New SBSE applications for Continuous Flow Integrative Sampler to analyze emerging compounds in water.

Transcription

1 New SBSE applications for Continuous Flow Integrative Sampler to analyze emerging compounds in water.

2 LABAQUA IN SUEZ Business Lines Environmental Technologies Infraestructures Management Solutions Knowledge Technologies Water quality and environmental control solutions LABAQUA

3 Labaqua Activities. Public Administrations Private Industries AIR QUALITY BIOSAFETY Municipalities INSPECTION AND ENVIRONMENTAL CONSULTANCY ANALYTICAL SERVICES

4 Basic Considerations: SAMPLING STEP THE FIRST STEP OF ANALISYS. -IT IS A CRUCIAL AND VERY IMPORTANT STEP -WHAT ABOUT NEW AVANCES IN SAMPLING TECHNOLOGY????.

5 Basic considerations: Spot Sampling Spot Sampling: A volume of water sample take in a determinate time and a determinate place. Advantages: - Easy and perfectly controlled. - Cheap (for one sample) and it is possible to prepare for each compound by and adequate method. Disadvantages: No information about the average concentrations. Problems with transport, storage and stability. High economic cost to evaluate the real fluctuations in the sampling points.

6 B. Motte A.-S. Lambert Equipe Ecotox. Which sampling strategy? Sampling strategy: sampling technique, frequency and configuration or settings of the automated sampler Adapted to the medium under study and to the use of the data Meet logistical, technical, and analytical costs [ng L -1 ] Calculation of fluxes: Hydrology, Nonpoint source pollution Evaluation of exposition: Microbiology, Ecotoxicology

7 M.-J. Capdeville L. Liger L. Liger Which sampling technique? Grab Fractionated Average

8 Passive sampling Cost-effective alternative for the monitoring of the aquatic environment Application in hydrosystems with micropollutant concentration variations Receiving phase Membrane Aquatic medium Micropollutants Placed in the aquatic medium: continuous sampling Time-weighted average concentrations Lower quantification limits One average concentration Calibration needed

9 Types of passive samplers For chemicals with diverse polarities Chemcatcher 2 < log K ow < 6 POCIS log K ow 3 SPMD log K ow > 3 Polar pesticides to PCB Pharmaceuticals Polar pesticides PAH PCB MESCO 3 < log K ow < 8 PAH PCB So far, there is no universal passive sampler

10 Basic considerations RECEIVING PHASE BARRIER Sampling rate, Rs : amount of contaminant accumulated per unit time. Rs (D, geometry, turbulence, temperature, biofilm) Lag time: Time in which contaminants reach the steady state along the different barriers. t ½ : Linear integrative period Practical and economical aspects: biofilm, analitycal method, cost per sampler, etc.

11 MORE IN DEPTH CONSIDERATIONS SLOW SAMPLER COMPROMISE FAST SAMPLER LOW influence with turbulence LOW Rs HIGH Lag time MEDIUM Rs HIGH influence with turbulence HIGH Rs LOW Lag time t ½!!!!!! MEDIUM Lag time PRC MEDIUM influence with turbulence (flow weigthed average concnetration) ONLY SOLUBLE FRACTION

12 Sorbed mass Determination of average concentrations Exposition Linear accumulation Time Equilibrium Calibration Linear accumulation M S (t) C W R Depends on exposure conditions S t Determination of time-weighted average concentrations C Exposition in situ M R in situ S t

13 To sum up Passive samplers Cost-effective alternative for the monitoring of the aquatic environment Application in hydrosystems with micropollutant concentration variations Time-weighted average concentrations Lower quantification limits One average concentration Calibration needed Low logistical and technical costs No universal sampler Medium analytical cost Easy deployment in the field Depends on exposure conditions Better conservation of the sample

14 CFIS-INTRODUCTION How can solve passive sampler limitations? Passive/Integrative Samplers CFIS

15 Funded projects on passive sampling Almost 10 years of R&D funded activities on passive sampling and the CFIS Dates Project (Funding Body) Ministerio de Industria, Turismo y Comercio Ministerio de Medio Ambiente IMPIVA Applus CDTI Ministerio de Medio Ambiente y medio rural y marino Ministerio de Ciencia e Innovación (Instituto Español de Oceanografía) AQUATIK (LIFE Programme) DEMAGUA (FEDER - Innterconnecta) CFIS-ECOPHARMA (FP7 - Eco-innovation)

16 The CFIS Filter and sleeve 2. Cell Electronic board Peristaltic pump 5. Battery 6. Filter

17 Wide range of compounds Use of various sorbents Gerstel Twisters Activated carbon/alginate beads Oasis HLB cartridges Empore Discs Hydrophobic pesticides, PAHs, PCBs, PBDEs, Alkylphenols BTEX, THMs, other VOCs Polar pesticides, Pharmaceuticals, PFOS and PFOA

18 To sum up Continuous Flow Integrative Sampler (CFIS) Time-weighted average concentrations Lower quantification limits Low logistical cost Medium technical and analytical costs Easy deployment in the field Better conservation of the sample No calibration needed Wide range of compounds Independent from exposure conditions Soluble and particulate fractions One average concentration

19 MATERIALS AND METHODS Analytical method Non-polar compounds. Sorbent: PDMS Twister: PDMS Volume = 49 µl Surface exposure= 125 mm 2 4 samples for device PDMS semi-tubes: PDMS Volume = 184 µl Surface exposure= 690 mm 2 4 samples for device

20 CFIS configuration and operations Continuous sampling Alternating sampling Flow rate 9 ml min -1 Sampling duration Up to 21 days Types of water Drinking water Freshwater Seawater Wastewater

21 Experimental Results CALIBRATION STRATEGY. HPLC pump Peristaltic pump Calibration solution Standard solution in methanol Stirrer Distilled water

22 Ms (ng) Ms (ng) Calibration PDMS SEMI-TUBES (3-56 days) M S M 0 R C t Slope= RsCw 30,00 25,00 20,00 15,00 10,00 y = 0,4247x + 2,6149 R² = 0,9451 5,00 S S W pcb-18 pcb-18 Linéaire (pcb-18) 0,00 0,00 10,00 20,00 30,00 40,00 50,00 60,00 t (days) Rs L/day. Good linearity RSD 20% (Cw=1ng/L) 35,00 30,00 25,00 20,00 15,00 10,00 5,00 y = 0,5262x - 0,4201 R² = 0,9625 pcb-101 pcb-101 0,00 0,00 10,00 20,00 30,00 40,00 50,00 60,00 t (days)

23 Rs obtained PDMS twister PDMS semi-tubes Compound t 50 (h) R s (L/day) R 2 Compound t 50 (h) R s (L/day) R 2 Lindane a α-hch a Fluorene b Lindane ª α-hch ª Fluorene b Phenanthrene c Phenanthrene c Fluoranthene c Fluoranthene c Chrysene c Chrysene c p,p -DDE c Benzo[a]pyren e c Benzo[g,h,i]pe rylene c p,p -DDE c Benzo[a]pyrene c Benzo[g,h,i]per ylene c Rs ml/day RSD < 20 % Rs 300 ml/day RSD < 20 %

24 LOQ LOQ= 10 pg/sorbent. Analytical method (TD-GC-MS) If Rs 300 ml /day, for 21 days 6.3 L 1.6 pg/l

25 Quality Control Electronic Control Internal Standart Deuterated compounds pre-absorved Voltage and Amperage Flow and capacity 25 % Temperature

26 Comparison with other devices ECLIPSE-PCBs-AXELERA PROJECT Silicon membrane SPMD Chemcatcher CFIS

27 Comparison with other devices Rs (L/day/cm²) Compound SPMD silicon membrane CFIS PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB Cw (ng/l) Compound SPMD silicon membrane CFIS PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB PCB

28 EVALUATION OF WWTP EFICENCY EDAR MOLINA DE SEGURA- ESAMUR. Influent WWTP DIAGRAM Grit Filter Primary Treatment Biologycal Treatment Secundary Treatment Terciary Treatment SAMPLE 1 SAMPLE 2 Reclained water SAMPLE 3 3 SAMPLING CAMPAIN. 5/7 SAMPLING TIME

29 4-NONILFENOL RESULTS CFIS device Inicial Spot sample Final Spot sampling European framework Directive(< 0.3)

30 LINDANE RESULTS CFIS device Inicial Spot sample Final Spot sampling European Framework Directive(< 0.3)

31 EMERGING COMPOUNDS

32 Watch List Article 8b of Directive 2008/105/EC- Emerging Pollutants Compound Estimated Log-Kow Reco. Method. Method Used PDMS absorption 17-Alpha-ethinylestradiol (EE2) 4.12 SPE LC-MS-MS SD LC-MS/MS Low 17-Beta-estradiol (E2), Estrone (E1) 3.90 SPE LC-MS-MS SD LC-MS/MS Low Diclofenac 4.02 SPE LC-MS-MS SD LC-MS/MS Yes 2,6-Ditert-butyl-4-methylphenol 5.02 SPE GC-MS TD-GC-MS Yes 2-Ethylhexyl 4-methoxycinnamate 5.80 SPE GC-MS TD-GC-MS Yes Macrolide antibiotics < 2 SPE LC-MS-MS -- No Methiocarb 2.8 SPE LC-MS-MS -- No Neonicotinoids < 1 SPE LC-MS-MS -- No Tri-allate 4.5 GC-MS or LC-MSMS No tested Yes? Oxadiazon 4.8 GC-MS or LC-MSMS No tested Yes?

33 Innovative Continuous Flow Integrative Sampler (CFIS) for Pharmaceutical Compounds Detection: CIFS ECOPHARMA CFIS - ECOPHARMA

34 Sampling Points: Matrices Sea Water Waste Water Continental Water

35 EMERGING AND OTHER POLLUTANTS IN WWTP- EFFLUENT Compound Average Concentration Samples Detected Diclofenac pg/l Sample 1,2,3 2,6-Ditert-butyl-4- methylphenol ng/l Samples 1,2,3 2-Ethylhexyl 4- methoxycinnamate ng/l Samples 1 Almizcles (Galaxolide y tonalide) 100 pg/l Samples 1,2,3 2-Naphthalenol 250 pg/l Samples 1,2,3 2-metilbenzotiazol 5 ng/l Samples 1,2,3

36 Conclusions 1.-An innovative sampler for the TWA monitoring with Rs independent from in-field turbulences has been developed. 2.-Because no membrane is present, lag time values can be considered as negligible. 3.-For non-polar compounds, PDMS in the twistertm format or PDMS Semi-tubes have been used, nevertheless many other formats can be used. This makes it possible to choose the desired Rs (sensitivity) and/or t ½ values. 4.-The fact that no PRC is needed makes the TWA calculation very easy and accurate because a single chromatographic analysis is needed 5.-Different sorbents can be installed inside the cell increasing the range of applications to polar compounds or metals. 6.-CFIS is the unique debice than permit the TOTAL POLUTION CONCENTRATION in water (soluble + paticulate). 7. PDMS is able to detect some emerging compounds listed in Watch list.

37 Thank you!