exhaustive characterization of pyrogenic
TRANSCRIPT
EXHAUSTIVE CHARACTERIZATION OF PYROGENIC SAMPLES USING GC×GC−ToF MS
L. RamosJ. Escobar-Arnanz
IQOG-CSIC, Madrid
G. BlancoMNCN-CSIC, Madrid
S. MekniE. EljarratD. Barceló
IDAEA-CSIC, Barcelona
Used tires: the problem
Annual global production:- 1.6 billion units/year- 17 million tones of
used tires/year
EU tire production:- 1994, 2.1 million tones- 2019, 19.3 million tones - Anticipated grow: 3.4%- EU cost of disposal:
600 million €/year
1999 EU directive: Landfill of Waste 99/31/EU2018 EU regulation: Anti-dumping duty and duty imposed on imports (Oct 2018/1579)
Used tires: the problem
Cross-linked structures of rubberin tires: vulcanization- Resistant to chemical, bio- andphoto-degradation, and to high T
Management:- Mechanical, thermal or chemicaldestruction
- Recovery of raw material or reprocessing: very difficult
Different chemical composition
% o
f to
tal w
eigh
t
0
5
10
15
20
25
30
Naturalrubber
Syntheticrubber
Carbonblack
Steel Others
Passenger tire Truck tire
Sienkiewicz et al., Waste Manage. (2012)
Used tires: the solution
Rubber wastes can be converted into energy and new polymer materials
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
The uncontrolled fire- From May 14th to June 2nd,
2016 (5 days latter in Madrid area)
- Only 15,000 T of tires remained unburnt
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 combustion of a tire landfill
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
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
- Dioxin-like PCBs- 2,3,7,8-PCDD/Fs- 16 EPA PAHs - Selected trace elements
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
Objectives
• Non-orientated characterization of the (semi-)volatile aromatic compounds present in soils collected in the surrounding the tire fire area by GC×GC−ToF MS
- Confirmation of previously described (and suspected) analytes (16 EPA PAHs; vulcanization additives and plasticizers)
- Organohalogenated compounds- Screening and tentative identification of other (semi-)
volatile analytes in the extracts
Materials and Methods
SAMPLES
✓ 1st sampling campaign:(May 17th, 2016; 3 days afterthe beginning of the fire)• 3 Soils: 20 g
• SP-1: 480 m• SP-2: 960 m• SP-3: 1450 m
✓ 2nd sampling campaign:(July 7th, 2016; 1 month after fire extinction)• 1 Ash: 5 g; SP-4: 100 m• 4 Soils: 20 g
• SP-4: 100 m• SP-5: 320 m• SP-6: 912 m• SP-7: 8760 m (reference soil)
SP-7
...
SP-1
SP-3SP-2
SP-4
SP-6
SP-5
Materials and Methods
QA/QC
• Procedural blanks: 1 every each 4 samples set• No noteworthy background interference
introduced• Recoveries (labelled comp): 65-104 %• RSD: 1-11 %• LODs (S/N, 3:1): 10-200 g/Kg
SAMPLE PREPARATION
PLE (ASE, 350; Dionex)• 1 g sample + 2 g Na2SO4
• Ethyl acetate (1500 psi, 120 ⁰C, 10 min, 2 cycles)
SAMPLE PRETREATMENT
• Sample drying until constant weight• Homogenization• Sample (1-2g) spiked with labelled
analytes• Equilibration overnight
JCA 1256 (2012) 222
Materials and Methods
DATA PROCESSING
LECO ChromaToF v. 4.2
GC×GC−ToF MS Pegasus 4D (Leco Instruments)
• Injection: splitless (1 μL, 275 ⁰C; splitless time, 2 min)• Carrier gas: He, 1 mL min-1
• 1D: HT-8 (30 m × 0.25 mm × 0.25 μm)• 2D: BPX-50 (1.7 m × 0.10 mm × 0.10 μm)• T oven offset, 30 ⁰C• Nitrogen quad-jet dual-stage cryogenic modulator• Modulation time, 6 s; thot, 0.6 s
GC×GC
• T transfer line, 275 ⁰C; T source, 250 ⁰C• EI, 70 eV• m/z: 75-750; 100 Hz
ToF MS
Results and Discussion
Generic sample preparation: soil profile
PLE: Ethyl acetate. Procedure blank
Results and Discussion
Generic sample preparation: soil profile
PLE: Ethyl acetate. Procedure blank
S-PLE: n-C6:DCM (1:1, v/v). In-cell purification (alumina)
ABC 406 (2014) 7667
Results and Discussion
Generic sample preparation: soil profile
PLE: Ethyl acetate. Procedure blank
S-PLE: n-C6:DCM (1:1, v/v). In-cell purification (alumina)
ABC 406 (2014) 7667
PLE: Ethyl acetate. No extra clean-up
Intern J Environ Anal Chem 94 (2014) 1264
General overview: Organohalogenated compounds
HT-8 × BPX-50Data processing
Minimum S/N, 30Similarity match, 750
General overview: Organohalogenated compounds
HT-8 × BPX-50Data processing
Minimum S/N, 30Similarity match, 750
SP-1
General overview: Organohalogenated compounds
HT-8 × BPX-50Data processing
Minimum S/N, 30Similarity match, 750
SP-1
Script functionCl/Br compounds
General overview: Identification criteria
HT-8 × BPX-50Identification criteria
- Authentic standards- Tentative identification
I. Individual (i.e. manual) confirmation of preliminary automatic assignmentII. Identification of potential isomers (structured chromatograms)III. Positive match of mass spectrum with commercial libraries/literature data IV. Mass spectrum interpretation
General overview: Identification criteria
HT-8 × BPX-50Identification criteria
- Authentic standards- Tentative identification
I. Individual (i.e. manual) confirmation of preliminary automatic assignmentII. Identification of potential isomers (structured chromatograms)III. Positive match of mass spectrum with commercial libraries/literature data IV. Mass spectrum interpretation
• Authentic standards:- 13: phenanthrene- 15: anthracene
• Tentative identification:I-II. Isomers:- 35, 38, 43: Me-
phenanthrene/anthracene - 57, 60, 62, 63, 65, 69: diMe-
phenanthrene/anthracene isomer
13 15 3538
39
4357 60
62
63 65
69
72
General overview: Identification criteria
HT-8 × BPX-50Identification criteria
- Authentic standards- Tentative identification
I. Individual (i.e. manual) confirmation of preliminary automatic assignmentII. Identification of potential isomers (structured chromatograms)III. Positive match of mass spectrum with commercial libraries/literature data IV. Mass spectrum interpretation
• Authentic standards:- 13: phenanthrene- 15: anthracene
• Tentative identification:I-II. Isomers:- 35, 38, 43: Me-
phenanthrene/anthracene - 57, 60, 62, 63, 65, 69: diMe-
phenanthrene/anthracene isomer
13 15 3538
39
4357 60
62
63 65
69
72
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
500
1000 192
165 95 139 115
Peak True - sample "Library Search", peak 1, at 0 s (Spec # 0)
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
0 189 94
74 95
Peak True - sample "Library Search", peak 1, at 0 s (Spec # 0) vs. Library Hit - similarity 925, "Phenanthrene, 1-methyl-"
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
500
1000 192
165 95 63 139 39 115
Library Hit - similarity 925, "Phenanthrene, 1-methyl-"
Comp # 35
General overview: Identification criteria
HT-8 × BPX-50Identification criteria
- Authentic standards- Tentative identification
I. Individual (i.e. manual) confirmation of preliminary automatic assignmentII. Identification of potential isomers (structured chromatograms)III. Positive match of mass spectrum with commercial libraries/literature dataIV. Mass spectrum interpretation
• Authentic standards:- 13: phenanthrene- 15: anthracene
• Tentative identification:I-II. Isomers:- 35, 38, 43: Me-
phenanthrene/anthracene - 57, 60, 62, 63, 65, 69: diMe-
phenanthrene/anthraceneisomer
13 15 3538
39
4357 60
62
63 65
69
72
- Tentative identificationIII. Positive match of mass spectrum with commercial libraries/literature
- 16, 74, 80: terphenyl
General overview: Identification criteria
50 100 150 200 250 300 350 400
500
1000 230
215
101 202
77 152
Caliper - sample "18071604:1-SENA 4-conc", 1458 , 2.500 sec , sec to 1458 , 2.500 sec , sec - 3468 , 2.457 sec , sec to 3468 , 2.939 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 230
215
113 202
88 150
Peak True - sample "18071604:1-SENA 4-conc", peak 650, at 1458 , 2.500 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 163
79
108 63 135 91
Library Hit - similarity 949, "o-Terphenyl"
50 100 150 200 250 300 350 400
500
1000 230
115 152 202 77 128
Caliper - sample "19071602:1-C-SENA 5.1", 1968 , 2.860 sec , sec to 1968 , 2.860 sec , sec - 600 , 0.000 sec , sec to 600 , 0.000 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 230
115 152 202 77 128 176
Peak True - sample "19071602:1-C-SENA 5.1", peak 1308, at 1968 , 2.860 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 230
115 152 202 77 176
Library Hit - similarity 961, "m-Terphenyl"
50 100 150 200 250 300 350 400
500
1000 230
115 152
101 202 77 128 169 276
Caliper - sample "19071602:1-C-SENA 5.1", 2040 , 2.940 sec , sec to 2040 , 2.940 sec , sec - 600 , 0.000 sec , sec to 600 , 0.000 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 230
115 152 101 202 77 128 176
Peak True - sample "19071602:1-C-SENA 5.1", peak 1399, at 2040 , 2.940 sec , sec
50 100 150 200 250 300 350 400
200
400
600
800
1000 163
149 70
181
Library Hit - similarity 965, "p-Terphenyl"
# 74 - p-Terphenyl # 80 - m-Terphenyl# 16 - o-Terphenyl
16
74 80 -Similarity match >750-Ratio m/z 215/230: o-terphenyl-Elution order: p- and m-terphenyl
General overview: Identification criteria
HT-8 × BPX-50Identification criteria
- Authentic standards- Tentative identification
I. Individual (i.e. manual) confirmation of preliminary automatic assignmentII. Identification of potential isomers (structured chromatograms)III. Positive match of mass spectrum with commercial libraries/literature dataIV. Mass spectrum interpretation
• Authentic standards:- 13: phenanthrene- 15: anthracene
• Tentative identification:I-II. Isomers:- 35, 38, 43: Me-
phenanthrene/anthracene - 57, 60, 62, 63, 65, 69: diMe-
phenanthrene/anthraceneisomer
13 15 3538
39
4357 60
62
63 65
69
72
PAHs and related compounds: EPA PAHs
74
78
0
4
8
12
16
20
24SP-1
SP-2
SP-3
SP-6
No
rma
lize
da
bu
nd
an
ce
s
(Normalized by abundance of 13C-BDE 28)
2-3 fused rings
4-5 fused rings 6-7 fused rings
EPA PAHs
80
180
280
380
480
580
680
780
1352
0
10
20
30
40AshSP-4SP-5SP-6SP-7N
orm
aliz
ed
ab
un
da
nce
s
(Normalized by abundance of 13C-BDE 28)
2-3 fused rings4-5 fused rings 6-7 fused rings
Reconstructed 2D bubble plot 1 2
3
4
85 6
7
9
10
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2t R
(s)
0
2
4
6
800 1200 1600 2000 2400 2800 3200 36002t R
(s)
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2t R
(s)
0
2
4
6
800 1200 1600 2000 2400 2800 3200 3600
2t R
(s)
1tR (s)
SP-4
SP-5
SP-6
SP-7
• Normalizedvalues
• SP-5-6: percentcontributionreferred to thatin SP-4
Reconstructed 2D bubble plot
0
1
2
3
4
5
6
800 1200 1600 2000 2400 2800 3200 3600
2t R
(s)
0
1
2
3
4
5
6
800 1200 1600 2000 2400 2800 3200 3600
2t R
(s)
1tR (s)
Ash
SP-4
• Normalizedvalues
• SP-4: percentcontributionreferred to thatin ash
Non-regulated PAHs and alkylated PAHs
• 16 additional non-substituted PAHs:✓ Most of them, 4 to 5 fused rings
• 29 alkylated PAHs:✓ Soils: most numerous classes: alkyl-
phenanthrene/anthracene (4 methyl and 7 dimethyl)✓ Ash: methyl-chrysene/benzo[a]anthracene (only
minor contributors in soils)
Non-regulated PAHs and alkylated PAHs
m/z
24
2
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
25
4
Ash SP-4
Me-chrysene/benzo[a]anthracene
Bynaphthalene
Heterocyclic PAHs
Compounds identified in samples
S-PACs, 15%
O-PACs, 8%
N-PACs, 5%
Other, 72%
Heterocyclic PAHs
Compounds identified in samples
S-PACs, 15%
O-PACs, 8%
N-PACs, 5%
Other, 72%
✓ 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
✓ 9 O-PACs• 9-H-fluoren-9-one• 9,10-anthracenedione• 2-Me-9,10-anthracenedione
✓ 5-N-PACs• NO azaarenes• Carbazole
S-PACs(20 comps)
SP-4
SP-5
SP-6
SP-7
Regulated and emerging halogenated compounds
✓No PCBs *✓No PCDD/Fs (LOD!) *
✓Some OCPs (p,p´-DDE, HCB,…;apparently not related to the fire even)
✓Minor amounts of specific PBDEs✓Several OPFRs
✓4 non-identified halogen-containing compounds
* Agree with Nadal et al. Environ. Intern. 97 (2016) 37
PBDEs and halogenated norbornenes
Analyte SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 Ash
BDE-28 nd nd nd nd nq nq nq nd
BDE-47 0.32 0.36 0.29 0.24 0.23 0.21 0.18 0.07
BDE-99 0.58 0.66 0.60 1.47 1.37 1.45 1.64 0.78
BDE-100 0.30 0.29 0.31 0.14 0.15 0.10 0.16 nq
BDE-154 nd nd nd 0.01 0.04 nq 0.01 nq
BDE-153 nd nd nd 0.04 0.05 0.03 0.07 nq
BDE-183 nd nd nd nd nd nd nd nd
BDE-209 0.07 0.05 0.09 0.11 0.11 0.13 0.08 nq
ΣPBDEs 1.27 1.36 1.29 2.01 1.95 1.92 2.14 0.85
Dec 602 nd nd nd nd nd nd nd nd
Dec 603 nd nd nd nd nq nq nd nd
Dec 604 nq nd nd nd nd nd nd nd
syn-DP nq nq nq 0.06 nd 0.02 nd 0.01
anti-DP 0.22 0.21 0.22 0.11 0.07 0.05 nd nq
ΣHNs 0.22 0.21 0.22 0.17 0.07 0.07 nd 0.01
➢ s-PLE; PBDEs: GC-MS-MS 1; HN: GC-NCI-qMS 2
1 Barón et al. Anal. Bioanal. Chem. 406 (2014) 76672 Barón et al. J. Chromatogr. A 1248 (2012) 154
Results as ng/g dw
OPFRs
➢ s-PLE; LC-QqQMS 3
3 Giulivo et al. J. Chromatogr. A 1474 (2016) 71
Analyte SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 Ash
TCEP 5.02 5.66 9.41 8.15 24.7 nq 0.10 7.53
TPPO 0.63 0.81 0.94 0.02 0.16 1.13 nd 0.57
TCPP 1.67 12.4 3.82 5.39 15.0 6.83 1.99 4.97
TDCPP nd nd nd nd 0.09 0.34 0.01 nd
TPHP 0.58 0.06 nd nd 0.05 2.28 1.35 nd
TBP 4.00 nd 6.19 nd 24.1 3.71 6.70 0.58
DCP 0.98 9.50 1.51 nd nd 1.83 nd 3.61
TBOEP 2.00 1.15 1.58 nd 3.06 1.35 nd 13.7
TCP 4.74 57.7 8.06 nd nd nd nd 61.1
EHDP 2.04 5.84 nd 154 1.29 86.1 26.7 474
IDPP nd nd nq nd nd nd nd nd
IPPP 0.35 0.33 14.1 nd 3.62 nd 12.8 nd
THP 1.69 nd nd nd nd nd nd nq
TEHP nq nq nd 3 3.38 nd nd 0.85
ΣOPFRs 23.7 93.4 45.6 170 75.5 104 49.6 567
Results as ng/g dw
OPFRs
➢ s-PLE; LC-QqQMS 3
3 Giulivo et al. J. Chromatogr. A 1474 (2016) 71
Analyte SP-1 SP-2 SP-3 SP-4 SP-5 SP-6 SP-7 Ash
TCEP 5.02 5.66 9.41 8.15 24.7 nq 0.10 7.53
TPPO 0.63 0.81 0.94 0.02 0.16 1.13 nd 0.57
TCPP 1.67 12.4 3.82 5.39 15.0 6.83 1.99 4.97
TDCPP nd nd nd nd 0.09 0.34 0.01 nd
TPHP 0.58 0.06 nd nd 0.05 2.28 1.35 nd
TBP 4.00 nd 6.19 nd 24.1 3.71 6.70 0.58
DCP 0.98 9.50 1.51 nd nd 1.83 nd 3.61
TBOEP 2.00 1.15 1.58 nd 3.06 1.35 nd 13.7
TCP 4.74 57.7 8.06 nd nd nd nd 61.1
EHDP 2.04 5.84 nd 154 1.29 86.1 26.7 474
IDPP nd nd nq nd nd nd nd nd
IPPP 0.35 0.33 14.1 nd 3.62 nd 12.8 nd
THP 1.69 nd nd nd nd nd nd nq
TEHP nq nq nd 3 3.38 nd nd 0.85
ΣOPFRs 23.7 93.4 45.6 170 75.5 104 49.6 567
Results as ng/g dw
GENERAL CONCLUSIONS
• Non-orientated characterization of the (semi-)volatile aromatic fraction on soils impacted by an uncontrolled tire fire by GC×GC−ToF MS
- 118 unique aromatic compounds detected- 105 unique compounds either positively or tentatively identified
• PAHs and related compounds, main toxic families detected• Minor contribution from other halogenated pollutants, except
some OPFRs
JCA 1536 (2018) 163
EXHAUSTIVE CHARACTERIZATION OF PYROGENIC SAMPLES USING GC×GC−ToF MS
L. [email protected]: Proj. Ref. AGL2016-80475-R; S2018/BAA-4393-CM