischprobe Donau 25.07.2014






Valsartansäure_2

OHO

NN

NN

Concentration of valsartan acid in the river Danube

Con

cent

ratio

n [n

g/L]

Injection volume: 100 µL


0 100 200 300 400 500 600 700 800 900

Concentration (ng/L)

0.0e0

5.0e5

1.0e6

1.5e6

2.0e6

2.5e6

3.0e6

3.5e6

Are

a

Calibration for O-Desmethylvenlafaxine_1: y = 4442.91208 x + 412.74888 (r = 0.99972) (weighting: None)

Standard

Excl. Standard

O-Desmethyl-Venlafaxine C16H25NO2 m/z: 264,1958

O H

O H

N

C H3

C H3

10 ng/L 50 ng/L 100 ng/L

API 6500 Qtrap

12000 cps 50000 cps 110000 cps

Concentration [ng/L]

Are

a


1 2 3 4 5 6 7 8 9

Visible Row Index

0

1

2

3

4

5

6

7

8

9

10

Cal

cula

ted

Con

cent

ratio

n









O-Desmethylvenlafaxine_1

6 ng/L

2 ng/L

7 ng/L

Concentration of O-Desmethyl-venlafaxine in the river Danube

Con

cent

ratio

n [n

g/L]

Injection volume: 100 µL


LC-QqQ-MS

GC- Q-MS

Acesulfam

Metformin

Glyphosate

Carbamazepine

Sucralose

Fluoxetine (PROZAC)

Naphthalin sulfonsäure

DDT

Benzo(a)pyrene

Result: Concentration of the targets

Targets

Strategy Target analysis

Trace org. substances


Trace org. substances

LC-QqQ-MS

GC- Q-MS

Strategy Non-Target-Screening

GC-HRMS

Result:

ass RT formular

279,0937 10 C12H11F2N5O

266,0957 5,2 C12H16N3O2S

217,0681 2,3 C13H13OS

324,2753 12,7 C15H32N8


0

100

200

300

400

500

600

700

800

900

1000

2 4 6 8 10 12 14 16 18

Retentionszeit [min]

Mas

se [

u]

ESI+: 799

ESI-: 233

Total: 1032

Mass – RT scatter plot Groundwater sample

Retention time

Mas

s m

/z


0

100

200

300

400

500

600

700

800

900

1000

2 4 6 8 10 12 14 16 18

Retentionszeit [min]

Mas

se [

u]

Retention time

Mas

s m

/z

ESI+: 3765

ESI-: 1144

Total: 4909

Mass – RT scatter plot Groundwater industrially influenced


Danube Features

Drinking water Features

Question

● removable

● ● not or partial removable

● transformation product

Removal and formation of organic trace substances during water treatment

Danube surface water

Drinking water

mass - RT scatterplots


Non-target screening Sample Number of components (identical)

KW 1 251 / 170 (85)

KW 2 374 / 214 (114)

KW 3 175 / 287 (65)

KW 4 286 / 301 (98)

0 4 8 12 16

Retentionszeit [ min ]

0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser

0 4 8 12 16


0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser

Scatter plots for raw and drinking water

Danube raw water Water treatment Drinking water

Non-Target-Screening: Comparison of Danube raw water and drinking water


Suspected target screening: Integration of data bases

0 4 8 12 16


0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser

0 4 8 12 16


0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser


Suspected target screening: Integration of data bases

N

N

N

N

N

0 4 8 12 16


0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser

0 4 8 12 16


0

200

400

600

800

1000

Mas

se [

u ]

Donaurohwasser


Correlation between QqQ (MRM) and TOF (MRMHR) of real water samples

concentration ng/L direct injection 100 µL


concentration ng/L direct injection 100 µL

Correlation between QqQ (MRM) and TOF (MRMHR) of real water samples


Background of different columns

UAqC18 (Restek)

Zorbax (Agilent)

Synergi polar RP (Phenomenex)

stationary phase

C18 C18 Phenylphase with polar endcapping

column dimension

250 x 4,6 mm 150 x 2,1 mm 150 x 4,6 mm

particle size 5 µm 3,5 µm 4 µm


UAqC18 and Synergi polar RP

Eluent A: MilliQ + 0,1 % HCOOH Eluent B: Acetonitril + 0,1 % HCOOH

Zorbax

Eluent A: MilliQ + 0,1 % HCOOH Eluent B: Acetonitril + 0,1 % HCOOH

0

20

40

60

80

100

0 10 20 30

Elue

nt B

[%]

time [min]

0

20

40

60

80

100

0 10 20 30

Elue

nt B

[%]

time [min]

HPLC method


• Metformin 130.10872 • Carbamazepin 237.10224 • Diclofenac 296.02396 • Metoprolol 268.19072 • Sulfamethoxazol 254.05939 • Amidotrizoesäure 614.77694 • Iopamidol 777.8614 • Iomeprol 777.8614 • Carboxy-Aciclovir 240.07273 • Guanylharnstoff 103.06144 • Lamotrigine-N-Oxid 272.01004 • Sulpirid-N-Oxid 358.14312 • Amisulpirid-N-Oxid 386.17442 • Tramadol-N-Oxid 280.19072 • Atrazin 216.10105 • Isoproturon 207.14919 • Desethylatrazin 188.06975 • Desphenyl-Chloridazon 146.01157 • 1-H-Benzotriazol 120.05562 • Tolyltriazol (Isomerengemisch) 134.07127 • 2,4,6-Triamnio-s-Triazin 127.07267

List of substances (AK-MIX 10 µg/L) (1)

Injection volume 10 µL


• Acesulfam 164.00121 • Metoprololsäure 268.15433 • Aciclovir 226.09347 • Lamotrigin 256.01513 • Sulpirid 342.1482 • Amisulprid 370.1795 • Tramadol 264.19581 • Isoproturon-monodemethyl 193.13354 • Isoproturon-didemethyl 179.11789 • 4-Hydroxy-diclofenac 312.01888 • Carbamazepin-Epoxid 253.09715 • Acetyl-Sulfamethoxazol 296.06995 • 4-Nitro-sulfamethoxazol 268.03865 • Desethyl-deisopropylatrazin 146.0228 • Atrazin-2-hydroxy 198.13494 • Desethylatrazin-2-hydroxy 170.10364 • Methyl-Desphenyl-Chloridazon 160.02722 • Chloridazon 222.04287 • 5,6-Dimethylbenzotriazol 148.08692 • 4-Hydroxy-1H-benzotriazole 136.05054 • 1-Hydroxy-benzotriazole 136.05054 • Iothalaminsäure 614.77694 • HMMM 391.22996

Injection volume 10 µL

List of substances (AK-MIX 10 µg/L) (2)


0,00E+00

1,00E+06

2,00E+06

3,00E+06

4,00E+06

5,00E+06

6,00E+06

7,00E+06

Inte

nsi

tät

[cp

s]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

100

200

300

400

500

600

700

800

900

1000

1100

Mas

s/C

harg

e [D

a]

Time [min]

TIC AK-Mix UAqC18 (Restek)


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

Time, min

0.0e0

5.0e3

1.0e4

1.5e4

2.0e4

2.5e4

3.0e4

3.5e4

4.0e4

4.5e4

5.0e4

5.5e4

6.0e4

6.5e4

7.0e4

Inte

nsity

, cps

AK-Mix UAqC18 (Restek)

XIC TOF-MS


0,00E+00

5,00E+05

1,00E+06

1,50E+06

2,00E+06

2,50E+06

3,00E+06

Inte

nsi

tät

[cp

s]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 100

200

300

400

500

600

700

800

900

1000

1100

Mas

s/C

harg

e [D

a]

Time [min]

TIC AK-Mix Zorbax (Agilent)


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

Time, min

0.0e0

1.0e4

2.0e4

3.0e4

4.0e4

5.0e4

6.0e4

7.0e4

8.0e4

9.0e4

1.0e5

1.1e5

1.2e5

1.3e5

1.4e5

1.5e5

Inte

nsity

, cps

AK-Mix Zorbax (Agilent)

XIC TOF-MS


0,00E+00

5,00E+06

1,00E+07

1,50E+07

2,00E+07

2,50E+07

3,00E+07

Inte

nsi

tät

[cp

s]

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

100

200

300

400

500

600

700

800

900

1000

1100

Mas

s/C

harg

e [D

a]

Time [min]

TIC AK-Mix Synergi polar RP (Phenomenex)


Background masses

Only the intensity of mass 149,044 m/z could be reduced by washing

Synergi polar RP von Phenomenex

149,044153,037 389,160


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32

Time, min

0.0e0

5.0e3

1.0e4

1.5e4

2.0e4

2.5e4

3.0e4

3.5e4

4.0e4

4.5e4

5.0e4

Inte

nsity

, cps

AK-Mix Synergi polar RP (Phenomenex)

at the beginning: 40 of 46 standards are detected after 100 injections: 44 of 46 standards are detected But considerable intensity loss in comparison with the UAqC18 and Zorbax column

XIC TOF-MS


0,00E+00

5,00E+06

1,00E+07

1,50E+07

2,00E+07

2,50E+07

3,00E+07

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

UAqC18

Zorbax

Synergi polar RP

TIC of AK-Mix


0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

Zorbax

0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

0 10 20 30

Inte

nsi

ty [

cps]

time [min]

ohneSpülen

Synergi polar

UAqC18

background reduced significantly by washing

XIC of Diclofenac


UAqC18 Zorbax

Synergi polar RP

0,00E+00

2,00E+02

4,00E+02

6,00E+02

8,00E+02

1,00E+03

1,20E+03

1,40E+03

0 10 20 30

Inte

nsi

ty [

cps]

time [min]

ohneSpülen

0,00E+00

2,00E+02

4,00E+02

6,00E+02

8,00E+02

1,00E+03

1,20E+03

1,40E+03

0 5 10 15 20 25 30

inte

nsi

tyt

[cp

s]

time [min]

0,00E+00

2,00E+02

4,00E+02

6,00E+02

8,00E+02

1,00E+03

1,20E+03

1,40E+03

0 5 10 15 20 25 30

Inte

nsi

tyt

[cp

s]

time [min]

XIC of Carboxy-Aciclovir


0,00E+00

1,00E+03

2,00E+03

3,00E+03

4,00E+03

5,00E+03

6,00E+03

7,00E+03

8,00E+03

9,00E+03

1,00E+04

0 10 20 30

Inte

nsi

ty [

cps]

time [min]

ohneSpülen

UAqC18 Zorbax

Synergi polar RP

0,00E+00

1,00E+03

2,00E+03

3,00E+03

4,00E+03

5,00E+03

6,00E+03

7,00E+03

8,00E+03

9,00E+03

1,00E+04

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

0,00E+00

1,00E+03

2,00E+03

3,00E+03

4,00E+03

5,00E+03

6,00E+03

7,00E+03

8,00E+03

9,00E+03

1,00E+04

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

XIC of 4-Hydroxy-Diclofenac


0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

1,60E+04

1,80E+04

0 10 20 30

Inte

nsi

tät

[cp

s]

time [min]

ohneSpülen

UAqC18 Zorbax

Synergi polar RP

0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

1,60E+04

1,80E+04

0 10 20 30

Inte

nsi

ty [

cps]

time [min]

0,00E+00

2,00E+03

4,00E+03

6,00E+03

8,00E+03

1,00E+04

1,20E+04

1,40E+04

1,60E+04

1,80E+04

0 5 10 15 20 25 30

Inte

nsi

ty [

cps]

time [min]

Keine Verbesserung durch Spülen

XIC of Desethylatrazin-2-hydroxy


Integrated monitoring sample

LC-HRMS/MS

quantitativ Target

qualitativ Non-Target


Thank you for your attention

Target and non-target water testing - claim and reality · Zweckverband Landeswasserversorgung W....

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Transcript of Target and non-target water testing - claim and reality · Zweckverband Landeswasserversorgung W....