QUÉ PUEDE HACER LA QUÍMICA POR EL MEDIO AMBIENTE? El papel de la química analítica

Transcription

1 QUÉ PUEDE HACER LA QUÍMICA POR EL MEDIO AMBIENTE? El papel de la química analítica L. Ramos Grupo de Química Ambiental Dpto. Análisis Instrumental y Química Ambiental l.ramos@iqog.csic.es VI Curso de Divulgación. Los Avances de la Química y su Impacto en la Sociedad

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 Chlordane DDT Dieldrin Endrin Heptachlor HCB Mirex Toxaphene PCB 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 Numerous families: not separated on a single column; analysis on 2 phases Low concentrations Sample Preparation - Extraction - Purification - Fractionation Instrumental Analysis Chromatographic separation - Detection Data analysis and Interpretation - Unambiguous identification - Quantitation Instrumental analysis: Gas Chromatography (GC)

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? Modulator 1 D 2 D Detector 1 D 2 D Fast GC (1-2 m, Standard (10-60 m, 0.25 mm, 0.5 µm) mm, µm) Non-polar (DB- 1, DB-5) Polar or shape selective (DB- 1701, Rtx-PCB)

12 GC GC schematic diagram Injector Detector Modulator 1 D 2 D 0 1 P M 2 X 3 4 X+Y Y t R X 2 t R Y 8 1 t R Intensity 2 t R X 2 t R X 2 t R Y 2 t R Y 2 t R X 2 t R X 2 t R Y 2 t R Y 2 t R X 2 t R Y 2 t R X 2 t R Y t R, 2 t R P M Raw data signal as recorded by the detector through the entire separation process

13 Intensity X Y t R t R 1 t R Y 1 t R X X Y 2 t R 2 t R X 2 t R Y 2 t 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 2 D oven with the coiled 2D column Peak modulation Original peak is chopped into 3-5 peaks Sensitivity enhancement occurs through focusing 2 D peaks are only ms wide Need detector capable of defining peaks - Hundreds of spectra/sec 1545

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 Peak capacity Chromatographic resolution ToF MS Deconvolution Analytical resolution Separation Analytical information from GC GC ToF MS Targeted Untargeted Specific analytes -Coelutions -Matrix effect Screening -Multi-class analysis -Non-target knowns Quantification (trace, ultra-trace level) Identification - 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 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 2 Y Axis tr (min) Title PCBs PCDD/Fs OCPs PBDEs PCNs CTTs PCTs X axis title 1 t R (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 hexahydroxanthenederivates (PBHDs) Tri-BHD 1 2 Deca-CB 3 4 Tetra-BHD Octa-CBs 5 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 " :1", 3258, sec, sec to 3258, sec, sec , sec, sec to 3258, sec, sec * new possible tri-bhd isomer **tri-bhd standard Newly identified tri- and tetra-bhd isomers further confirmed by GC-QqQ MS tri-bhd MRM 466 -> 387 MRM 466 -> 385 MRM 468 -> 387 A tetra-bhd MRM MRM > -> 387 MRM 546 -> MRM 546 -> 385 MRM 544 -> 385 MRM 544 -> 385 tetra-bhd tetra-bhd B

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 Cl Number of Br

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% 27% 70% Cl Br Cl-Br

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 Declared illegal on Extension, 117,000 m 2-70,000-90,000 T of tires Uncontrolled tire fire - From May 14 th to June 2 nd, 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 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 78 PAHs and related compounds: EPA PAHs (Normalized by abundance of 13 C-BDE 28) Normalized abundances SP-1 SP-2 SP-3 SP fused rings 4-5 fused rings 6-7 fused rings Reconstructed 2D bubble plot Normalized abundances SP-5-6: percent contribution referred to that in SP-4 2 tr (s) 2 tr (s) 2 tr (s) SP-4 (92 comp) SP-5 (87 comp) SP-6 (46 comp) 2 tr (s) SP-7 (34 comp) t R (s)

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 B Me-chrysene/ benzo[a]anthracene m/z 242 Bynaphthalene m/z 254 Comp. # 112 Comp. # Peak True - sample " :1-SENA 4-conc", peak 2878, a Peak True - sample " :1-SENA 4-conc", peak 2879, a t 2892, sec, sec t 2892, sec, sec Library Hit - similarity 970, "Chrysene, 1-methyl-" Library Hit - similarity 978, "2,2'-Binaphthalene"

29 Heterocyclic PAHs Compounds identified in samples Other; 72% S-PACs; 15% O-PACs; 8% N-PACs; 5% 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 SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 Ash TCEP nq TPPO nd 0.57 TCPP TDCPP nd nd nd nd nd TPHP nd nd nd TBP 4.00 nd 6.19 nd DCP nd nd 1.83 nd 3.61 TBOEP nd nd 13.7 TCP nd nd nd nd 61.1 EHDP nd IDPP nd nd nq nd nd nd nd nd IPPP nd 3.62 nd 12.8 nd THP 1.69 nd nd nd nd nd nd nq TEHP nq nq nd nd nd 0.85 ΣOPFRs Giulivo et al. J. Chromatogr. A 1474 (2016) 71

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