Perfluorinated compounds in L’Albufera Natural Park Yolanda Pico 1 , Matthias Onghena 1 , Marinella Farré 2 , Cristina Blasco 1 and Damià Barceló 2,3,4 1 Nutrition and Bromatology Laboratory, University of Valencia, Valencia, Spain. 2 Department of Environmental Chemistry, IDAEA-CSIC, Barcelona, Spain 3 Catalan Institute for Water Research (ICRA), Girona, Spain 4 King Saud University, Riyadh, Saudi Arabia Analysis, fate and risks of organic contaminants in river basins under water scarcity Valencia, 7-8 February 2011 Xuquer River Basin Xuquer River Basin
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Xuquer River Basin - CSIC compounds... · La Llosa Vell de Sueca La Llosa. Logo grupo ¾CARTRIDGES: OASIS WAX (6 cc) and HLB (6 cc) ... La Llosa Vellde Sueca La Llosa Logo grupo A12
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Perfluorinated compounds in L’Albufera Natural Park
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
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Xuquer River BasinXuquer River Basin
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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
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A
B
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D
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Tancat de la PipaConstructed wetland
Constructed wetland
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ObjectiveObjective
To demonstrate the spatial distributions of PFCs levels and their distribution in water and sediments from the L’Albufera Natural Park (Valencia, Spain).
Sampling in LSampling in L’’Albufera Natural ParkAlbufera Natural Park
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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
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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
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SolidSolid--phase extraction (SPE) of waterphase extraction (SPE) of water
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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
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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.
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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
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
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Individual PFCs (%-composition)
0% 20% 40% 60% 80% 100%
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% composition
Sampling site
PFBS
PFPA
PFHxA
PFHpA
PFOA
PFNA
i,p‐PFNA
PFOS
PFDA
PFDS
0% 20% 40% 60% 80% 100%
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% composition
Sampling site
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Distribution between water and sediments
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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
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L’Albufera Natural Park (this study) Orge River, France (Labadie and Chevreuil 2011)
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.
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AcknowledgementAcknowledgement
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“Assessing and predicting effects on water quantity andquality in Iberian rivers caused by global change”