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(2) La OMS relaciona 13 millones de muertes en el mundo con factores ambientales.
(3) La contaminación es un proceso global que no entiende de fronteras. Los nuevos usos crean nuevas fuentes potenciales de contaminantes.
(4) Why Chemistry?. Throughout human history, chemistry has helped us survive. Turning stones into tools, making fire, creating ceramics, and preserving food were some of the earliest benefits of chemistry.
(5) Herramientas para la protección del medio ambiente y el hombre Legislación Monitorización Evaluación. Contaminantes Orgánicos Persistentes (COPs) Persistent Organic Pollutants (POPs). • Adopted on 22 May 2001; entered into force on 17 May 2004 • Compounds that once released in the environment, • Remain for a exceptionally long time: persistent • Accumulate in the fatty tissue of living organisms including humans: lipophilic • Widely distributed throughout the environment: longrange transport • Toxic to both humans and wildlife.
(6) The “dirty dozen”. Aldrin. Endrin. Toxaphene. Chlordane. Heptachlor. PCB. DDT. Dieldrin. Mirex HCB. PCDD. PCDF. Other chlorinated compounds. Other brominated compounds. 26 chemicals or groups of chemicals are regulated as POPs under the Stockholm Convention.
(7) Environmental trace analysis: POPs Challenges –> The analytical procedure • Low concentrations • Complex matrices • Many classes. Sample Preparation - Extraction. • Numerous families: not separated on a single column; analysis on 2 phases • Low concentrations. Instrumental Analysis. - Purification. Chromatographic separation. - Fractionation. - Detection. Instrumental analysis: Gas Chromatography (GC). Data analysis and Interpretation - Unambiguous identification - Quantitation.
(8) Analysis of PCBs by GC-µECD. J. Sep. Sci. 27 (2004) 595. The risk of interference increases as the complexity of the matrix increases and as the initial sample size decreases. JCA 1152 (2007) 254.
(9) …and as the sample preparation procedure is simplified. GC-MS (SIM) can add the required selectivity, but…. … then information regarding other analytes is lost.
(10) Is GC´GC necessary?. GC´GC: the concept.
(11) GC´GC: the concept. Match between separator and sample dimensionality in GC´GC. GC´GC schematic diagram Injector. Detector. ? Modulator. 1D. 2D 0. 1D. Standard (1060 m, 0.25 mm, 0.5 µm). X X+Y. 2D. PM 1 2. Fast GC (1-2 m, 3 0.10-0.18 mm, 4 0.10-0.18 µm) 5. Y Non-polar (DB1, DB-5) 1t. R. Polar or shape selective (DB1701, Rtx-PCB). 6. 2t X 2t Y R R. 7 8.
(12) GC´GC schematic diagram Injector. Detector. Modulator. 1D. 2D 0. PM 1 2 3. X. 4 5. Y. X+Y. 6 7. 1t. R. 2. Intensity. 2t X 2t Y R R. tRX 2. t RX 2. 2. 2 2. 2. t RX. 1. 2. t RY. t RX 2. t RY 2. t RX. t RY. t RY. t RY. 2. 8. 2. 3. 4. 5. t RX. 6. 2. tRY. 7. 1t , 2t R R. PM. Raw data signal as recorded by the detector through the entire separation process.
(13) Intensity. X. Y 7. 1t. 1t 1t. R. 6. 5. R. RY 1t. X. 4. 3. 2. 1 2t. Y. R. RX. 2t. RX. 2t 2t. RY. R. Reconstruction of the two-dimensional contour-plot from the collected high-speed secondary chromatograms. Similar signal intensities are connected by contour lines. Typical GC´GC set-up.
(14) Quad-jet dual-stage cryogenic modulator. 2D. oven with the coiled 2D column. Peak modulation 1545 • Original peak is “chopped” into 3-5 peaks • Sensitivity enhancement occurs through focusing •. 2D. peaks are only 200-400 ms wide. • Need detector capable of defining peaks - Hundreds of spectra/sec.
(15) GC´GC features. • Higher peak capacity: more chromatographic peaks per space • Eliminates the need for second column confirmation - (Allow) multiple classes in the same run - (May) eliminate need for extract fractionation • Fast analysis - Requires fast detector: FID, µECD, ToF MS • Provides structured chromatograms for excellent selectivity • Improved sensitivity. Structured chromatograms HP-1 ´ HT-8. JCA 958 (2002) 203.
(16) GC´GC−ToF MS Two complementary options to achieve separation of co-eluting peaks Co -elution GCxGC. ToF MS. Peak capacity. Deconvolution. Chromatographic resolution. Analytical resolution. Separation. Analytical information from GC´GC−ToF MS. Targeted. Untargeted. Specific analytes. Screening. -Coelutions. -Multi-class analysis. -Matrix effect. -Non-target knowns. Quantification. Identification. (trace, ultra-trace level). - Unknown knowns - Unknowns.
(17) Target analysis Challenging separations: Pesticide analysis Rtx-1 ´ Rtx-200. JCA 1186 (2008) 202. Target analysis Challenging separations: EU PAHs in sediments DB17-MS. BaA, MW, 228. DB5-MS. Chr, MW, 228. Optima d-6. CCP, MW, 226. ABC 393 (2009) 1697.
(18) Target analysis Challenging separations: EU PAHs in sediments DB-5 ´ BPX-50. 16. 5. 13. 7 8. 6. 10. 11. 15. 1 4. 3 2. 14 12. 9. BaA (2),Chr (4); MW, 228 CCP (3); MW, 226 BbF (6), BjF (7), BkF(8); MW, 252 IcdP (10); MW, 276 BghiP (11); 278. Untargeted analysis: Screening Multi-class analysis: Organohalogenated compounds HT-8 x BPX-50 PCBs PCDD/Fs OCPs PBDEs PCNs CTTs PCTs. 6. 5. 3. 2. tR (min) Y Axis Title. 4. 2. 1. 0 0. 20. 40. 60. 80. 100. 120. 140. 160. X 1 axis title. tR (min). JCA 1186 (2008) 312.
(19) Untargeted analysis: Screening Multi-class analysis: OBs in bluefin tuna: PBDEs Roof-tile subclasses: Tentative identification of other PBDEs. JCA 1218 (2011) 6995. Untargeted analysis: Identification: Unknowns Naturally produced OBs in bluefin tuna Polybrominated hexahydroxanthene derivates (PBHDs) 1. Tri-BHD. 3 Octa-CBs. 5. 2. Deca-CB. 4. Tetra-BHD. Nona-CBs. • New tri- and tetra-BHD derivates tentatively assigned JCA 1218 (2011) 6995.
(20) Untargeted analysis: Unknown knowns Newly identified tri- and tetra-BHDs in tuna Newly identified tri- and tetra-BHDs in tuna muscle Caliper - sample "0510092:1", 3258 , 4.481 sec , sec to 3258 , 4.4 81 sec , sec - 3258 , 4.150 sec , sec to 3258 , 4.196 sec , sec 1000. 305. 225. **tri-BHD standard. * new possible tri-BHD isomer. 900. 800. 700. 600. 387. 500. 400 466 300. 200. 100 331. 200. 250. 300. 350. 400. 450. 500. Newly identified tri- and tetra-BHD isomers further confirmed by GC-QqQ MS MRM 466 466 MRM MRM 466 466 MRM MRM 468 468. tri-BHD tri-BHD. -> -> -> -> -> ->. 387 387 385 385 387 387. A. tetra-BHD tetra-BHD. MRM MRM 546 546 MRM 546 MRM 546 MRM 544 MRM 544. -> -> -> -> -> ->. B B. 387 387 385 385 385 385 tetra-BHD tetra-BHD.
(21) Untargeted analysis: Unknowns New mixed halogenated carbazole. EST 48 (2014) 9591. ASSESSMENT OF THE ORGANOHALOGENATED BURDEN IN BIOLOGICAL SAMPLES BY NON-TARGET GC´GC−TOF MS. J. Escobar-Arnanz IQOG-CSIC. X. Ortiz M. Pena-Abaurrea E. Reiner Environment Canada.
(22) HT-8 x BPX-50.
(23) Untargeted analysis: Unknowns Organohalogenated compounds in tuna muscle HT-8 x BPX-50. > 5000 peaks!. Scripts: Isotope cluster search Number of Cl1. Number of Br-. 1. 2. 3. 4. 2. 3. 4. 5. 6.
(24) HT-8 x BPX-50. Scripts. Automatic data filtering by classifications and scripts: Tuna muscle ü 354 filtered by the script function • 269 Cl/Br compounds >50% identified by library (similarity >750). Percent distribution 3.2%. Cl. 27%. Br Cl-Br 70%.
(25) CHARACTERIZATION OF AROMATIC ORGANIC COMPOUNDS GENERATED IN AN UNCONTROLLED TIRE LANDFILL FIRE BY GC´GC−TOF MS J. Escobar-Arnanz IQOG-CSIC, Madrid. G. Blanco. MNCN-CSIC, Madrid. S. Mekni E. Eljarrat D. Barceló. IDAEA-CSIC, Barcelona. Used tires: stockpiled or illegally dumped. Seseña´s dump -. The largest one in Spain and one of the largest in EU Used since 2002 Declared illegal on 2015 Extension, 117,000 m2 70,000-90,000 T of tires. Uncontrolled tire fire. - From May 14th to June 2nd, 2016 (5 days latter in Madrid area) - Only 15,000 T of tires remained unburnt.
(26) Characterization of aromatic organic compounds in soils: Uncontrolled combustion of a tire landfill. •. Main focus on VOCs and PAHs (target). Steer et al. (1995): PCDD/Fs (target) Wang et al. (2007): GC-qMS; 165 PAHs - EPA PAHs and 4-7 rings PAHs >> alkyl-PAHs - S-, O- and N-PAHs • Downard et al. (2015): GC-qMS - 4-5 rings PAHs - N- and O-PAHs • •. Seseña´s fire (target) •. Nadal et al. (2016): GC-HRMS, LC-FD - PCBs - PCDD/Fs - EPA PAHs - Selected trace elements. General overview: Organohalogenated compounds HT-8 x BPX-50 SP-1. Scripts.
(27) PAHs and related compounds: EPA PAHs (Normalized by abundance of 13C-BDE 28). Normalized abundances. 78 74 SP-1. 24. SP-2. 20. SP-3. 16. SP-6. 12 8 4 0. 2-3 fused rings 6-7 fused rings. 3. 8. 6 (s). 4. 2t R. Reconstructed 2D bubble plot. 4-5 fused rings. SP-4. 4 1. 2. 5. 7. 6. 10. 2. 9. 0 800. 1200. 1600. 2000. 2400. 2800. 3200. (s) 2t R. 3600. SP-5. 6. (87 comp). 4 2 0 800. 1200. 1600. 2000. 2400. 2800. 3200. 2t R. (s). 6. 3600. SP-6. (46 comp). 4 2 0 800. 1200. 1600. 2000. 2400. 2800. 3200. (s). 4 2. 3600. SP-7. 6 2t R. • Normalized abundances • SP-5-6: percent contribution referred to that in SP-4. (92 comp). (34 comp). 0 800. 1200. 1600. 2000 1t R. 2400 (s). 2800. 3200. 3600.
(28) Other non-regulated PAHs. •. 16 additional non-substituted PAHs: ü Most of them, 4 to 5 fused rings. •. 29 alkylated PAHs: ü Soils: most numerous classes: alkylphenanthrene/anthracene (4 methyl and 7 dimethyl) ü Ash: methyl-chrysene/benzo[a]anthracene (only minor contributors in soils). •. 34 heterocyclic PAHs. Non-regulated PAHs and alkylated PAHs Ash. SP-4. Bynaphthalene. m/z 254. Me-chrysene/ benzo[a]anthracene. m/z 242. B. Caliper - sample "18071604:1-SENA 4-conc", 2892 , 5.200 sec Caliper - sample "18071604:1-SENA 4-conc", 2892 , 5.360 sec , sec to 2892 , 5.200 sec , sec - 600 , 0.000 sec , sec to , sec to 2892 , 5.360 sec , sec - 600 , 0.000 sec , sec to 600 , 0.000 sec , sec 600 , 0.000 sec , sec 1000. 1000. 500. 500. 76. Comp. # 112. 87 91 95 99. 77 81. Comp. # 113. 87. 60 70 80 90 100 60 70 80 90 100 Peak True - sample "18071604:1-SENA 4-conc", peak 2878, a Peak True - sample "18071604:1-SENA 4-conc", peak 2879, a t 2892 , 5.200 sec , sec t 2892 , 5.360 sec , sec 242. 1000. 500. 500 126. 120 87. 800. 167 86. 150. 163. 50 100 150 200 250 300 350 Library Hit - similarity 970, "Chrysene, 1-methyl-" 1000. 254. 1000. 400. 226. 50 100 150 200 250 300 Library Hit - similarity 978, "2,2'-Binaphthalene" 1000 800. 139. 350. 400.
(29) Heterocyclic PAHs Compounds identified in samples. S-PACs; 15% O-PACs; 8% N-PACs; 5% Other; 72%. ü 20 S-PACs • DBT(/naphtho-thiophene) • 5 Me-DBT/naphtho-thiophene • 5 di-Me-DBT/naphtho-thiophene • Phenyl-benzothiazole • Benzo[b]naphtho[2,1-d]thiophen ü 9 O-PACs • 9-H-fluoren-9-one • 9,10-anthracenedione • 2-Me-9,10-antracenedione ü 5-N-PACs • No azaarenes • Carbazole. S-PACs (20 comps). SP-4. SP-5. SP-6. SP-7.
(30) Regulated and emerging halogenated compounds üNo PCBs * üNo PCDD/Fs (LOD!) * üSome OCPs (p,p´-DDE, HCB,…;apparently not related to the fire even) üMinor amounts of PBDEs and halogenated norbornenes üSeveral OPFRs ü4 non-identified halogen-containing compounds. * Agree with Nadal et al. Environ. Intern. 97 (2016) 37. OPFRs Ø s-PLE; LC-QqQMS 3. Results as ng/g sample Analyte TCEP TPPO TCPP TDCPP TPHP TBP DCP TBOEP TCP EHDP IDPP IPPP THP TEHP ΣOPFRs 3. SP-1 5.02 0.63 1.67 nd 0.58 4.00 0.98 2.00 4.74 2.04 nd 0.35 1.69 nq 23.7. SP-2 5.66 0.81 12.4 nd 0.06 nd 9.50 1.15 57.7 5.84 nd 0.33 nd nq 93.4. SP-3 9.41 0.94 3.82 nd nd 6.19 1.51 1.58 8.06 nd nq 14.1 nd nd 45.6. SP-4 8.15 0.02 5.39 nd nd nd nd nd nd 154 nd nd nd 3 170. SP-5 24.7 0.16 15.0 0.09 0.05 24.1 nd 3.06 nd 1.29 nd 3.62 nd 3.38 75.5. Giulivo et al. J. Chromatogr. A 1474 (2016) 71. SP-6 nq 1.13 6.83 0.34 2.28 3.71 1.83 1.35 nd 86.1 nd nd nd nd 104. SP-7 0.10 nd 1.99 0.01 1.35 6.70 nd nd nd 26.7 nd 12.8 nd nd 49.6. Ash 7.53 0.57 4.97 nd nd 0.58 3.61 13.7 61.1 474 nd nd nq 0.85 567.
(31) FINAL REMARKS The Environmental Analytical Chemistry: • Evaluates the efficiency of law implementation through. monitoring programs. • Contributes to early detection of emerging. environmental issues. • GC×GC–ToF MS is a powerful instrumental technique • Adapt to the problem at hand • Identification of non-targeted and unknown compounds. La química analítica protege el medio ambiente L. Ramos l.ramos@iqog.csic.es.
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