Sara VALSECCHI, Stefano POLESELLO CNR-IRSA, Water …...Perfluoroalkyl acids Two primary classes of...

Sara VALSECCHI, Stefano POLESELLO

CNR-IRSA, Water Research Institute

Brugherio, Italy

[email protected]

Conventional

Volume

Sample Loop

Large Volume

Sample Loop

Preconcentration

Column

1.9µm Hypersil Gold

Analytical Column

Thermo solution: EQUAN system

EQUAN Filling Large Volume Sample Loop

EQUAN Sample to preConcentration Column

EQUAN Transfer to Analytical Column

EQUAN preConcentration Column washing

& LC/MS/MS Analysis

On-line vs off-line SPE extraction Pro

Small sample volume (up to 20 mL)

Limited sample handling (only filtration (centrifugation) and matrix modification if needed)

Reduction of total analytical time

Green Chromatography

Cons

Less choice in extraction phases respect to off-line SPE

No replicates on the same sample extract

No possibility to add an internal standard after extraction, but only as a surrogate before extraction

12 25

On-line vs off-line SPE extraction Pro

Small sample volume (up to 20 mL)

Limited sample handling (only filtration and matrix modification if needed)

Reduction of total analytical time

Green Chromatography

Cons

Less choice in extraction phases respect to off-line SPE

No replicates on the same sample extract

No possibility to add an Recovery Standard (IS type 1) after extraction, but only as a Surrogate (IS type 2) prior to sample extration

Perfluoroalkyl acids

Widely diffused in the environment: additives in industrial and consumer product (protective coating for textiles, paper treatment, metal plating, pesticides etc)

Water soluble, persistent and bioaccumulable compounds

Perfluoroalkyl acids Two primary classes of perfluorinated acids

Need for a multiresidue analytical method

PFOS included in the new upcoming Priority List of the WFD

Perfluoroalkyl Sulfonates

PFBS C4F9SO3-

PFHS C6F13SO3-

PFOS C8F17SO3-

PFDS C10F21SO3-

Perfluoroalkyl Carboxylic Acids

PFBA C3F7COOH

PFPeA C4F9COOH

PFHxA C5F11COOH

PFHpA C6F13COOH

PFOA C7F15COOH

PFNA C8F17COOH

PFDA C9F19COOH

PFUnA C10F21COOH

PFDoA C11F23COOH

PFTrA C12F25COOH

PTFA C13F27COOH

LC-MS/MS analytical methods

Perfluorinated compounds:

Liquid Chromatography: Thermo Accela 1250 pump

TRAP Column: 50x2.1 mm (1.9 µm) Thermo GOLD Hypersil (between

the HPLC pump and the injection valve)

Column: 50x2.1 (1.9 µm) Thermo GOLD PFP

Mobile Phase: [A] 2mM NH4OAc+5%MeOH; [B] MeOH

Flow Rate = 300 µL/min

Column Temperature: ambient

Gradient method

Mass Spectrometry: Thermo Quantum Access Max

• ESI in negative mode

• MRM

RT: 7.51 - 10.02

8 9 10

Time (min)

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10

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8.438.878.42

8.88 9.10

9.118.21

8.219.12

8.20

9.139.36

8.199.38

8.18 9.63

NL:4.34E6

TIC MS 200ppt_pH7-8_01

LC-MS/MS analytical methods RT: 6.52 - 12.13

7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0

Time (min)

0

50

100

0

50

100

0

50

100

0

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0

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0

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100

RT: 8.23AA: 215563

RT: 8.54AA: 149810

RT: 8.45AA: 481991

RT: 8.86AA: 164751

RT: 8.67AA: 1578497 RT: 9.23

AA: 2899073

RT: 8.61AA: 44487

RT: 8.90AA: 253706

RT: 9.62AA: 575933

RT: 9.84MA: 5969 10.26 10.729.487.67 7.997.46 9.01 10.898.37 11.487.32 8.60 11.247.11 12.1111.676.70

RT: 9.15AA: 71196

RT: 10.05AA: 75323

RT: 9.43MA: 48643

RT: 10.49MA: 64211

10.4610.579.497.07 7.597.09 8.17 11.388.03 11.088.52 10.24 11.429.629.378.67 8.86 12.056.876.64

NL: 7.10E4

TIC F: - c ESI SRM ms2 312.892 [119.130-119.132, 268.897-268.899] MS ICIS TWM23may_00

NL: 1.50E5


NL: 6.38E5


NL: 1.08E5

TIC F: - c ESI SRM ms2 462.908 [218.923-218.925, 418.868-418.870] MS TWM23may_00

NL: 3.65E4


NL: 1.67E4

TIC F: - c ESI SRM ms2 562.902 [268.810-268.812, 518.832-518.834] MS TWM23may_00

PFUnA

PFHpA

PFOA

PFNA

PFDA

PFHxA

Widely diffused in urban discharges, surface and ground waters

Sources: hospitals, household medicines, breeding farm

Large number of possible pollutants, belonging to very different classes: acids, bases and neutral compounds

Some of them are included in the upcoming Priority List of the WFD: Diclofenac, 17-ethinylestradiol

Need for a multiresidue analytical method

Pharmaceutical residues

“Our” Pharmaceutical Residues EPA 1694 Group1 EPA 1694 Group2 EPA 1694 Group4

Cotinine Sulfamethoxazole Enrofloxacin Epitetracycline Albuterol

Acetaminophen Diphenhydramine Azithromicin Oxytetracycline Ranitidine

1,7-Dimethylxanthine Diltiazem Tylosin Doxycicline Cimetidine

Codeine Carbamazepine Sarafloxacin Demeclocycline

Caffeine Erythromycin Roxithromicin Clorotetracycline

Trimethoprim Fluoxetine Cloxacillin Tetracycline

Thiabendazole Digoxin Norfloxacin Anhydrotetracycline

Clarithromicin Lincomycin Lomofloxacin

Ampicillin Sulfadiazine Oxacillin

Ciprofloxacin Cefotaxime Miconazole

Sulphathiazole Sulfamerazine Ofloxacin

Digoxigenin Sulfamethizole

Sulfachloropyrydazine Sulfamethoxine

Penicillin V Penicillin G

LC-MS/MS analytical methods

Pharmaceutical residues: Internal method modified

from EPA 1694

Liquid Chromatography: Thermo Accela 1250 pump

Column: 100x2.1 (3 µm) Thermo Betasil C18

Mobile Phase: [A] 0.1% HCOOH (0.5mL HCOOH in 0.5 L water); [B] ACN

Flow Rate = 300µL/min


Gradient method

Mass Spectrometry: Thermo Quantum Access Max

• H-ESI (250°C) in positive mode

• MRM

RT: 4.48 - 11.51

5 6 7 8 9 10 11

Time (min)

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4

6

8

10

12

14

16

18

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9.69

9.789.245.50 5.71

9.845.73

5.499.85

9.0510.01

10.039.04

5.74

9.026.216.22

5.48 6.91 10.046.93

7.384.7910.13

7.408.10

8.13

NL:3.50E7

TIC MS 2000ppt_3

On-line extraction methods Pharmaceuticals:

Column: 20x2.1 mm(12 µm) Thermo GOLD aQ

Mobile Phase: 2% ACN (10 mL ACN in 0.5 L water)



Sample injection volume = 1000 µL

Gradient elution

Perfluorinated:

Column: 20x2.1 mm (12 µm) Thermo GOLD aQ

Mobile Phase: 2mM NH4OAc+5%MeOH



Sample injection volume = 1-5 mL

Gradient elution

On-line extraction optimisation: loop volume effect

RT: 3.06 - 10.85 SM: 7G

4 5 6 7 8 9 10

Time (min)

0

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RT: 4.44MA: 49784

RT: 8.88MA: 230441

NL: 5.00E4

TIC F: - c ESI SRM ms2 498.883 [80.318-80.320, 99.099-99.101] MS 200ppt_perfluor3

NL: 5.00E4

TIC F: - c ESI SRM ms2 498.883 [80.318-80.320, 99.099-99.101] MS 200ppt_perfluor5ml2

RT: 3.74 - 10.35 SM: 7G

4 5 6 7 8 9 10

Time (min)

0

10

20

30

40

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70

80

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RT: 4.73AA: 1969388

RT: 9.15AA: 8583298

NL: 3.20E6

TIC F: - c ESI SRM ms2 462.908 [218.923-218.925, 418.868-418.870] MS ICIS 200ppt_perfluor3

NL: 3.20E6

TIC F: - c ESI SRM ms2 462.908 [218.923-218.925, 418.868-418.870] MS ICIS 200ppt_perfluor5ml2

1 mL

5 mL

PFOS PFOA

4.6-fold 4.4-fold

On-line extraction optimisation: matrix modification effect

Recovery on preconcentration column:

affinity for stationary phase


Recovery on preconcentration column:

affinity for stationary phase

Chromatographic separation:

sample solubility effect


Effect on a homologue series of perfluorinated compounds which differ for the increasing number (n) of CF2 groups

On-line extraction optimisation: effects of sample pH

pH=7.8

pH=3.5

PFBS (C4) PFOS (C8)

1-fold 20-fold RT: 5.50 - 7.50

5.5 5.6 5.7 5.8 5.9 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5

Time (min)

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RT: 6.54

AA: 12383 RT: 7.46

AA: 15446RT: 7.13

AA: 8258

RT: 6.75

AA: 4441RT: 6.59

AA: 8341RT: 7.30

AA: 8235

RT: 6.86

AA: 8863RT: 7.01

AA: 6931RT: 6.40

AA: 276RT: 6.28

AA: 14.43

RT: 6.02

AA: 4.22

RT: 6.13

AA: 7.47

RT: 5.85

AA: 6.52

RT: 5.71

AA: 3.30

RT: 5.61

AA: 2.07

RT: 6.53

AA: 285531

RT: 6.29

AA: 403RT: 6.81

AA: 228RT: 5.84

AA: 9.50

RT: 6.04

AA: 18.86

RT: 5.66

AA: 14.03

RT: 6.18

AA: 5.80

RT: 7.08

AA: 5.69

RT: 7.42

AA: 17.46

RT: 7.29

AA: 6.12

RT: 7.15

AA: 1.65

NL: 7.00E4

TIC F: - c ESI SRM ms2

298.891

[80.217-80.219,

99.120-99.122] MS

ICIS 100ppt_01

NL: 7.00E4


298.891

[80.217-80.219,

99.120-99.122] MS

ICIS

100ppt_GOLDaQ_5mL

AC_01

RT: 5.90 - 7.90 SM: 7G

5.9 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9

Time (min)

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RT: 6.94

AA: 400570

RT: 7.37

AA: 18359

RT: 7.26

AA: 5939RT: 7.63

AA: 2804RT: 7.87

AA: 3537RT: 6.37

AA: 28.88

RT: 6.61

AA: 8.11

RT: 6.74

AA: 0.24

RT: 6.03

AA: 4.61

RT: 6.91

AA: 422797

RT: 7.39

AA: 41866RT: 7.21

AA: 15249RT: 7.83

AA: 1128

RT: 7.64

AA: 1449RT: 5.93

AA: 240

RT: 6.55

AA: 10.91

RT: 6.39

AA: 4.95

RT: 6.25

AA: 0.50

NL: 1.50E5


398.851

[80.083-80.085,

98.988-98.990] MS

ICIS 100ppt_01

NL: 1.50E5


398.851

[80.083-80.085,

98.988-98.990] MS

ICIS

100ppt_GOLDaQ_5mL

AC_01



pH=7.8

pH=3.5

PFHxA (C6) PFOA (C8)

1-fold 8-fold

RT: 5.70 - 7.70

5.7 5.8 5.9 6.0 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7

Time (min)

0

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RT: 6.78

AA: 411917RT: 7.26

AA: 105966

RT: 7.35

AA: 58670

RT: 7.49

AA: 143156RT: 7.65

AA: 63409RT: 6.69

AA: 931

RT: 6.52

AA: 2612

RT: 6.36

AA: 2215

RT: 6.08

AA: 770

RT: 5.81

AA: 914

RT: 6.76

AA: 3251154

RT: 7.03

AA: 6764RT: 7.20

AA: 5176

RT: 7.45

AA: 5753

RT: 6.51

AA: 2828

RT: 6.33

AA: 1141

RT: 6.23

AA: 1583

RT: 5.75

AA: 661

RT: 5.84

AA: 381

RT: 5.98

AA: 339

RT: 6.08

AA: 127

NL: 1.00E6


312.892

[119.130-119.132,

268.897-268.899] MS

ICIS 100ppt_01

NL: 1.00E6


312.892

[119.130-119.132,

268.897-268.899] MS

ICIS

100ppt_GOLDaQ_5mLA

C_01

RT: 6.20 - 8.20

6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2

Time (min)

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RT: 7.19

AA: 2937582

RT: 7.55

AA: 6387

RT: 7.49

AA: 4530RT: 7.88

AA: 7082

RT: 7.71

AA: 3264

RT: 6.42

AA: 2959

RT: 7.06

AA: 1149

RT: 6.92

AA: 1045

RT: 8.12

AA: 1236

RT: 6.22

AA: 549

RT: 7.17

AA: 3732194

RT: 7.79

AA: 41369RT: 7.41

AA: 3396

RT: 7.96

AA: 9980

RT: 6.28

AA: 747

RT: 8.19

AA: 464

RT: 6.41

AA: 553

RT: 6.94

AA: 351

RT: 6.55

AA: 289

RT: 6.71

AA: 129

RT: 7.00

AA: 24.17

NL: 1.40E6


412.900

[169.003-169.005,

368.863-368.865] MS

ICIS 100ppt_01

NL: 1.40E6


412.900

[169.003-169.005,

368.863-368.865] MS

ICIS

100ppt_GOLDaQ_5mLA

C_01

RT: 6.70 - 8.70 SM: 7G

6.7 6.8 6.9 7.0 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7

Time (min)

0

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RT: 7.65

AA: 1471169

RT: 8.55

AA: 3723

RT: 8.17

AA: 2186

RT: 8.03

AA: 2396

RT: 8.30

AA: 1110

RT: 7.36

AA: 745

RT: 6.80

AA: 1463

RT: 7.04

AA: 743

RT: 8.44

AA: 506

RT: 7.64

AA: 1361899

RT: 8.59

AA: 9302RT: 7.86

AA: 1171

RT: 6.76

AA: 2381

RT: 8.18

AA: 1676

RT: 7.93

AA: 2371

RT: 8.35

AA: 786

RT: 7.17

AA: 578

RT: 7.06

AA: 336

RT: 7.25

AA: 312

NL: 4.00E5


512.922

[268.863-268.865,

468.870-468.872] MS

ICIS 100ppt_01

NL: 4.00E5


512.922

[268.863-268.865,

468.870-468.872] MS

ICIS

100ppt_GOLDaQ_5mLA

C_01

RT: 7.20 - 9.20 SM: 7G

7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8.0 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 9.0 9.1 9.2

Time (min)

0

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RT: 8.22

AA: 484055

RT: 8.45

AA: 456

RT: 8.58

AA: 956

RT: 8.71

AA: 315

RT: 7.35

AA: 286

RT: 9.12

AA: 400

RT: 7.94

AA: 224

RT: 8.81

AA: 195

RT: 7.70

AA: 150

RT: 7.58

AA: 129

RT: 8.88

AA: 104

RT: 7.84

AA: 1.09

RT: 7.47

AA: 2.72

RT: 8.19

AA: 448533

RT: 8.03

AA: 346

RT: 8.70

AA: 717

RT: 8.50

AA: 220

RT: 8.91

AA: 241

RT: 9.07

AA: 343

RT: 7.40

AA: 82.16

RT: 7.67

AA: 73.59

RT: 7.53

AA: 15.90

RT: 7.85

AA: 15.84

RT: 7.99

AA: 1.65

NL: 1.30E5


612.912

[318.825-318.827,

568.854-568.856] MS

ICIS 100ppt_01

NL: 1.30E5


612.912

[318.825-318.827,

568.854-568.856] MS

ICIS

100ppt_GOLDaQ_5mLA

C_01



pH=7.8

pH=3.5

PFDA (C10) PFDoDA (C12)

1-fold 1-fold

Direct Injection: effects of sample pH

pH=7.8

pH=3.5

PFBA (C4) PFBS (C4)

RT: 1.61 - 4.67

1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6

Time (min)

0

10

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0

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RT: 3.03

AA: 99341

RT: 2.78

AA: 39475

RT: 2.69

AA: 4944RT: 3.14

AA: 743RT: 2.56

AA: 1255RT: 2.38

AA: 786RT: 3.26

AA: 189RT: 3.56

AA: 33.60

RT: 4.20

AA: 31.10

RT: 4.55

AA: 15.80

RT: 2.14

AA: 17.72

RT: 4.03

AA: 11.78

RT: 1.77

AA: 14.68

RT: 3.86

AA: 2.39

RT: 3.70

AA: 10.57

RT: 4.43

AA: 3.21

RT: 3.14

AA: 134692

RT: 2.95

AA: 148RT: 3.56

AA: 14.40

RT: 1.99

AA: 12.73

RT: 4.38

AA: 3.94

RT: 4.27

AA: 6.07

RT: 3.82

AA: 2.58

RT: 2.64

AA: 5.74

RT: 2.30

AA: 7.94

RT: 2.11

AA: 0.81

RT: 4.56

AA: 1.31

RT: 4.03

AA: 3.54

RT: 2.87

AA: 1.55

RT: 1.77

AA: 0.64

RT: 1.63

AA: 0.89

NL: 5.00E4

TIC F: - c ESI SRM

ms2 298.891

[80.217-80.219,

99.120-99.122] MS

ICIS 10ppb_fresh_01

NL: 5.00E4

TIC F: - c ESI SRM

ms2 298.891

[80.217-80.219,

99.120-99.122] MS

ICIS

10ppbACID_fresh_01

RT: 0.00 - 4.01

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0

Time (min)

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RT: 1.01

AA: 242531

RT: 2.98

AA: 25624RT: 3.61

AA: 29852RT: 3.15

AA: 8740RT: 2.82

AA: 11335RT: 3.86

AA: 9895

RT: 2.51

AA: 11865RT: 2.21

AA: 13356

RT: 1.97

AA: 6595RT: 1.69

AA: 2724

RT: 3.25

AA: 2404

RT: 1.32

AA: 1197RT: 0.16

AA: 4483

RT: 1.28

AA: 774

RT: 0.74

AA: 411

RT: 1.67

AA: 708946

RT: 3.02

AA: 46202RT: 3.16

AA: 7189RT: 3.75

AA: 12702RT: 3.48

AA: 14258

RT: 2.73

AA: 10094

RT: 2.29

AA: 10846

RT: 2.10

AA: 7723RT: 2.54

AA: 2649

RT: 0.58

AA: 11373RT: 0.73

AA: 12215

RT: 1.98

AA: 2740

RT: 1.44

AA: 4324

RT: 0.34

AA: 6171RT: 1.21

AA: 4173

RT: 0.10

AA: 1576

RT: 1.01

AA: 1287

NL: 8.60E4

TIC F: - c ESI SRM

ms2 212.898

[168.914-168.916]

MS ICIS

10ppb_fresh_01

NL: 8.60E4

TIC F: - c ESI SRM

ms2 212.898

[168.914-168.916]

MS ICIS

10ppbACID_fresh_

01

RT: 7.15 - 11.32 SM: 5G

8 9 10 11

Time (min)

0

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100

0

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100

0

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0

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RT: 7.94AA: 159708

RT: 8.08AA: 124816

RT: 8.97AA: 5009907

RT: 9.23AA: 6711618

RT: 8.91AA: 4556

RT: 9.95AA: 401427

RT: 10.24AA: 593383

NL: 2.98E4

TIC F: - c ESI SRM ms2 298.891 [80.217-80.219, 99.120-99.122] MS ICIS 200ppt_perfluornoac5mltest4_5

NL: 2.86E4

TIC F: - c ESI SRM ms2 298.891 [80.217-80.219, 99.120-99.122] MS ICIS 200ppt#(nomix)-03

NL: 2.10E6


NL: 2.10E6


NL: 1.71E5


NL: 1.71E5


5% methanol in the sample before extraction

On-line extraction optimisation: effect of solvent addition

PFBS

C4

PFOA

C8

PFDoA

C12

5% MeOH

5% MeOH

5% MeOH

50% methanol in the sample before injection

Direct Injection: effect of solvent addition

PFPeA (C5) PFDoDA (C12)

RT: 1.64 - 4.61 SM: 7G

1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6

Time (min)

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

RT: 3.00

AA: 2583458

RT: 3.34

AA: 32982RT: 3.76

AA: 49358RT: 3.49

AA: 34503

RT: 4.21

AA: 53223RT: 3.93

AA: 28883

RT: 2.66

AA: 25498

RT: 2.16

AA: 11119

RT: 2.29

AA: 9273

RT: 2.41

AA: 19748

RT: 2.05

AA: 19610

RT: 1.87

AA: 33537

RT: 2.98

AA: 4964122

RT: 3.93

AA: 47371

RT: 3.54

AA: 20081RT: 4.19

AA: 24533

RT: 2.68

AA: 18931RT: 4.31

AA: 8440

RT: 2.28

AA: 13915

RT: 2.43

AA: 15820

RT: 3.42

AA: 8382

RT: 1.88

AA: 37198

RT: 3.30

AA: 3896

NL: 5.60E5


262.913

[69.041-69.043,

218.936-218.938] MS

ICIS 30ppb_usepa_01

NL: 5.60E5


262.913

[69.041-69.043,

218.936-218.938] MS

ICIS

30ppbacid_da60ppbme

oh_04

2-fold RT: 3.44 - 6.38 SM: 7G

3.6 3.8 4.0 4.2 4.4 4.6 4.8 5.0 5.2 5.4 5.6 5.8 6.0 6.2

Time (min)

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

0

10

20

30

40

50

60

70

80

90

100

Re

lative

Ab

un

da

nce

RT: 4.81

AA: 683146

RT: 3.72

AA: 1085

RT: 5.22

AA: 1905

RT: 3.58

AA: 722

RT: 5.03

AA: 498

RT: 5.80

AA: 2992

RT: 4.32

AA: 494

RT: 5.37

AA: 684

RT: 4.53

AA: 323

RT: 5.59

AA: 825

RT: 6.14

AA: 721

RT: 6.04

AA: 600

RT: 6.30

AA: 538

RT: 4.11

AA: 147

RT: 3.88

AA: 118

RT: 4.80

AA: 2087542

RT: 4.56

AA: 988

RT: 5.11

AA: 2138RT: 5.33

AA: 2871

RT: 5.01

AA: 447 RT: 5.76

AA: 2679

RT: 5.99

AA: 2159

RT: 4.15

AA: 1243

RT: 5.62

AA: 559

RT: 6.10

AA: 353

RT: 5.50

AA: 875

RT: 6.26

AA: 714

RT: 3.94

AA: 145

RT: 3.83

AA: 53.55

RT: 3.63

AA: 42.66

RT: 4.41

AA: 2.21

NL: 3.00E5


612.912

[318.825-318.827,

568.854-568.856] MS

ICIS 30ppb_usepa_01

NL: 3.00E5


612.912

[318.825-318.827,

568.854-568.856] MS

ICIS

30ppbacid_da60ppbmeo

h_04

50% MEOH

0% MEOH

3-fold

Cotinine

On-line extraction optimisation: Matrix modification for pharmaceuticals

0

200000

400000

600000

800000

1000000

1200000

1400000

Higher sensitivity

at alkaline pH

Miconazole


0

200000

400000

600000

800000

1000000

1200000

Higher sensitivity

at acid pH

Fluoxetine


0

200000

400000

600000

800000

1000000

1200000

1400000

No evident effect

On-line method performance : Linearity

R² = 0,9941

0

200000

400000

600000

800000

1000000

1200000

0 200 400 600 800 1000 1200

are

a

pg

PFPeA (C5)

R² = 0,9997

0,0

200000,0

400000,0

600000,0

800000,0

1000000,0

1200000,0

1400000,0

1600000,0

0,0 100,0 200,0 300,0 400,0 500,0

PFDoDA (C12)

R² = 0,9956

0

50000

100000

150000

200000

250000

0 200 400 600 800 1000

are

a

pg

PFOS (C8)

R² = 0,9901

0

100000

200000

300000

400000

500000

0 200 400 600 800 1000

are

a

pg

PFBS (C4)

Linearity: OnLine vs Direct injection

0,E+00

5,E+05

1,E+06

2,E+06

2,E+06

3,E+06

3,E+06

4,E+06

4,E+06

5,E+06

5,E+06

0 200 400 600 800 1000 1200

are

a

pg

PFPeA (C5)

0,E+00

5,E+04

1,E+05

2,E+05

2,E+05

3,E+05

0 200 400 600 800 1000

are

a

pg

PFOS (C8)

0,E+00

1,E+05

2,E+05

3,E+05

4,E+05

5,E+05

6,E+05

7,E+05

0 200 400 600 800 1000

are

a

pg

PFBS (C4)

0,E+00

2,E+05

4,E+05

6,E+05

8,E+05

1,E+06

1,E+06

1,E+06

2,E+06

0 100 200 300 400 500

are

a

pg

PFDoDA (C12)

On Line 5 mL

Direct Injection 20 uL

0

20

40

60

80

100

120

140

160

180

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFBS PFHxS PFOS

%

Recovery

TW spring TW ground water River 1 River 2

On-line method performance: recovery on real samples

On-line method performance: Ripetibility and LOQ

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnDA PFDoDA PFBS PFHxS PFOS

LOQ ng/L

20 4 1 5 3 1 1 1 2 10 20 10

Riproducibility (RSD%)

7-33 5-17 5-12 4-17 8-17 2-24 8-25 4-26 13-37 5-16 4-13 5-27

EU Survey on the distribution of perfluorinated compound

McLachlan et al. (2007) Riverine discharge of perfluorinated carboxylates from the European Continent. Environ. Sci. Technol

41, 7260-7265

Convenzione IRSA-MATT Realizzazione di uno studio di valutazione del Rischio Ambientale e Sanitario associato alla contaminazione da sostanze perfluoro-alchiliche (PFAS) nel Bacino del

Po e nei principali bacini fluviali italiani

• asta del fiume Po

• principali tributari del fiume Po

• altri principali bacini fluviali dell’Italia (Adige, Arno e Tevere)

• zone di molluschicoltura e pescicoltura della laguna di Venezia e

del Delta del Po

• studi ecotossicologici di laboratorio e di campo

Survey on the distribution of perfluorinated compound in river Po basin (Northern Italy)

Po-SMT

Po-VA

Po-PI

Po-IP

Po-SBP

Po-RE

Po-PLS

Survey on the distribution of perfluorinated compound in river Po basin (Northern Italy)

0

20000

40000

60000

80000

100000

120000

Po-SMT(115)

Po-VA(215)

Po-PI(350)

Po-IP(420)

Po-SBP(500)

Po-RE(520)

Po-PLS(572)

µg

/s

PFOS

PFBS

PFDA

PFNA

PFOA

PFHp

PFHxA

PFPeA

Adda (390)

Tanaro (235)

Distribuzione di PFPeA e PFHxA nei principali bacini fluviali italiani

Conclusions

On-line extraction methods allow the analysis of

surface and drinking waters with limited sample

preparation (filtration (centrifugation) and matrix

modification)

Analytical times, sample manipulation and lab

wastes are drastically reduced

Preliminary results: two runs (pH 3.5 and pH 10.5)

for a mixed class of chemicals

Optimisation of multiresidue methods is a

compromise between sample productivity and limits

of detection

Acknowledgments

We thank Thermo Scientific for having invited us to

present our results

We also warmly acknowledge the precious support of

the Thermo staff, Claudia Martins, Federico Guidugli,

in developing on-line methods

Sara VALSECCHI, Stefano POLESELLO CNR-IRSA, Water …...Perfluoroalkyl acids Two primary classes of...

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