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L.RamosGrupodeQuímicaAmbiental
Dpto.AnálisisInstrumentalyQuímicaAmbiental
e-mail:[email protected]
¿QUÉPUEDEHACERLAQUÍMICAPORELMEDIOAMBIENTE?
Elpapeldelaquímicaanalítica
VICurso deDivulgación.LosAvancesdelaQuímicaysuImpactoenlaSociedad
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LaOMSrelaciona13millonesdemuertesenelmundoconfactoresambientales
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Lacontaminación esunproceso globalquenoentiendedefronteras
Losnuevosusoscreannuevasfuentespotencialesdecontaminantes
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WhyChemistry?Throughouthumanhistory,chemistryhashelpedussurvive.Turningstonesintotools,makingfire,creatingceramics,andpreservingfoodweresomeoftheearliestbenefitsofchemistry
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Herramientasparalaproteccióndelmedioambienteyelhombre
Legislación
Monitorización
Evaluación
Contaminantes Orgánicos Persistentes (COPs)PersistentOrganicPollutants(POPs)
• Adoptedon22May2001;enteredintoforceon17May2004
• Compoundsthatoncereleasedintheenvironment,• Remainforaexceptionallylongtime:persistent• Accumulateinthefattytissueoflivingorganismsincludinghumans:lipophilic
• Widelydistributedthroughouttheenvironment:long-rangetransport
• Toxic tobothhumansandwildlife
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DieldrinAldrin Chlordane DDT
Endrin Heptachlor HCBMirex
ToxaphenePCDD PCDFPCB
The“dirtydozen”
Otherchlorinatedcompounds
Otherbrominatedcompounds
26chemicalsorgroupsofchemicalsareregulatedasPOPsundertheStockholmConvention
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Dataanalysisand
Interpretation- Unambiguousidentification- Quantitation
InstrumentalAnalysis
Chromatographicseparation- Detection
SamplePreparation- Extraction- Purification- Fractionation
Environmentaltraceanalysis:POPsChallenges–>Theanalyticalprocedure
• Lowconcentrations• Complexmatrices• Manyclasses
• Numerousfamilies:notseparatedonasinglecolumn;analysison2phases
• Lowconcentrations
Instrumentalanalysis:GasChromatography(GC)
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J.Sep.Sci.27(2004)595
Analysis ofPCBs byGC-µECD
JCA1152(2007)254
The risk ofinterference increases asthe complexity ofthematrix increases andasthe initial sample size decreases
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…andasthe sample preparation procedure is simplified
GC-MS(SIM) canaddtherequiredselectivity,but…
…theninformation regardingotheranalytesislost
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IsGC´GC necessary?
GC´GC:theconcept
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GC´GC:theconcept
MatchbetweenseparatorandsampledimensionalityinGC´GC
GC´GC schematicdiagram
Injector
1D 2DModulator
Detector
1tR
PM
Y
X
2tRY2tRX
X+Y
0
1
2
3
4
5
6
7
8
Injector
1D 2DModulator
Detector
1tR
PM
Y
X
2tRY2tRX
X+Y
0
1
2
3
4
5
6
7
8
Standard (10-60m,0.25mm,0.5µm)
Non-polar (DB-1,DB-5)
1D FastGC(1-2m,0.10-0.18mm,0.10-0.18µm)
Polarorshapeselective(DB-1701,Rtx-PCB)
2D
?
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GC´GC schematicdiagram
Injector
1D 2DModulator
Detector
1tR
PM
Y
X
2tRY2tRX
X+Y
0
1
2
3
4
5
6
7
8
Injector
1D 2DModulator
Detector
1tR
PM
Y
X
2tRY2tRX
X+Y
0
1
2
3
4
5
6
7
8
PM
2tRX 2tRY
2tRX
2tRX2tRX
2tRX
2tRX
2tRY
2tRY2tRY
2tRY
2tRY
1 2 3 4 5 6 7
Inte
nsity
1tR, 2tR
PM
2tRX 2tRY
2tRX
2tRX2tRX
2tRX
2tRX
2tRY
2tRY2tRY
2tRY
2tRY
1 2 3 4 5 6 7
Inte
nsity
1tR, 2tR
Rawdatasignalasrecordedbythedetectorthroughtheentireseparationprocess
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1tR
2tR
Intensity
YX
XY
1tRX1tRY
2tRY2tRX
7654321
1tR
2tR
1tR
2tR
Intensity
YX
XYY
1tRX1tRY
2tRY2tRX
7654321
1tR
2tR
Reconstructionofthetwo-dimensionalcontour-plotfromthecollectedhigh-speedsecondarychromatograms.Similarsignalintensitiesareconnectedbycontourlines
TypicalGC´GCset-up
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Quad-jetdual-stagecryogenicmodulator
2Dovenwiththecoiled2Dcolumn
Peakmodulation
• Originalpeakis“chopped”into3-5peaks
• Sensitivityenhancementoccursthroughfocusing
• 2Dpeaksareonly200-400ms wide
• Needdetectorcapableofdefiningpeaks
- Hundredsofspectra/sec
1545
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GC´GC features
• Higherpeakcapacity:morechromatographicpeaksperspace• Eliminatestheneedforsecondcolumnconfirmation
- (Allow)multipleclassesinthesamerun- (May)eliminateneedforextractfractionation
• Fast analysis- Requiresfastdetector:FID,µECD,ToF MS
• Providesstructuredchromatogramsforexcellentselectivity• Improvedsensitivity
Structuredchromatograms
HP-1´ HT-8
JCA958(2002)203
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GC´GC−ToF MS
Twocomplementaryoptionstoachieveseparationofco-elutingpeaks
GCxGC ToF MS
Co -elution
Peak capacity Deconvolution
Separation
Analyticalresolution
Chromatographicresolution
GCxGC
Co -elution
Peak capacity Deconvolution
Separation
Analyticalresolution
Chromatographicresolution
AnalyticalinformationfromGC´GC−ToF MS
Targeted
Specificanalytes-Coelutions-Matrixeffect
Quantification(trace,ultra-trace
level)
Untargeted
Screening-Multi-classanalysis-Non-targetknowns
Identification- Unknownknowns
- Unknowns
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TargetanalysisChallengingseparations:Pesticideanalysis
Rtx-1´ Rtx-200
JCA1186(2008)202
BaA,MW,228
Chr,MW,228
CCP,MW,226
TargetanalysisChallengingseparations:EUPAHsinsediments
ABC393(2009)1697
DB17-MS
DB5-MS
Optimad-6
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TargetanalysisChallengingseparations:EUPAHsinsediments
1
2
3
5
4
7
6 8
9
1011
12
13
14
15
16 DB-5´ BPX-50
BaA (2),Chr(4);MW,228CCP(3);MW,226BbF (6),BjF (7),BkF(8);MW,252IcdP (10);MW,276BghiP (11);278
Untargetedanalysis:ScreeningMulti-classanalysis:Organohalogenated compounds
0 20 40 60 80 100 120 140 1600
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title0 20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
Y Axis
Title
X axis title
PCBsPCDD/FsOCPsPBDEsPCNsCTTsPCTs
HT-8 xBPX-50
1tR (min)
2 tR(m
in)
JCA1186(2008)312
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Roof-tilesubclasses:Tentativeidentificationofother PBDEs
Untargetedanalysis:ScreeningMulti-classanalysis:OBsinbluefin tuna:PBDEs
JCA1218(2011)6995
1
23 4
Deca-CB
Nona-CBsOcta-CBs
Tri-BHD
Tetra-BHD
Untargetedanalysis: Identification:UnknownsNaturallyproducedOBsinbluefin tuna
JCA1218(2011)6995
5
Polybrominated hexahydroxanthene derivates (PBHDs)
• Newtri- andtetra-BHDderivates tentativelyassigned
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200 250 300 350 400 450 500
100
200
300
400
500
600
700
800
900
1000 305 225
387
466
331
Caliper - sample "0510092:1", 3258 , 4.481 sec , sec to 3258 , 4.481 sec , sec - 3258 , 4.150 sec , sec to 3258 , 4.196 sec , sec
*newpossibletri-BHDisomer
**tri-BHDstandard
Untargetedanalysis:UnknownknownsNewlyidentifiedtri- andtetra-BHDsintuna
Newlyidentifiedtri- andtetra-BHDsintunamuscle
Newlyidentifiedtri- andtetra-BHDisomersfurtherconfirmedby GC-QqQ MS
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
MRM546->385MRM546->387
MRM544->385
A
B
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
MRM546->385MRM546->387
MRM544->385
tetra-BHD
MRM546->385MRM546->387
MRM544->385
A
B
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
MRM546->385MRM546->387
MRM544->385
A
B
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
tri-BHD
MRM466->387MRM466->385MRM468->387
tetra-BHD
MRM546->385MRM546->387
MRM544->385
tetra-BHD
MRM546->385MRM546->387
MRM544->385
A
B
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EST48(2014)9591
Untargetedanalysis:UnknownsNewmixedhalogenatedcarbazole
J.Escobar-ArnanzIQOG-CSIC
X.OrtizM.Pena-AbaurreaE.ReinerEnvironment Canada
ASSESSMENTOFTHEORGANOHALOGENATEDBURDENINBIOLOGICALSAMPLESBY
NON-TARGETGC´GC−TOFMS
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HT-8 xBPX-50
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Untargetedanalysis:UnknownsOrganohalogenatedcompoundsintunamuscle
HT-8 xBPX-50
>5000peaks!
Scripts:Isotopeclustersearch
Number of Cl-
1 2 3 4 5 6
Num
ber o
f Br-
1
2
3
4
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Scripts
HT-8xBPX-50
Automaticdatafilteringbyclassificationsandscripts:Tunamuscle
ü 354filteredbythescriptfunction• 269Cl/Brcompounds>50%identifiedbylibrary(similarity>750)
70%
27%
3.2%
Percentdistribution
Cl
Br
Cl-Br
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CHARACTERIZATIONOFAROMATICORGANICCOMPOUNDSGENERATEDINANUNCONTROLLED
TIRELANDFILLFIREBYGC´GC−TOFMS
J.Escobar-ArnanzIQOG-CSIC,Madrid
G.BlancoMNCN-CSIC,Madrid
S.MekniE.EljarratD.Barceló
IDAEA-CSIC,Barcelona
Uncontrolledtirefire- FromMay14th toJune2nd,
2016(5dayslatterinMadridarea)
- Only15,000Toftiresremainedunburnt
Usedtires:stockpiledorillegallydumped
Seseña´s dump- ThelargestoneinSpainandoneofthelargestinEU- Usedsince2002- Declaredillegalon2015- Extension,117,000m2
- 70,000-90,000Toftires
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Characterizationofaromaticorganiccompoundsinsoils:Uncontrolledcombustionofatirelandfill
• MainfocusonVOCsandPAHs(target)• Steeretal.(1995):PCDD/Fs(target)• Wangetal.(2007):GC-qMS;165PAHs
- EPAPAHsand4-7ringsPAHs>>alkyl-PAHs- S-,O- andN-PAHs
• Downard etal.(2015):GC-qMS- 4-5ringsPAHs- N- andO-PAHs
Seseña´s fire(target)• Nadaletal.(2016):GC-HRMS,LC-FD
- PCBs- PCDD/Fs- EPAPAHs- Selectedtraceelements
Generaloverview:Organohalogenatedcompounds
HT-8xBPX-50
SP-1
Scripts
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PAHsandrelatedcompounds:EPAPAHs
74
78
0
4
8
12
16
20
24 SP-1SP-2SP-3SP-6
Normalizedabundances
(Normalizedbyabundanceof13C-BDE28)
2-3fusedrings
4-5fusedrings 6-7fusedrings
Reconstructed2Dbubbleplot
• Normalizedabundances
• SP-5-6:percentcontributionreferred tothatinSP-4
1 2
3
48
5 67
9
10
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2 t R(s
)
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2 t R(s
)
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2 t R(s
)
0246
800 1200 1600 2000 2400 2800 3200 3600
2 t R(s
)
1tR (s)
SP-4(92comp)
SP-5(87comp)
SP-6(46comp)
SP-7(34comp)
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Othernon-regulatedPAHs
• 16additionalnon-substitutedPAHs:ü Mostofthem,4to5fusedrings
• 29alkylatedPAHs:ü Soils:mostnumerousclasses:alkyl-
phenanthrene/anthracene(4methyland7dimethyl)ü Ash:methyl-chrysene/benzo[a]anthracene(only
minorcontributorsinsoils)
• 34heterocyclicPAHs
Non-regulatedPAHsandalkylatedPAHs
m/z
242
B
60 70 80 90 100
500
1000
95 76 87 99 91
Caliper - sample "18071604:1-SENA 4-conc", 2892 , 5.200 sec , sec to 2892 , 5.200 sec , sec - 600 , 0.000 sec , sec to 600 , 0.000 sec , sec
50 100 150 200 250 300 350 400
500
1000 242
120 87 163
Peak True - sample "18071604:1-SENA 4-conc", peak 2878, at 2892 , 5.200 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 167 86
56
108 252
Library Hit - similarity 970, "Chrysene, 1-methyl-"
Comp.#11260 70 80 90 100
500
1000
77 87 81
Caliper - sample "18071604:1-SENA 4-conc", 2892 , 5.360 sec , sec to 2892 , 5.360 sec , sec - 600 , 0.000 sec , sec to 600 , 0.000 sec , sec
50 100 150 200 250 300 350 400
500
1000 254
126
226 150
Peak True - sample "18071604:1-SENA 4-conc", peak 2879, at 2892 , 5.360 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 139
338 111
75 319 169
Library Hit - similarity 978, "2,2'-Binaphthalene"
Comp.#113
m/z
254
Ash SP-4
Me-chrysene/benzo[a]anthracene
Bynaphthalene
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HeterocyclicPAHs
Compoundsidentifiedinsamples
S-PACs;15%
O-PACs;8%
N-PACs;5%
Other;72%
ü 20S-PACs• DBT(/naphtho-thiophene)• 5Me-DBT/naphtho-thiophene• 5di-Me-DBT/naphtho-thiophene• Phenyl-benzothiazole• Benzo[b]naphtho[2,1-d]thiophen
ü 9O-PACs• 9-H-fluoren-9-one• 9,10-anthracenedione• 2-Me-9,10-antracenedione
ü 5-N-PACs• Noazaarenes• Carbazole
S-PACs(20comps)
SP-4
SP-5
SP-6
SP-7
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Regulatedandemerginghalogenatedcompounds
üNoPCBs*üNoPCDD/Fs(LOD!)*
üSomeOCPs(p,p´-DDE,HCB,…;apparentlynotrelatedtothefireeven)
üMinoramountsofPBDEsandhalogenatednorbornenesüSeveralOPFRs
ü4non-identifiedhalogen-containingcompounds
* AgreewithNadaletal.Environ.Intern.97(2016)37
OPFRs
Ø s-PLE;LC-QqQMS 3.Resultsasng/gsample
3 Giulivo etal.J.Chromatogr.A1474(2016)71
Analyte SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 AshTCEP 5.02 5.66 9.41 8.15 24.7 nq 0.10 7.53TPPO 0.63 0.81 0.94 0.02 0.16 1.13 nd 0.57TCPP 1.67 12.4 3.82 5.39 15.0 6.83 1.99 4.97TDCPP nd nd nd nd 0.09 0.34 0.01 ndTPHP 0.58 0.06 nd nd 0.05 2.28 1.35 ndTBP 4.00 nd 6.19 nd 24.1 3.71 6.70 0.58DCP 0.98 9.50 1.51 nd nd 1.83 nd 3.61TBOEP 2.00 1.15 1.58 nd 3.06 1.35 nd 13.7TCP 4.74 57.7 8.06 nd nd nd nd 61.1EHDP 2.04 5.84 nd 154 1.29 86.1 26.7 474IDPP nd nd nq nd nd nd nd ndIPPP 0.35 0.33 14.1 nd 3.62 nd 12.8 ndTHP 1.69 nd nd nd nd nd nd nqTEHP nq nq nd 3 3.38 nd nd 0.85ΣOPFRs 23.7 93.4 45.6 170 75.5 104 49.6 567
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FINALREMARKS
TheEnvironmentalAnalyticalChemistry:
• Evaluatestheefficiencyoflawimplementationthroughmonitoringprograms
• Contributestoearlydetectionofemergingenvironmentalissues
• GC×GC–ToF MSisapowerfulinstrumentaltechnique
• Adapttotheproblemathand• Identificationofnon-targetedandunknowncompounds
Laquímica analítica protegeelmedio ambiente