exhaustive characterization of pyrogenic

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


• 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





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


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


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




S-PLE: n-C6:DCM (1:1, v/v). In-cell purification (alumina)

ABC 406 (2014) 7667




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




SP-1




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





• 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








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




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




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


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




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




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


50 100 150 200 250 300 350 400

500

1000 242

120

87 163


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


50 100 150 200 250 300 350 400

500

1000 254

126

226 150


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

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

exhaustive characterization of pyrogenic

Documents