Applicability of Water Passive Samplers to Assess the Chemical Pollution and Ecotoxicity of Catalan Rivers

Transcription

1 Applicability of Water Passive Samplers to Assess the Chemical Pollution and Ecotoxicity of Catalan Rivers NEUS ROIG 1, 2, MARTÍ NADAL 2, JORDI SIERRA 1, 3, ANTONI GINEBREDA 4, MARTA SCHUHMACHER 1,2 AND JOSÉ L. DOMINGO 1 1 Department of Chemical Engineering, ETSEQ, Universitat Rovira i Virgili, Països Catalans 26, 43007, Tarragona, Catalonia, Spain 2 Laboratory of Toxicology and Environmental Health, IISPV, Universitat Rovira i Virgili, Sant Llorenç 21, 43201, Reus, Catalonia, Spain 3 Laboratory of Soil Science, Faculty of Pharmacy, Universitat de Barcelona, Av. Joan XXIII s/n, 08028, Barcelona, Catalonia, Spain 4 Department of Environmental Chemistry, IDAEA, Spanish Council for r Scientific Research (CSIC), Jordi Girona 18-26, 08034, Barcelona, Catalonia, Spain

2 Introduction Water pollution Sediment and water associated toxicity River pollution Sediment pollution Water passive samplers: allow to calculate time averaged concentrations for a period of time & calculate the effective concentration of pollutants that could be bioavailable. The combination of bioassays with chemical analyses is essential to infer probable adverse biological effects of river pollution.

3 Objective Assess the pollution and relative ecotoxicological status of surface water compartments in Catalonia. Analyse the metal concentration in sediment and water of 11 Catalan rivers crossing agricultural, urban and industrial areas Assess the utility and behaviour of water passive samplers methods such as Diffusive Gradient in Thin Films (DGT) and Semipermeable Membrane Device (SPMDs) Study the ecotoxicity of sediment and water with cheap and fast bioassays (bacteria and algae)

4 Materials and Methods Sampling sites Sediment sampling: 3 subsamples at 0 5 cm depth Forest Urban areas Agriculture Industrial areas 1. Muga 2. Fluvià 3. Ter 4. Tordera 5. Besòs 6. Infanta s Channel 7. Llobregat 8. Foix 9. Francolí 10. Segre 11. Ebre Water sampling: water collected with glass amber bottle (total water and filtered water). Acidified with HNO 3 65% DGTs: 3 days in running water SPMDs: 21 days in running water

5 Materials and Methods Water passive samplers Diffusive gradient in thin layer (DGT) Based on a resin (Chelex) for ion exchange Used for free metals and weakly complexed metals (bioavailable fraction) 3 days sampling

6 Materials and Methods Water passive samplers Semi permeable Membrane Device (SPMD) Adsorb non polar organic compounds Semi permeable membrane of polyethylene which contains triolein Inside Can calculate total water volume (L) 21 days sampling

7 Materials and Methods Physico chemical parameters of river water: Dissolved Oxygen level (6.50 mg/l mg/l) ph ( ) Temperature Nutrients Chemical analysis Sediment: grinded and digested by microwave device (HNO 3 65%) DGT s resin layer: Extraction in HNO 3 1M Total water and filtered water acidified with HNO 3 65% Potentially Toxic Elements analysis by Inductively Coupled Plasma (ICP OES and ICP MS) As Cd Cr Hg Mn Ni Pb V Zn

8 Materials and Methods Ecotoxicity tests Sample Extraction method Target organism Method SEDIMENT Sediment Aqueous extract with 1:2 (w:vol) dilution of sediment and NaCl2% Organic Extract: extraction as US EPA Method 3546 and remaining residue dissolved in DMSO Vibrio fischeri Pseudokirschneriella subcapitata Microtox 90% Aqueous Extracts Test (for aqueous extracts) Microtox Basic Test (for organic extracts) OECD Method 201 (for aqueous and organic extracts) WATER DGTs SPMDs SPMDs DGTs Extraction with n hexane, evaporated and remaining residue dissolved in DMSO Resin layer Desorption with HNO 3 1M and neutralized with NaOH Vibrio fischeri Pseudokirschneriella subcapitata Vibrio fischeri Microtox Basic Test OECD Method 201 Microtox Basic Test Toxicity Index (TI) : TI = blank EC50 value/ sample EC50 value TI 1 Non Toxic TI=1 4.9 Marginally Toxic TI=5 9.9 Moderatelly Toxic TI>10 Highly Toxic

9 % benchmark Tordera Besòs Infanta'sC. Llobregat Foix Francolí Segre Ebre Ter Fluvià Muga Results. Potentially Toxic Elements in Sediments Units in % of US EPA sediment benchmark As Cd Cr Hg Zn Mn Ni Pb

10 Results. Potentially Toxic Elements in River Waters % As As HAsO 4 2 Total water Filtered water DGT Units in % of US EPA benchmark for freshwaters Anionic forms Dissolved in river water (total water ~ filterable fraction) No adsorbed by anionic exchange of DGT devices % V V H 2 VO 4 /HVO 4 2

11 Results. Potentially Toxic Elements in River Waters Total water Filtered water DGT % Mn Mn Mn 2+ % Units in % of US EPA benchmark for freshwaters Ni Ni Ni 2+ Cationic forms Adsorbed by river suspended solids (total water > filterable fraction) Adsorbed by DGT devices but in less intensity % Zn Zn 2+

12 Results. Potentially Toxic Elements in River Waters % Cd Cd Total water Filtered water DGT Cd 2+ Units in % of US EPA benchmark for freshwaters Cationic form Highly adsorbed by DGT devices, specially Pb and Cd % Muga Fluvià Ter Tordera Besòs Pb Pb Infanta'sC. Llobregat Foix Pb (OH) + / Pb 2+ Francolí Segre Ebre

13 Results. Potentially Toxic Elements in River Waters % Cr Cr Total water Filtered water DGT Units in % of US EPA benchmark for freshwaters Reduced form: Cr (III) Cationic form More adsorbable by DGTs Oxidised form: Cr (VI) Anionic form Less adsorbable by DGTs More soluble and toxic

14 Results. Ecotoxicological analysis DGTs TI V.fischeri Ebro is the most toxic for metals (moderatelly toxic) WATER SPMDs TI V.fischeri Besòs has the highest toxicity index due to non polar pollutants (Moderatelly toxic) TI P.subcapitata Aqueous extracts TI V.fischeri TI P.subcapitata Aqueous extracts are Non Toxic or marginally toxic in nearly all the cases except for Infanta s Channel (Moderately toxicity). SEDIMENT Organic extracts TI V.fischeri TI P.subcapitata Organic extract showed higher toxicity Besòs and Infanta s channel were classified as Highly toxic due to non polar pollutants. Good correlation between toxicity of organic extracts of sediments and SPMDs Non Tox Marginally Moderatelly Highly

15 Results Self Organizing Maps Fluvià Muga Segre Ebre Foix Francolí Ter Tordera Llobregat Besòs Infanta sc.

16 Conclusions Potentially Toxic Elements content of all Catalan river waters are relatively low, being most samples below the freshwater screening EPA benchmarks. DGTs are useful for sampling those metals that form cations in river conditions following this sequence: Pb >> Cr (III)> Cd > Ni ~ Zn > Mn >>> V~ Cr (VI) ~ As ~ Hg. Able to quantify Cd, even at concentrations below the detection limit Passive sampling methodologies (DGT & SPMD) allow assessing river water toxicity distinguishing between toxicity derived from metals and non polar pollutants.

17 Conclusions Sediments were seen to accumulate higher concentrations of metals than river waters being in industrial and urban areas, far above freshwater sediment screening EPA benchmarks. Sediment toxicity is higher than water toxicity. It demonstrate that sediments pollution is an important aspect to take into account for predicting hypothetical scenarios in case of floods, an usual phenomenon in Mediterranean rivers. The combination of chemical and ecotoxicological methods has been very useful for the characterization of river pollution and ecotoxicity.

18 Applicability of Water Passive Samplers to Assess the Chemical Pollution and Ecotoxicity of Catalan Rivers NEUS ROIG 1, 2, MARTÍ NADAL 2, JORDI SIERRA 1,3, ANTONI GINEBREDA 4, MARTA SCHUHMACHER 1,2 AND JOSÉ L. DOMINGO 1 1 Department of Chemical Engineering, ETSEQ, Universitat Rovira i Virgili, Països Catalans 26, 43007, Tarragona, Catalonia, Spain 2 Laboratory of Toxicology and Environmental Health, IISPV, Universitat Rovira i Virgili, Sant Llorenç 21, 43201, Reus, Catalonia, Spain 3 Laboratory of Soil Science, Faculty of Pharmacy, Universitat de Barcelona, Av. Joan XXIII s/n, 08028, Barcelona, Catalonia, Spain 4 Department of Environmental Chemistry, IDAEA, Spanish Council for r Scientific Research (CSIC), Jordi Girona 18-26, 08034, Barcelona, Catalonia, Spain We gratefully acknowledge Catalan Agency of Water (ACA) of Generalitat de Catalunya., Peter Anders Bergqvist and specially all colleges of AGA group Thank you for your attention