Logo grupo

Perfluorinated compounds in L’Albufera Natural Park

Yolanda Pico1, Matthias Onghena1, Marinella Farré2, Cristina Blasco1 and Damià Barceló2,3,4

1 Nutrition and Bromatology Laboratory, University of Valencia, Valencia, Spain.2 Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain3Catalan Institute for Water Research (ICRA), Girona, Spain4 King Saud University, Riyadh, Saudi Arabia

Analysis, fate and risks of organic contaminants in river basinsunder water scarcity

Valencia, 7-8 February 2011

Logo grupo

Xuquer River BasinXuquer River Basin

Logo grupo

Logo grupo

Surface: 21,000 ha

Location: 12 km south of Valencia

Sourronded by towns, industry, agriculture and leisure zones

Crossed by roads and a motorway

Water input:

•Fresh water : 64 spots•Undepurated urban sewage waters•Water from WWTP

Logo grupo

A

B

C

D

Logo grupo

Tancat de la PipaConstructed wetland

Constructed wetland

Logo grupo

ObjectiveObjective

To demonstrate the spatial distributions of PFCs levels and their distribution in water and sediments from the L’Albufera Natural Park (Valencia, Spain).

Logo grupo

EXPERIMENTALEXPERIMENTAL

Extraction

LC ‐MS/MS

Sampling

Evaporation

Logo grupo

PFC Empirical Formula

Molecular Weight Isotopically labelled IS

PFBS C4F9SO3− 300,00 MPFOS

PFPA C5HF9O2 264.08 MPFHxAPFHxA C6HF11O2 314.08 MPFHxAPFHpA C7HF13O2 364.08 MPFOAPFOA C8HF15O2 414.07 MPFOAPFOS C8F17SO3

− 500.013 MPFOS

PFNA C9HF17O2 464.08 MPFOAi,p-PFNA C9HF17O2 464.08 MPFOAFFDA C10HF19O2 514.08 MPFDAFFDS C10F21SO3

− 600.08 MPFOS

Logo grupo

Sampling in LSampling in L’’Albufera Natural ParkAlbufera Natural Park

12

3

4

56

7

8 9

10

1112

CamCamíí del Recdel Rec

Portet de CatarrojaPortet de Catarroja

RabisanxoRabisanxoFont del FluxFont del Flux

Font del FluxFont del Flux

Av. AlacantAv. Alacant

Alzira/AlmussafesAlzira/Almussafes

Benifaio/AlmussafesBenifaio/Almussafes

DretaDreta

La LlosaLa Llosa Vell de SuecaVell de Sueca

La LlosaLa Llosa

Logo grupo

CARTRIDGES:OASIS WAX (6 cc) and HLB (6 cc)

PRE‐CONDITIONINGWAX  → 4 ml ,1 % NH4OH in MeOH HLB  → 5 ml MeOH

→ 4 ml MeOH → 5 H2O→ 4 H2O

WATER SAMPLES→ 200 mL previously filtered through a Whatman GF/Fglass microfiber membrane filters of 0.2 µm.

ELUTIONWAX  → 4 ml Buffer 25 Mm  CH3COONH4 HLB  → 5 H2O

→ 4 ml MeOH → 5 ml MeOH→ 4 ml 1 % NH4OH IN MeOH

Evaporation to 1 mL injetion LC-MS

-

SolidSolid--phase extraction (SPE) of waterphase extraction (SPE) of water

Logo grupo

FRESH SEDIMENT 5g

EXTRACT WITH 10 mL 1 % CH3COOH→ Vortex mixed, sonicated 15 min at 40 ºC→ Centrifuged at 3000 rpm 2 min→ Decanted the supernantant to a 50 mL clean Falcon tube

REEXTRACT TWICE 2.5 mL 90:10 (v/v) MeOH-1 % CH3COOH→ Vortex mixed, sonicated 15 min at 40 ºC→ Centrifuged at 3000 rpm 2 min→ Decanted the supernantant to the 50 mL previous Falcon tube

Evaporation to 1 mL injetion LC-MS

4 -

Ultrasonic extraction of sedimentsUltrasonic extraction of sediments

The extracts combined in the second tube were diluted to 40 mL with distilled waterbefore being passed through the SPE cartridge in a similar fashion as was described above in the water extraction procedure.

Logo grupo

Mobile phase A → 10 mM CH3COONH4 in H2OMobile phase B → 10 mM CH3COONH4 in MeOHGradient:

Analytical column: Luna C18(2) (150 x 2 mm I.D, 3 µm)Flujo: 0,3 ml/min

Interfase: Z-spray in negative ionization modeCapillary_ 3.0 VSource temperature: 125 ºCDesolvation temperature: 350 ºCDesolvation gas-flow: 600 Lh-1

Cone gas-flow: 60 Lh-1

4 -

LCLC--MS/MS conditionsMS/MS conditions

90 % A: 10 % B0.8 min 10 min

10 % A: 90 % B 30 min

90 % A: 10 % B

15 min

SEPARATION:

MASS SPECTROMETRY:

Logo grupo

LCLC--MS/MS conditionsMS/MS conditions

PFCs SRM1 a Product ion Identification

CE (V) SMR2 b Product Ion identification

CE (V)

PFPA 263 → 219 [M-H-CO2]- 10 -- -- --PFBS 299 → 80 [SO3]- 30 299→ 99 [FSO3]- 25PFHxA 313 → 269 [M-H-CO2]- 15 313 → 119 [C2F5]- 15

MPFHxA 315 → 270 [M-H-CO2]- 10 --- --- ---PFHpA 363 → 319 [M-H-CO2]- 10 363 → 169 [C3F7]- 10PFOA 413 → 369 [M-H-CO2]- 15 413→169 [C3F7]- 10

MPFOA 417 → 372 [M-H-CO2]- 10 --- --- ---PFOS 499 → 80 [SO3]- 45 499→ 98.5 [FSO3]- 45

MPFOS 503 → 80 [SO3]- 40 --- --- ---PFNA 463 → 419 [M-H-CO2]- 10 463→ 219 [C4F9]- 10

i,p-PFNA 463 → 419 [M-H-CO2]- 10 463→219 [C4F9]- 10PFDA 513 → 469 [M-H-CO2]- 10 513→ 169 [C3F7]- 10

MPFDA 515 → 470 [M-H-CO2]- 10 -- -- 45L-PFDS 599 → 80 [SO3]- -100 599 → 469 [FSO3]- -100

aQuantifier precursor-product ion transitionbQualifier precursor-product ion transition

Logo grupo15

HydrophilicRetention of polars

RESULTADOS Y DISCUSIONRESULTADOS Y DISCUSION

Logo grupo

MLOD (ng L-1)

MLOQ (ng L-1)

Recovery at MLOQ

(% ± RSD)

Calibration curves with matrix matched standards % Matrix

effectr Range (ng L-1)

PFBA 1.5 5 69 ± 13 0.9989 5–5000 17PFPA 1.5 5 96 ± 10 0.9997 5–5000 13PFHxA 0.15 0.5 101 ± 11 0.9996 0.5–500 5PFHpA 0.15 0.5 73 ± 9 0.9998 0.5–500 8PFOA 0.02 0.05 97 ± 7 0.9995 0.05–500 2PFOS 0.02 0.05 110 ± 8 0.9994 0.05–50 1PFNA 0.03 0.1 99 ± 8 0.9993 0.01–100 2i,p-PFNA 0.02 0.05 90 ± 10 0.9995 0.05–50 5PFDA 0.02 0.05 98 ± 12 0.9998 0.05–50 6L-PFDS 0.02 0.05 89 ± 11 0.9988 0.05–50 3

a Validation of the analytical methodologyValidation of the analytical methodology

1 MPFHxA; 2 MPFOA; 3 MPFOS; 4 MPFDA

Logo grupo

MLOD (ng g-1)

MLOQ (ng g-1)

Recovery (at MLOQ, % ± RSD)

Calibration curves in matrix matched standards % Matrix

effectAbsolute Relative r Range (ng g-1)

PFBA3 0.02 0.2 44 ± 19 62 ± 16 0.9989 0.2–200 34PFPA1 0.02 0.2 56 ± 17 82 ± 14 0.9997 0.2–200 28PFHxA1 0.007 0.02 68 ± 15 100 ± 13 0.9996 0.02-20 32PFHpA2 0.007 0.02 62 ± 16 85 ± 10 0.9998 0.02-20 27PFOA2 0.0007 0.002 73 ± 10 98 ± 9 0.9995 0.002-2 13PFOS3 0.0007 0.002 71 ± 12 97 ± 11 0.9994 0.002-2 12PFNA4 0.004 0.01 74 ± 15 103 ± 8 0.9993 0.01–10 14i,p-PFNA4 0.005 0.01 70 ± 14 97 ± 7 0.9995 0.01–10 11PFDA4 0.004 0.01 72 ± 13 99 ± 5 0.9998 0.01–10 -10L-PFDS3 0.004 0.01 69 ± 12 98 ± 6 0.9988 0.01–10 8

17

Validation of the analytical methodologyValidation of the analytical methodology

1 MPFHxA; 2 MPFOA; 3 MPFOS; 4 MPFDA

Logo grupo

Site PFBS PFPA PFHxA PFHpA PFOA PFNA I,p-PFNA PFOS PFDA PFDS Σ PFCs

L’Albufera Natural Park1 5.5 5.4 n.d. n.d. 15.44 6.99 5.44 29.57 n.d. n.d. 68.342 1.6 n.d. 0.50 0.94 120.23 18.48 12.5 58.12 3.07 1.06 216.503 <5 n.d. 5.85 1.01 114.02 0.27 n.d. 1.26 <0.05 1.29 125.224 n.d. n.d. 6.90 8.55 101.05 10.03 3.89 24.50 <0.05 0.002 154.945 n.d. n.d. 0.78 1.51 15.17 2.30 0.26 1.40 1.16 <0.05 23.106 n.d. <5 <0.5 <0.5 23.27 1.28 1.68 32.44 0.24 0.015 60.867 n.d. n.d. n.d. n.d. 14.01 <0.05 <0.05 1.30 <0.05 <0.05 15.398 n.d. n.d. n.d. n.d. 1.24 <0.05 n.d. 1.10 0.44 0.25 3.0589 <5 n.d. n.d. n.d. 6.64 0.016 0.05 3.48 <0.05 <0.05 11.8710 <5 n.d. 0.55 <0.5 0.99 0.22 0.011 0.94 2.53 1.04 8.0311 <5 n.d. 4.32 5.17 103.42 0.20 0.08 8.98 <0.05 0.81 124.5012 <5 n.d. 3.72 18.40 78.6 0.35 0.02 7.53 10.00 0.55 120.72

Min n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 0.99Max 5.50 5.40 6.90 18.48 120.23 18.48 5.40 58.12 10.00 1.29 120.23Mean 1.22 0.58 1.89 2.99 49.50 3.36 2.05 14.29 1.46 0.43 77.71SD 1.55 1.58 2.56 5.52 48.97 5.74 3.74 18.18 2.89 0.49 69.76

PFCs in water samples (ng/L)PFCs in water samples (ng/L)

Logo grupo

12

3

4

56

7

8 9

10

1112

Camí del Rec

Portet de catarroja

Rabisanxo Font del Flux

Font del Flux

Av. Alacant

Alzira/Almussafes

Benifaio/Almussafes

Dreta

La Llosa Vell de Sueca

La Llosa

Logo grupo

A12

A11A2A3

Logo grupo

LCLC--MS/MS chromatogramsMS/MS chromatograms

21

Time2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00

%

0

100

MRM of 16 Channels ES-299 > 98.5

2.65e412.78

Time2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00

%

0

100

MRM of 16 Channels ES-263 > 219

2.24e412.58

Time2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00

%

0

100

MRM of 16 Channels ES-413 > 369

5.62e3

Time2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00

%

0

100

MRM of 16 Channels ES-413 > 369

35015.06 15.66

Time2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00

%

0

100

MRM of 16 Channels ES-499 > 98.5

1.51e415.46

15.06

PFPA

PFBS

PFOA

i,p-PFNA PFNA

PFOS

Sample 1

Logo grupo

Levels of perfluorinated compounds in water

Country, City Concentraction (ng/L) Observations Reference

USA, Tenessee PFOS: 18,4 -144; PFOA: < 25-598

40 River water samples Hansen et al. (2002)

Japan PFOS : 1,68 (mean) Different geographical locations

Saito et al. (2003)

Japan; Osaka & Tohoku

PFOS: <LOD-12,0; PFOA: 0,7-40

Tap water from Osaka 40ng/L Saito et al. (2004)

Canada-USA, Ontario Lakes

PFOS: 21 -70; PFOA: 25-50

Levels of N-EtFOSAA and FOSA below LOQ

Boilanger et al. 2004

China, ríos Perarl & Yangtze

PFOS: <0,01-99; PFOA 0,85-260

So et al. (2007)

Sri Lanka PFOS: 0,66-47; PFOA: 0,83-12,4

Water samples taken at different locations

Guruge et al. (2007)

Japan; Hyogo PFOS: 2,1 PFOA: 17

Mean values Yoshida et al. (2007)

Alemania, Ruhr River PFOS: <2-193; PFOA: <2-3640

Weremiuk et al. (2006)

USA, New York PFOS: 1,6 -756; PFOA: 15-49

51 samples of 9 systems (lakes, river, channels)

Sinclair et al. (2006)

Spain, Tarragona PFOS: 0,24 -5,88; PFOA: 0,22-24,9

Drinking water Ericsson et al. (2008)

22

Logo grupo23

PFOS (Boudreau et al. 2004)(PNEC 0.01 nM)

PFOA (Colombo et al. 2008)(PNEC 30 µM)

Sample Conc. (nM) RQ (MEC/PNEC)

Conc. (nM) RQ (MEC/PNEC)

1 0.031 5.91 0.037 0.0012

2 0.240 11.62 0.290 0.0097

3 0.228 0.25 0.275 0.0092

4 0.202 4.90 0.244 0.0081

5 0.030 0.28 0.037 0.0012

6 0.047 6.49 0.056 0.0019

7 0.028 0.26 0.034 0.0011

8 0.002 0.22 0.003 0.0001

9 0.013 0.70 0.016 0.0005

10 0.002 0.19 0.002 0.0001

11 0.207 1.80 0.250 0.0083

12 0.157 1.51 0.037 0.0063

Logo grupo

PFCs in sediment samples (ng/L)PFCs in sediment samples (ng/L)Site PFBS PFHxS PFHxA PFHpA PFOA PFNA i,p-PFNA PFOS PFDA PFDS ΣPFCs

L’Albufera Natural Park1 <0.2 <0.2 <0.02 <0.02 0.53 0.18 1.52 4.30 <0.01 0.040 6.732 <0.2 <0.2 <0.02 <0.02 7.20 0.94 1.23 4.80 1.04 2.00 17.383 <0.2 <0.2 <0.02 <0.02 10.2 0.11 n.d. 0.13 n.d. n.d. 10.664 n.d. n.d. 0.098 0.125 2.4 1.24 n.d. 2.20 n.d. n.d. 6.075 n.d. n.d. 0.009 0.015 0.24 0.04 0.05 0.42 0.14 0.02 0.936 n.d. n.d. <0.02 <0.02 0.9 0.04 0.05 4.70 0.05 0.20 5.957 n.d. n.d. <0.02 <0.02 0.4 <0.01 n.d. 0.10 n.d. n.d. 0.528 n.d. n.d. <0.02 <0.02 0.03 <0.01 <0.01 0.20 n.d. n.d. 0.259 n.d. n.d. <0.02 <0.02 0.07 0.04 n.d. 0.30 n.d. n.d. 0.4210 n.d. n.d. <0.02 <0.02 0.03 0.14 n.d. 0.20 n.d. n.d. 0.3811 n.d. n.d. 0.079 0.075 10.9 0.09 n.d. 1.39 0.01 1.50 13.89512 n.d. n.d. 0.034 0.945 5.4 0.16 <0.01 2.80 1.25 0.80 11.39

Min n.d. n.d. <0.02 <0.02 0.03 0.01 n.d. 0.1 n.d. n.d. 0.25Max <0.02 <0.02 0.98 0.94 10.90 1.24 1.52 4.80 1.25 2.00 17.38Mean 0.02 0.02 0.03 0.10 3.19 0.25 0.24 1.79 0.21 0.38 6.22SD 0.03 0.03 0.03 0.27 4.14 0.40 0.54 1.91 0.44 0.68

Logo grupo

River Basin Location Concentration (ng g-1 dw) Ref.

PFOS PFOA

The Petaluma The Salinas The San Lorenzo

The San FranciscoBay Area, USA

n.d. – 1.3 (1.2) n.d. – 0.23 (0.002) Higgins et al. (2005)

The Willamette River Oregon, USA n.d. 0.018Higgins et al. (2005)

The Ariake Sea Japan 0.09–0.014 (0.011) 0.84–1.1 (0.96) Nakata (2006)The Roter Main River Bayreuth, Germany 0.02–0.31 (0.24) 0.02–0.02 (0.04) Becker (2008)The Hun River;The Taizi RiverThe Daliao River

The Central Liaoning City Cluster, China

0.016–0.97 (0.29) 0.002–0.35 (0.30) Bao et al. (2009)

The Zhujiang River Guangzhou, China <0.012–3.1 (0.58) 0.09–0.29 (0.21) Bao et al. (2010)The Huangpu River Shanghai, China <0.012–0.46 (0.011) 0.20–0.64 (0.43) Bao et al. (2010)

L’Albufera Valencia, Spain <0.002-0.87 (0.09) 0.02.-0.48 (0.08) The present study

Levels of perfluorinated compounds in sediments

Logo grupo

Individual PFCs (%-composition)

0% 20% 40% 60% 80% 100%

1

2

3

4

5

6

7

8

9

10

11

12

% composition

Sampling   site

PFBS

PFPA 

PFHxA 

PFHpA 

PFOA 

PFNA 

i,p‐PFNA 

PFOS 

PFDA 

PFDS 

0% 20% 40% 60% 80% 100%

1

2

3

4

5

6

7

8

9

10

11

12

% composition

Sampling    site

Logo grupo

Distribution between water and sediments

Logo grupo

Csed = sediment concentration (ng/kg) Cw = water concentration (ng/L)

KD = Csed/Cw KOC = KD × 100/fOC

KD= Distribution constant fOC = sediment organic carbon fraction

Logo grupo

L’Albufera Natural Park (this study) Orge River, France (Labadie and Chevreuil 2011)

The Netherlands(Kwadijk et al. 2010)

Tokio Bay, Japan(Ahrens et al. 2010)

log KD log Koc log KD log Koc log KD log KD log Koc

PFBS 1.47 ± 0.32 (n=3) 2.79 ± 0.43 (n=3) —— —— 1.42 ± 0.50 —— ——

PFPA 1.11 ( n=1) 2.31 ( n=1) —— —— —— —— ——

PFHxA 1.18 ± 0.22 (n=8) 2.62 ± 0.37 (n=8) 0.8 ± 0.0 2.1 ± 0.2 —— —— ——

PFHpA 1.26 ± 0.37 (n=8) 2.70 ± 0.42 (n=8) 0.8 ± 0.1 2.1 ± 0.2 —— —— ——

PFOA 1.55 ± 0.30 (n=12) 2.98 ± 0.26 (n=12) —— —— 1.83 ± 0.40 0.04 ± 0.03 1.9 ± 0.1

PFNA 2.14 ± 0.54 (n=12) 3.56 ± 0.53 (n=12) 1.5 ± 0.1 2.9 ± 0.1 2.89 ± 0.53 0.6 ± 0.1 2.4 ± 0.1

i,p-PFNA 1.92 ± 0.35 (n=5) 3.33 ± 0.21 (n=5) —— —— —— —— ——

PFOS 2.15 ± 0.22 (n=12) 3.58 ± 0.25 (n=12) 2.4 ± 0.2 3.7 ± 0.2 2.35 ± 0.35 2.1 ± 0.1 3.8 ± 0.1

PFDA 2.34 ± 0.24 (n=5) 3.74 ± 0.27 (n=5) 2.4 ± 0.2 3.8 ± 0.2 2.87 ± 0.23 1.8 ± 0.1 3.6 ± 0.1

PFDS 3.17 ± 0.11 (n=5) 4.51 ± 0.13 (n=5) —— —— —— —— ——

Average Log KD and Log Koc in Sediments

Logo grupo

Correlation between log KOC and PFCs

Logo grupo31

CONCLUSIONSCONCLUSIONS

Concentrations of PFCs in the Jucar River Basin of Spain were similar as those reported in other European, American and Asian countries.

Among 12 target PFCs measured, PFOA and PFOS were consistently found at the greatest concentrations throughout the environmental media.

Occurrence and spatial distribution of detected PFCs in water and sediment between upstream and downstream indicated the input from existing PFCs sources in Spain,

Concentrations of PFOS or PFOA found at some locations were sufficient to potentially cause adverse effects to some wildlife, thus monitoring effort of such PFCs should be of great attention in Spain.

Logo grupo

AcknowledgementAcknowledgement

32

“Assessing and predicting effects on water quantity andquality in Iberian rivers caused by global change”

Consolider-Ingenio 2010 (CSD2009-00065)

http://www.idaea.csic.es/scarceconsolider

Logo grupo33

Thank You for Your Attention

Logo grupo

Any Question?

34