1

ER1: Ana M. Ballesteros Gómez IVM-VU University Amsterdam (01-04-2012/30-3-2014) Supervision: Pim E.G. Leonards

INFLAME NETWORK ASSEMBLY MEETING

28th APRIL 2014, AMSTERDAM

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MAIN RESEARCH RESULTS

IVM-VU

1. Development/comparison of different analysis techniques for FRs (BFRs and

PFRs)

2. Analysis of RDP and BDP in plastics of electronic products

3. Identification and analysis of a novel BFR (TTBP-TAZ) in plastics and dust

COLLABORATIONS:

University of Antwerp, Toxicological Centre:

- A. Ionas (ESR1), A. Covaci : identification and use of alternative analysis

methods for novel FR and plasticizers

- (Secondment Oct-Nov 2013) C.Erratico, N. van de Eede, A. Ionas, A

Covaci: Metabolism studies with microsomes incubations with EHDPHP

University of Amsterdam (VU), Department of Analytical Chemistry

- W. Jonker, J. Kool. LC microfractionation/toxicity of electronic products

leachate (ongoing)

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DIRECT PROBE -APCI-HRTOF

GC-APCI-HRTOF Separation, sensitivity and matrix effects improved in comparison with LC

GCxGC-APCI-HRTOF

First time of

coupling GCxGC

with HRTOF

GC-APCI, GCxGC-APCI and DIP-APCI-RTOFMS

4

GC or LC (APCI-HRTOF)?

GC-APCI

PBDEs

(tri- till

octa-)

New

BFRs

except

DBDPE

PFRs

LC-APCI

Nona-

and

Deca

BDE

HBCD RDP, BDP,

TTBP-TAZ

Better sensitivity

Less matrix effects

Separation of isomers of

TBP, TMPP

Better sensitivity, prevent

thermal degradation or peak

widening in transfer line

Separation of isomers of

HBCD

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1. Solvent extraction (50mg with

20mL DCM, 24 h shaking+10 min

sonicating) validated with ENFIRO

PAC polymers

2. Ultracentrifugation (10.000 rpm, 5

min)

3. Dilution with methanol 10-1000

times

4. Analysis by LC-APCI(+)-HRTOF

ANALYSIS OF PBDPP (RDP) AND BPA-BDPP (BDP) IN PLASTIC PRODUCTS

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PRODUCTS 2012 RBDPP

w/w BPA-BDPP

w/w Other PFRs

powerboard 1 0.002 0.01 TPHP

powerboard 2 n.d. n.d. -

adaptor 1 0.3 0.06 TPHP

adaptor 2 0.02 0.05 TPHP

Television n.d. n.d. -

LCD television 0.06 0.07 TPHP, TCEP,TMP

P Children toy 1 n.d. n.d. TBOEP

Children toy 2 n.d. n.d. -

Children toy 3 0.003 0.005 -

Power button of a vacuum cleaner

n.d. n.d. -

Plastic adorn 0.3 0.2 TPHP, TMPP

Heat sealer 0.05 0.15 TPHP, TMPP

PRODUCTS BEFORE 2005

RBDPP w/w

BPA-BDPP w/w

Other PFRs

Scanner 1 n.d. n.d. -

Scanner 2 n.d. n.d. -

Scanner 3 n.d. n.d. -

Television 1 5.7 n.d. TPHP

Television 2 n.d. n.d. -

Television 3 n.d. n.d. -

Television 4 n.d. n.d. -

PC monitor n.d. n.d. -

Television monitor

0.007 n.d. TPHP

Flatscreen TV monitor

n.d. n.d. TPHP

Printer 1 7.8 n.d. TPHP

Printer 2 0.005 n.d. -

Printer 3 n.d. n.d. -

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TTBP-TAZ is first time reported in samples in this study

There are no analytical method reported for this compound

Solvent extraction without clean-up

Analysis by LC-APCI(+)-HRTOF-MS

Novel Triazine-based Flame Retardant (TTBP-TAZ) in Plastic Consumer Products and Dust

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Identification by DP(+)-HRTOFMS

0.0

0.5

1.0

1.5

2.0

5x10

Intens.

200 300 400 500 600 700 800 900 1000 1100 m/z

1067.2997

0.00

0.25

0.50

0.75

1.00

1.25

4x10

Intens.

1045 1050 1055 1060 1065 1070 1075 1080 1085 1090 m/z

TTBP-TAZ

DP-APCI(+)-HRTOF-MS spectra of the power board sample 1 containing TTBP-TAZ

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Presence of TTBP-TAZ in products and dust

aQuantitation limit 60 ng g-1

TTBP-TAZ average concentrations and ranges in ng g-1 in dust

Sampling site Number of samples

containing TTBP-TAZ

Median aRange (ng g-1)

On electronics (n=8) 4 535 (1070-22150)

Around electronics (n=7) 4 220 (220-3950)

In floor dust (n=2) 1 - (<20-160) aQuantitation limit 60 ng g-1

TTBP-TAZ concentration ranges in weight percentage (% w/w) in plastic consumer

products purchased in 2012

Product Number of samples containing

TTBP-TAZ

Concentration

range (% w/w)

Electrical power boards and

adaptors (n=4) 4 (0.01-0.8)

Children toys (n=4) 0 -

Televisions (n=2) 2 (0.06, 1.9)

Other household appliances (n=3) 2 (0.3, 0.6)

10

0

0.2

0.4

0.6

0.8

1

1.2

1.4

1.6

1.8

2

Pe

rce

nta

ge b

y w

eig

ht

of

mat

eri

al

2,4,6-TBP

TTBP-TAZ

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A. Ballesteros, C. Erratico, N. van de Eede, A. Ionas, P. Leonards, A. Covaci METABOLISM STUDIES ON EHDPP

Incubation with human liver microsomes or cytosol

Analysis by QTOF (and QQQ) for identification based on accurate mass and

fragmentation patterns (due to lack of standards)

Targeted screening (Meteor software, in silico model) and untargeted screening

(Agilent software)

5.- SECONDENT AT UNIVERSITY OF ANTWERPT (OCTOBER-NOVEMBER 2013)

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CH3

CH3

OP

O

O

O

EHDPHP

(1)

(2)

(3)

(4)

(5)

(8)

(6)

(7)

Monohydroxilated metabolites with –OH in the alkyl chain (OH1-8)

OH

CH3

CH3

OP

O

O

O

OH

CH3

CH3

OP

O

O

O

Monohydroxilated metabolites with –OH in the phenyl group (OH9)

O

CH3

CH3

OP

O

O

O

Metabolites with one ketone group (O1 and O2)

OH

CH3

CH3

OP

O

O

O

OH Dihydroxilated metabolites (OH2 1-10)

OH

CH3

CH3

OP

O

O

O

O Metabolites with one OH- and one ketone group (OOH1-OOH5)

O

O

PO

O

O

CH3

CH3O

OHO

OHOH

OH Phase-II glucuronide- conjugates (GLUC1-8)

OHP

O

O

O

Hydrolysis metabolite (DPHP)

Phase-II glucuronide- conjugates (GLUCb1)

OP

O

O

OCH3

OCH3

OHO

OOH

OH OH

OH

38 metabolites

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(A)

100 200 300 400 500

100

50

0

251.0449

[C12H12O4P]+

69.0695

[ C5H9 ]+

153.0718

[C12H9]+ 379.1659

[C20H28O5P]+

m/z

Rel

ativ

e ab

un

dan

ce

127.1089

43.0169

69.0682 251.0407

109.1027

[C8H13]+

[C8H15O]+

O

CH3

CH3

OP

O

O

O

[C20H26O5P]+ [C12H12O4P]+

377.1442

(B)

100 200 300 400 500

100

50

0

m/z

Rel

ativ

e ab

un

dan

ce

[C5H9]+

(C)

100 200 300 400 500

100

50

0

m/z

Rel

ativ

e ab

un

dan

ce

251.0440

143.1057

97.1014

[C12H12O4P]+

[C8H15O2]+

393.1384

[C20H26O6P]+

251.0456

127.1084

57.0336

145.1205

[C8H13]+

109.1027

[C8H15O]+

395.1176

[C12H12O4P]+ (D)

100 200 300 400 500

100

50

0

m/z

Rel

ativ

e ab

un

dan

ce

OH

CH3

CH3

OP

O

O

O

OH

CH3

CH3

OP

O

O

O

O

OH

CH3

CH3

OP

O

O

O

OH

[C20H28O6P]+

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RELATIVE ABUNDANCE OF METABOLITES

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…OVERVIEW MAIN RESEARCH RESULTS

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Publications in international journals-INFLAME

1. Ballesteros-Gómez, Ana; de Boer, Jacob; Leonards, Pim .E.G. Novel Analytical Methods for Flame Retardants and Plasticizers based on Gas Chromatography, Comprehensive Two-Dimensional Gas Chromatography and Direct Probe Coupled to Atmospheric Pressure Chemical Ionization-High Resolution Time-of-Flight-Mass Spectrometry, Analytical Chemistry, 85 (2013) 9572–9580 2.Ballesteros Gómez, Ana; Brandsma, S.H.; de Boer, Jacob; Leonards, Pim E.G.; Analysis of two alternative organophosphorus flame retardants in electronic and plastic consumer products: resorcinol bis-(diphenylphosphate) (PBDPP) and bisphenol A bis (diphenylphosphate) (BPA-BDPP)"2014, doi:10.1016/j.chemosphere.2013.12.099 3. Ballesteros Gómez, Ana; Brandsma, S.H.; de Boer, Jacob; Leonards, Pim E.G. Direct probe atmospheric pressure photoionization/atmospheric pressure chemical ionization high-resolution mass spectrometry for fast screening of flame retardants and plasticizers in products and waste. 2014 Analytical and Bionalytical Chemistry. DOI 10.1007/s00216-014-7636-8 4. Ballesteros-Gómez, Ana; de Boer, Jacob; Leonards, Pim .E.G. A Novel Brominated Triazine-based Flame Retardant (TTBP-TAZ) in Plastic Consumer Products and Indoor Dust. 2014 Environ. Sci. Technol., Just Accepted Manuscript DOI: 10.1021/es4057032 5.- Ballesteros-Gómez, Ana; Claudio A. Erratico,, Nele Van den Eede,, Alin C. Ionas,, Pim E.G. Leonards, Adrian Covaci. In vitro metabolism of 2-ethylhexyldiphenyl phosphate (EHDPHP) with human liver subcellular fractions (in preparation)

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Contribution to conferences

INVITED ORAL PRESENTATIONS 1. Novel analytical methods for flame retardants based on high resolution MS-MicroTOF II: GC-APCI, GCxGC-APCI and DP-APCI/APPI. Workshop: 2013 Bruker Daltonics Users’ Meeting, Eindhoven (The Netherlands). 2013 ORAL CONTRIBUTIONS 1. New screening tools for flame retardants in e-waste based on GC, GCxGC and direct probe coupled to APCI-HRTOF. Authors: Ballesteros-Gomez A (presenting author), de Boer, Jacob.; Leonards, Pim Conference: BFR2013, San Francisco (California).2013 2. New screening tools for flame retardants in e-waste based on GC, GCxGC and direct probe coupled to APCI-HRTOF. Authors: Ballesteros-Gomez, Ana (presenting author), de Boer, Jacob; Leonards, Pim Conference: Dioxin2013, Daegu (South Korea).2013 CO-AUTHOR 1. Oral contribution. 1. Identification of novel halogenated flame retardants using spectra-less databases. Authors: Ionas, Alin (presenting author); Ballesteros-Gomez, Ana; Leonards, Pim; Covaci, Adrian Conference: Dioxin2013, Daegu (South Korea).2013 2. Poster. Identification strategies for flame retardants emplying spectra-less databases. Authors: Ionas, Alin; Ballesteros-Gomez, Ana; Leonards, Pim; Covaci, Adrian Conference: Dioxin2013, Daegu (South Korea).2013

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PRESS RELEASES

1. Chemical & Engineering News, 4 April 2014, ISSN 0009-2347, American Chemical Society. :http://cen.acs.org/articles/92/web/2014/04/Scientists-Uncover-New-Brominated-Flame.html

2. C2W (Chemisch2Weekblad). VU betrapt kunststofindustrie op geheim ingrediënt, 14 April 2014, http://www.c2w.nl/vage-vlamvertrager.366677.lynkx

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RESEARCH PROPOSALS

NWO (Netherlands, IVM-VU University) 3 year Junior Researcher (July 2014)

FWO (Belgium, University of Antwerpt) 1 year postdoct (June 2014)

After INFLAME: postdoctoral researcher at University of Antwerp,

A. Covaci

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a.m.ballesterosgomez@gmail.com

Thank you for your attention !