Sara VALSECCHI, Stefano POLESELLO CNR-IRSA, Water …...Perfluoroalkyl acids Two primary classes of...
Transcript of Sara VALSECCHI, Stefano POLESELLO CNR-IRSA, Water …...Perfluoroalkyl acids Two primary classes of...
Sara VALSECCHI, Stefano POLESELLO
CNR-IRSA, Water Research Institute
Brugherio, Italy
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
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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)
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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
TIC F: - c ESI SRM ms2 362.895 [169.003-169.005, 318.872-318.874] MS ICIS TWM23may_00
NL: 6.38E5
TIC F: - c ESI SRM ms2 412.900 [169.003-169.005, 368.863-368.865] MS ICIS TWM23may_00
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
TIC F: - c ESI SRM ms2 512.922 [268.863-268.865, 468.870-468.872] MS ICIS TWM23may_00
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
Column Temperature: ambient
Gradient method
Mass Spectrometry: Thermo Quantum Access Max
• H-ESI (250°C) in positive mode
• MRM
RT: 4.48 - 11.51
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Time (min)
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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)
Flow Rate = 1200 µL/min
Column Temperature: ambient
Sample injection volume = 1000 µL
Gradient elution
Perfluorinated:
Column: 20x2.1 mm (12 µm) Thermo GOLD aQ
Mobile Phase: 2mM NH4OAc+5%MeOH
Flow Rate = 1200 µL/min
Column Temperature: ambient
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)
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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)
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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
On-line extraction optimisation: matrix modification effect
Recovery on preconcentration column:
affinity for stationary phase
Chromatographic separation:
sample solubility effect
On-line extraction optimisation: matrix modification 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
TIC F: - c ESI SRM ms2
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
TIC F: - c ESI SRM ms2
398.851
[80.083-80.085,
98.988-98.990] MS
ICIS 100ppt_01
NL: 1.50E5
TIC F: - c ESI SRM ms2
398.851
[80.083-80.085,
98.988-98.990] MS
ICIS
100ppt_GOLDaQ_5mL
AC_01
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
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)
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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
TIC F: - c ESI SRM ms2
312.892
[119.130-119.132,
268.897-268.899] MS
ICIS 100ppt_01
NL: 1.00E6
TIC F: - c ESI SRM ms2
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
TIC F: - c ESI SRM ms2
412.900
[169.003-169.005,
368.863-368.865] MS
ICIS 100ppt_01
NL: 1.40E6
TIC F: - c ESI SRM ms2
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)
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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
TIC F: - c ESI SRM ms2
512.922
[268.863-268.865,
468.870-468.872] MS
ICIS 100ppt_01
NL: 4.00E5
TIC F: - c ESI SRM ms2
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)
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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
TIC F: - c ESI SRM ms2
612.912
[318.825-318.827,
568.854-568.856] MS
ICIS 100ppt_01
NL: 1.30E5
TIC F: - c ESI SRM ms2
612.912
[318.825-318.827,
568.854-568.856] MS
ICIS
100ppt_GOLDaQ_5mLA
C_01
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
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)
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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
50
100
0
50
100
0
50
100
0
50
100
Rela
tive
Ab
un
da
nce 0
50
100
0
50
100
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
TIC F: - c ESI SRM ms2 462.908 [218.923-218.925, 418.868-418.870] MS ICIS 200ppt_perfluornoac5mltest4_5
NL: 2.10E6
TIC F: - c ESI SRM ms2 462.908 [218.923-218.925, 418.868-418.870] MS ICIS 200ppt#(nomix)-03
NL: 1.71E5
TIC F: - c ESI SRM ms2 612.912 [318.825-318.827, 568.854-568.856] MS ICIS 200ppt_perfluornoac5mltest4_5
NL: 1.71E5
TIC F: - c ESI SRM ms2 612.912 [318.825-318.827, 568.854-568.856] MS ICIS 200ppt#(nomix)-03
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
TIC F: - c ESI SRM ms2
262.913
[69.041-69.043,
218.936-218.938] MS
ICIS 30ppb_usepa_01
NL: 5.60E5
TIC F: - c ESI SRM ms2
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
TIC F: - c ESI SRM ms2
612.912
[318.825-318.827,
568.854-568.856] MS
ICIS 30ppb_usepa_01
NL: 3.00E5
TIC F: - c ESI SRM ms2
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
On-line extraction optimisation: Matrix modification for pharmaceuticals
0
200000
400000
600000
800000
1000000
1200000
Higher sensitivity
at acid pH
Fluoxetine
On-line extraction optimisation: Matrix modification for pharmaceuticals
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