development and comparison of gas chromatography-mass ...€¦ · web viewsupporting information....

Supporting Information

Development and comparison of gas chromatography-mass spectrometry techniques for analysis of flame retardants

Jakob Gustavssona,*, Lutz Ahrensa, Minh A. Nguyena, Sarah Josefssona,b, Karin Wiberga

aDepartment of Aquatic Sciences and Assessment, Swedish University of Agricultural Sciences, Box 7050, SE-75007, Uppsala, Sweden

bGeological Survey of Sweden, Box 670, 75128 Uppsala, Sweden

*Corresponding author

Email: [email protected]

Phone: +4618673142

Pages: 47

Tables: 14

Figures: 2

Table S1 Previously applied clean-up materials for PBDEs, HFRs and OPFRs in literature.Group PBDE HFR

PBDEs 24-DBP

26-DBP DBHCTD DP 246-

TBP HBCDD OBTMPI

TBP-DBPE HBB TBCO PBEB BATE BEH-

TEBP BTBPE ATE EH-TBB DBE-DBCH

Neutral silica[1-6] X X X X X X X X X X X

Neutral silica +Alumina [7] X X

Neutral silica + GPC [8]

Alumina [9, 10] X X X X X X X X

Acidified silica [11, 12] X X X X X X X X XMultilayer silica (Basic/neutral/acidified

(/AgNO3)) [13, 14] X X X X X X X X X X X X X X X

Acid treatment beforeacidified-silica + neutral

silica [15]X X X X X X X X X X X X

Florisil [10-12, 16, 17] X X X X X X X X X X X X

SPE (Oasis HLB) [18]

HFR OPFR

DBDPE PBT TBBPA-DBPE TEP TDCIPP TCP TCIPP TPP TNBP TCEP TiBP TNBP TPHP TBOEP TEHP TMP EHDPP TiPPP

Neutral silica [1-6] X X X X X X X X X X X X X X X

Neutral silica + Alumina [7] X X

Neutral silica + GPC [8] X X X X X X X X X X

Alumina [9, 10] X X X X

Acidified silica [11, 12] XMultilayer silica (Basic/neutral/acidified

(/AgNO3)) [13, 14] X

Acid treatment beforeacidified-silica + neutral

silica [15]X X

Florisil [10-12, 16, 17] X X X X X X X X X X X X X X X

SPE (Oasis HLB) [18] X X X X X

S2

Table S2 Structure, molecular formula, CAS no., retention time and physico-chemical properties of all PBDEs (n = 27) included in this study.a Abbreviation Name Structure Molecular

formula CAS no. MWb tRc Bpd SW

e log KOW

flog

KOCg

log KOA

h VPi Hj pKa

k

BDE3 4-bromodiphenylether C12H9BrO 101-55-3 249.1 6.55 310.0 5.69 4.94 3.71 7.66 1.5E-1 4.7E-5 na

BDE72,4-

dibromodiphenylether

C12H8Br2O 147217-71-8 328.0 7.82 344.0 1.27 4.99 3.74 8.11 3.7E-3 1.87E-5 na

BDE15di(4-Bromophenyl)

ether C12H8Br2O 2050-47-7 328.0 8.19 344.0 1.27 5.83 4.21 8.95 1.5E-2 1.87E-5 na

BDE172,2’,4-

tribromodiphenyl ether

C12H7Br3O 147217-75-2 406.9 9.11 374.8 0.268 5.88 4.23 9.40 3.1E-4 7.45E-6 na

S3

BDE282,4,4’-

tribromophenylether

C12H7Br3O 41318-75-6 406.9 9.28 374.8 0.268 5.88 4.23 9.50 3.1E-4 7.45E-6 na

BDE472,2',4,4'-

Tetrabromodiphenylether

C12H6Br4O 5436-43-1 485.8 10.47 405.5 5.4E-2 6.77 4.73 10.7 3.2E-5 3.0E-6 na

BDE492,2′,4,5′-


C12H6Br4O 243982-82-3 485.8 10.15 405.5 5.4E-2 6.77 4.73 10.7 3.2E-5 3.0E-6 na

BDE662,3′,4,4′-


C12H6Br4O 189084-61-5 485.8 10.30 405.5 5.4E-2 6.77 4.73 10.7 3.2E-5 3.0E-6 na

S4

BDE712,3′,4′,6-


C12H6Br4O 189084-62-6 485.8 10.19 405.5 5.4E-2 6.77 4.73 10.7 3.2E-5 3.0E-6 na

BDE773,3',4,4'-


C12H6Br4O 93703-48-1 485.8 10.71 405.5 5.4E-2 7.61 5.19 10.7 3.2E-5 3.0E-6 na

BDE852,2',3,4,4'-

Pentabromodiphenylether

C12H5Br5O 82346-21-0 564.7 11.65 436.2 1.1E-2 7.66 5.22 12.0 3.3E-6 1.2E-6 na

BDE992,2',4,4',5-


C12H5Br5O 32534-81-9 564.7 11.28 436.2 1.1E-2 6.841 4.76 11.2 1.4E-4 1.2E-6 na

S5

BDE1002,2',4,4',6-


C12H5Br5O 189084-64-8 564.7 11.04 436.2 1.1E-2 7.66 5.22 12.0 3.3E-6 1.2E-6 na

BDE1192,3′,4,4′,6-


C12H5Br5O 189084-66-0 564.7 11.13 436.2 1.1E-2 7.66 5.22 12.0 3.3E-6 1.2E-6 na

BDE1263,3′,4,4′,5-


C12H5Br5O 366791-32-4 564.7 11.75 436.2 1.1E-2 8.50 5.69 12.8 3.3E-6 1.2E-6 na

BDE1382,2′,3,4,4′,5′-

Hexabromodiphenylether

C12H5Br5O 182677-30-1 643.6 12.53 466.9 2.1E-3 8.55 5.71 13.3 3.8E-7 4.7E-7 na

S6

BDE1532,2',4,4',5,5'-


C12H4Br6O 68631-49-2 643.6 12.15 466.9 2.1E-3 8.55 5.71 13.3 3.8E-7 4.7E-7 na

BDE1542,2′,4,4′,5,6′-


C12H4Br6O 207122-15-4 643.6 11.84 466.9 2.1E-3 8.55 5.71 13.3 3.8E-7 4.7E-7 na

BDE1562,3,3’,4,4’,5-

hexabromodiphenylether

C12H4Br6O 405237-85-6 643.6 12.69 466.9 2.1E-3 8.55 5.71 13.3 3.8E-7 4.7E-7 na

BDE183

2,2',3,4,4',5',6-Heptabromodipheny

lether

C12H3Br7O 207122-16-5 722.5 12.96 497.6 3.9E-4 9.44 6.20 14.6 4.4E-8 1.9E-7 na

S7

BDE1842,2’,3,4,4’,6,6’-

heptabromodiphenylether

C12H3Br7O 117948-63-7 722.5 12.80 497.6 3.9E-4 9.44 6.20 14.6 4.4E-8 1.9E-7 na

BDE1912,3,3’,4,4’,5’,6-

heptabromodiphenylether

C12H3Br7O 446255-30-7 722.5 13.18 497.6 3.9E-4 9.44 6.20 14.6 4.4E-8 1.9E-7 na

BDE1962,2’,3,3’,4,4’,5,6’-octabromodiphenyl

etherC12H2Br8O 32536-52-0 801.4 14.07 528.3 7.4E-5 10.3 6.70 15.8 4.9E-9 7.5E-8 na

BDE1972,2’3,3’,4,4’,6,6’-

octabromodiphenylether

C12H2Br8O 117964-21-3 801.4 13.87 528.3 7.4E-5 10.3 6.70 15.8 4.9E-9 7.5E-8 na

S8

BDE2062,2',3,3',4,4',5,5',6-

Nonabromodiphenyl ether

C12H1Br9O 63936-56-1 880.3 15.17 559.0 1.4E-5 11.2 7.19 17.1 5.4E-10 2.3E-8 na

BDE2072,2',3,3',4,4',5,6,6'-

Nonabromodiphenylether

C12H1Br9O 437701-79-6 880.3 14.93 559.0 1.4E-5 11.2 7.19 17.1 5.4E-10 2.3E-8 na

BDE209Decabromo

diphenylether

C12Br10O 109945-70-2 959.2 16.53 589.7 2.6E-6 12.11 7.68 18.4 6.2E-10 1.2E-8 na

aPhysico-chemical properties (except pKa) were modeled using EPIsuite 4.1 (US EPA); na = not available; bMW = molecular weight; ctR = retention time (min) using GC-conditions given in Section 2.3; dBp = boiling point (°C); eSW= water solubility (mg L-1, 25°C); fKOW = octanol-water partition coefficient; gKOC = organic carbon-water partition coefficient; hKOA = octanol-air partition coefficient; iVp

= vapour pressure; jH= Henry’s law constant (atm m3 mole-1); kacid dissociation values (pKa) from Bergman et al. (2012) [19]. lExperimental value from EPIsuite 4.1.

S9

Table S3 Structure, molecular formula, CAS no., retention time and physico-chemical properties of all HFRs (n = 46) included in this study.a

Abbreviation Name Structure Molecular formula CAS no. MWb tR

c Bpd SWe log

KOWf

log KOC

glog

KOAh VP

i Hj pKak

2,4-DBP 2,4-Dibromophenol C6H4Br2O 615-58-7 251.9 3.69 269.7 3536 3.29 2.87 8.66 2.1 8.9E-8 7.86

2,6-DBP 2,6-Dibromophenol C6H4Br2O 608-33-3 251.9 4.04 269.7 3536 3.29 2.95 8.80 0.57 8.9E-

8 na

4-BP 4-Bromophenol C6H5BrO 106-41-2 173.0 - 223.0 14308 2.40 2.53 7.80 1.2 1.5E-7 na

4´-PeBPO-BDE208Pentabromophenoxy-

nonabromo-diphenyl ether

C18Br14O2 58965-66-5 1367 - 808.7 1.4E-6 16.9 10.38 26.5 4.9E-

186.5E-

12 na

S10

2,4,6-TBP 2,4,6-Tribromophenol C6H3Br3O 118-79-6 330.8 6.18 310.1 788 4.131 3.38 10.0 0.040 3.6E-

8

6.32 ±

0.23

ATE Allyl 2,4,6-tribromophenylether C9H7Br3O 221-913-2 370.9 6.89 323.2 1.3 5.59 4.07 8.6 0.014 2.7E-

5 na

BATE2-Bromoallyl 2,4,6-

tribromophenylether

C9H6Br4O na 449.8 8.35 359.1 0.59 5.98 4.29 9.7 9.8E-4

5.3E-6 na

BEH-TEBPBis(2-ethyl-1-

hexyl)tetrabromophthalate

C24H34Br4O4 26040-51-7 706.1 13.56 539.8 1.9E-6 11.95 7.40 16.9 2.3E-

93.0E-

7 na

S11

BTBPE1,2-Bis(2,4,6-

tribromophenoxy)ethane

C14H8Br6O2 37853-59-1 687.6 13.2 502.2 2.2E-4 9.15 6.10 15.7 3.2E-

87.3E-

9 na

DBDPE1,2-Bis(2,3,4,5,6-

pentabromophenyl)ethane

C14H4Br10 84852-53-9 971.2 17.47 600.9 9.7E-7 13.64 11.84 19.2 2.5E-

116.4E-

8 na

α-DBE-DBCH (TBECH)

1,2-Dibromo-4-(1,2-dibromoethyl) cyclohexane C8H12Br4 3322-93-8 427.8 8.16 336.8 0.92 5.24 4.55 8.0 0.014 4.2E-

5 na

β-DBE-DBCH(TBECH)

1,2-Dibromo-4-(1,2-dibromoethyl) cyclohexane C8H12Br4 3322-93-8 427.8 8.16 336.8 0.92 5.24 4.55 8.0 0.014 4.2E-

5 na

S12

DBHCTD Hexachlorocyclo-pentadienyldibromocyclooctane C13H12Br2Cl6 51936-55-1 540.8 11.31 414.8 1.4E-

4 7.91 6.87 11.1 1.4E-5

1.8E-5 na

DBNPG Dibromoneopentylalcohol C5H10Br2O2 3296-90-0 261.9 5.58 307.0 10158 0.85 0.69 7.84 8.6E-

44.1E-

9 13.6

DBS (2,2-Dibromovinyl)benzene C8H6Br2 31780-26-4 261.9 4.39 273.4 75.8 3.55 3.08 5.90 0.78 1.1E-

4 na

anti-DP Dechlorane Plus C18H12Cl12 13560-89-9 653.7 13.91 486.8 6.5E-7 11.27 9.78 14.8 9.4E-

87.4E-

6 na

S13

syn-DP Dechlorane Plus C18H12Cl12 13560-89-9 653.7 13.67 486.6 6.5E-7 11.27 9.78 14.8 9.4E-

87.4E-

6 na

EH-TBB 2-Ethylhexyl 2,3,4,5-tetra-bromobenzoate C15H18Br4O2 183658-27-7 549.9 11.33 432.9 3.4E-

3 8.75 5.70 12.3 4.6E-6

6.4E-6 na

HBB Hexabromo-benzene C6Br6 87-82-1 551.5 10.02 370.7 0.23 6.07 1 5.27 9.1 2.2E-

62.2E-

5 na

α-HBCDD Hexabromo-cyclododecane C12H18Br6 3194-55-6 641.7 12.34 462.0 3.1E-

3 7.74 6.72 10.5 2.3E-6

4.6E-5 na

S14

β-HBCDD Hexabromo-cyclododecane C12H18Br6 3194-55-6 641.7 12.34 462.0 3.1E-

3 7.74 6.72 10.5 2.3E-6

4.6E-5 na

γ-HBCDD Hexabromo-cyclododecane C12H18Br6 3194-55-6 641.7 12.34 462.0 3.1E-

3 7.74 6.72 10.5 2.3E-6

4.6E-5 na

HEEHP-TEBP2-(2-hydroxyethoxy) ethyl-

2-hydroxy-propyl-3,4,5,6-tetrabromophthalate

C15H16Br4O7 20566-35-2 627.9 11.43 537.5 769 3.83 2.00 17.8 3.2E-12

2.7E-16 na

OBTMPI

4,5,6,7-Tetrabromo-1,1,3-trimethyl-

3-(2,3,4,5-tetrabromophenyl)-indane

C18H12Br8 1084889-51-9 867.5 15.86 572.2 8.7E-7 13.03 11.31 17.8 2.1E-

104.6E-

7 na

S15

PBB-Acr Pentabromobenzylacrylate C10H5Br5O2 59447-55-1 556.7 10.91 411.7 0.13 6.89 4.67 12.4 1.8E-

57.5E-

8 na

PBBBr Pentabromobenzyl-bromide C7H2Br6 38521-51-6 565.5 10.56 389.2 0.067 7.33 6.36 10.9 8.5E-

56.9E-

6 na

PBCH Pentabromochloro-cyclohexane C6H6Br5Cl 87-84-3 513.1 8.90 373.2 0.45 4.721 4.10 9.1 4.6E-

49.6E-

7 na

PBEB Pentabromoethyl-benzene C8H5Br5 85-22-3 500.6 9.46 363.2 0.11 7.48 6.49 10.0 6.2E-

47.9E-

5 na

S16

PBP Pentabromo-phenol C6HBr5O 608-71-9 488.6 9.57 374.8 34 5.96 4.39 12.6 6.8E-

65.6E-

94.4±0.33

PBPAEPentabromo-phenyl allyl

etherC9H5Br5O 3555-11-1 528.7 9.95 386.0 0.052 7.37 5.06 11.1 1.2E-

44.2E-

6 na

PBT Pentabromo-toluene C7H3Br5 87-83-2 486.6 9.23 351.6 0.35 6.99 6.07 9.6 2.0E-

56.0E-

5 na

TBBPA Tetrabromo-bisphenol A C15H12Br4O2 79-94-7 543.9 12.14 454.6 4.3E-

3 6.25 5.42 18.2 9.1E-7

2.3E-13

7.5/8.5 ± 0.1

S17

TBBPA-BAE Tetrabromo-bisphenol Abis(allyl ether) C21H20Br4O2 25327-89-3 624.0 - 508.7 3.4E-

6 10.02 6.58 15.3 2.7E-7

1.3E-7 na

TBBPA-BDBPE Tetrabromo-bisphenol A-bis(2,3-dibromo-propyl ether) C21H20Br8O2 21850-44-2 943.6 14.03 646.9 9.4E-

7 11.52 7.41 20.3 8.5E-13

4.1E-11 na

TBBPA-DHEE Tetrabromo-bisphenol Adihydroxyethyl ether C19H20Br4O4 4162-45-2 632.0 13.92 574.1 2.3E-

2 6.78 3.96 17.9 5.3E-12

1.8E-13 13.8

TBBP-DBPETetrabromo-bisphenol-S-bis(2,3-dibromopropyl)

etherC18H14Br8O4S 42757-55-1 965.6 - 705.9 9.7E-

7 9.52 6.33 21.8 1.0E-14

1.2E-14 na

S18

α-TBCO1,2,5,6-

Tetrabromo-cyclooctane

C8H12Br4 3194-57-8 427.8 8.49 342.8 1.5 5.24 4.55 8.0 9.4E-3

4.2E-5 na

β-TBCO1,2,5,6-

Tetrabromo-cyclooctane

C8H12Br4 3194-57-8 427.8 8.49 342.8 1.5 5.24 4.55 8.0 9.4E-3

4.2E-5 na

TBCT 1,2,3,4-Tetrabromo-5-chloro-6-methylbenzene C7H3Br4Cl 39569-21-6 442.2 8.70 339.4 0.38 6.74 5.85 9.1 3.7E-

31.1E-

4 na

TBNPA Tribromoneopentylalcohol C5H9Br3O 1522-92-5 324.8 5.84 299.7 852 2.25 1.76 8.5 5.6E-

31.3E-

8 13.7

S19

TBP-DBPE 2,3-Dibromopropyl-2,4,6-tribromophenyl ether C9H7Br5O 35109-60-5 530.7 9.88 393.7 0.080 6.34 4.49 11.1 8.3E-

54.7E-

7 na

TBX 2,3,5,6-tetrabromo-p-xylene C8H6Br4 23488-38-2 421.8 8.35 331.9 0.53 6.65 5.77 8.8 5.5E-

31.7E-

4 na

TCBPA Tetrachloro-bisphenol-A C15H12Cl4O2 27360-90-3 366.1 10.81 438.3 0.40 6.22 4.84 16.2 3.8E-7

2.8E-12 na

TDBP-TAZTO

1,3,5-tris(2,3-dibromopropyl)-1,3,5-triazine-

2,4,6(1H,3H,5H)-trione

C12H15Br6N3O3 52434-90-9 728.7 13.54 669.5 1.4E-5 7.37 4.92 23.7 1.5E-

101.2E-

18 na

S20

TEBP-Anh 3,4,5,6-Tetrabromophthalicanhydride C8Br4O3 632-79-1 463.7 10.03 394.1 65 5.63 3.58 10.8 2.7E-

61.6E-

7 na

TTBP-TAZ2,4,6-tris(2,4,6-

tribromophenoxy)-1,3,5-triazine

C21H6Br9N3O3 25713-60-4 1067 18.00 767.7 1.1E-6 11.46 7.25 21.5 9.3E-

172.4E-

12 na



S21

Table S4 Structure, molecular formula, CAS no., retention time and physico-chemical properties of all OPFRs (n = 29) included in this study.a

Abbreviation Name Structure Molecular formula CAS no. MWb tR

c Bpd SWe log

KOWf

log KOC

glog

KOAh VP

i Hj pKak

BADP Bisphenol A bis(diphenyl phosphate) C39H34O8P2 5945-33-5 692.7 - 480.0 1.9E-6 10.0 6.24 21.7 2.7E-6 4.6E-14 na

bBDBP bis(2,3-Dibromopropyl)phoshate C6H11Br4O4P 5412-25-9 497.7 - 434.9 220 2.53 2.43 13.3 6.0E-7 4.3E-13 na

CDP Cresyl diphenylphosphate C19H17O4P 26444-49-5 340.3 - 452.9 1.5 5.25 3.19 10.3 1.4E-5 4.2E-8 na

mDEP/dDEP Diethyl phosphate(mono & di) C4H11O4P 598-02-7 154.1 - 258.8 4.0E5 0.32 1.21 7.57 1.8E-3 1.4E-9 na

S22

DMP Dimethylphosphate C2H7O4P 813-78-5 126.1 - 222.9 1.0E6 -0.66 0.66 6.84 46 7.8E-10 na

EHDPP 2-Ethylhexyldiphenyl phosphate C20H27O4P 1241-94-7 362.4 10.00 443.0 0.18 5.731 3.87 8.4 4.5E-3 2.5E-7 na

IDP Isodecyl diphenylphosphate C22H31O4P 29761-21-5 390.5 10.82 466.2 1.7E-2 7.28 3.71 10.2 6.3E-6 4.4E-7 na

RDP Resorcinol bis(diphenyl phosphate) C30H24O8P2 57583-54-7 574.5 15.43 480.0 6.9E-3 7.41 4.80 18.3 2.7E-6 2.9E-13 na

S23

TBOEP Tri(2-butoxyethyl)phosphate C18H39O7P 78-51-3 398.5 9.99 433.8 604 3.00 2.83 13.1 1.7E-4 1.2E-11 na

TBPP Tris(4-tert-butylphenyl)phosphate C30H39O4P 78-33-1 494.6 13.25 480.0 4.1E-5 10.43 6.47 15.0 2.7E-6 6.9E-7 na

TCEP Tris(2-chloroethyl)phosphate C6H12Cl3O4P 115-96-8 285.5 7.00 351.7 5597 1.63 1.83 5.31 0.052 3.3E-6 na

TCIPP Tri(1-chloro-2-propyl)phosphate C9H18Cl3O4P 13674-84-5 327.6 7.14 365.5 740 2.591 2.46 8.2 7.5E-3 6.0E-8 na

S24

T2CPP tris(2-Chloropropyl)phosphate C9H18Cl3O4P 6145-73-9 327.57 7.14 346.5 740 2.89 2.63 8.50 7.0E-3 6.0E-8 na

T3CPP Tri(3-chloropropyl)phosphate C9H18Cl3O4P 26248-87-3 327.57 7.14 386.5 157 3.11 2.75 8.72 6.4E-4 6.0E-8 na

o-TCP ortho-Tritolylphosphate C21H21O4P 1330-78-5 368.4 10.58 476.1 0.14 6.34 4.21 12.0 4.7E-6 5.4E-8 na

m-TCP meta-Tritolylphosphate C21H21O4P 1330-78-5 368.4 10.86 476.1 0.14 6.34 4.21 12.0 4.7E-6 5.4E-8 na

S25

p-TCP para-Tritolylphosphate C21H21O4P 1330-78-5 368.4 11.19 476.1 0.14 6.34 4.21 12.0 4.7E-6 5.4E-8 na

TDCIPP Tris(1,3-dichloroisopropyl)phosphate C9H15Cl6O4P 13674-87-8 430.9 9.57 458.7 30 3.651 3.05 10.6 3.8E-5 2.6E-9 na

TEHP Tris(2-ethylhexyl)phosphate C24H51O4P 78-42-2 434.7 9.57 446.3 2.8E-4 9.49 6.28 15.0 8.1E-5 7.9E-8 na

TEP Triethylphosphate C6H15O4P 78-40-0 182.2 - 233.3 11525 0.87 1.47 6.63 22 3.6E-8 na

S26

TiPP Triisopropylphosphate C9H21O4P 513-02-0 224.2 - 254.5 16352 2.12 2.20 6.38 18 1.4E-6 na

TiPPP Tri(2-Isopropylphenyl)phosphate C27H33O4P 64532-95-2 452.5 11.24 480.0 4.9E-4 9.07 5.72 14.0 2.7E-6 2.9E-7 na

TMP Trimethylphosphate C3H9O4P 512-56-1 140.1 - 174.2 1.0E6 -0.60 0.669 5.88 55 7.2E-9 na

TNBP Tributylphosphate C12H27O4P 126-73-8 266.3 6.35 327.0 101 41 3.24 8.2 0.47 1.4E-6 na

S27

TPeP Tripentylphosphate C15H33O4P 2528-38-3 308.4 7.86 362.9 2.9 5.29 3.96 8.8 2.2E-3 7.5E-6 na

TPHP Triphenylphosphate C18H15O4P 115-86-6 326.3 9.82 441.3 4.7 4.70 3.24 8.46 6.3E-5 3.3E-6 na

TPP Tripropylphosphate C9H21O4P 513-08-6 224.2 4.46 284.2 3474 1.871 2.06 6.4 3.1 6.8E-7 na

TTBNPP Tris(tribromoneopentyl)phosphate C15H24Br9O4P 19186-97-1 1020 5.91 480.0 1.2E-5 8.05 5.48 20.0 2.7E-6 2.7E-14 na

S28

V6 Tetrakis(2-Chloroethyl)dichloroisopentyl diphosphate C13H24Cl6O8P2 38051-10-4 583.0 12.91 480.0 33 3.31 2.86 15.5 2.7E-6 1.6E-14 na



S29

Table S5 Supplier and chemical purity of FR standards (alphabetic order).

Standard Supplier Chemical purity (%)

α-DBE-DBCH Wellington Laboratories, Guelph, ON, Canada >98β-DBE-DBCH Wellington Laboratories, Guelph, ON, Canada >98

α-HBCDD Wellington Laboratories, Guelph, ON, Canada >98β-HBCDD Wellington Laboratories, Guelph, ON, Canada >98γ-HBCDD Wellington Laboratories, Guelph, ON, Canada >98α-TBCO Wellington Laboratories, Guelph, ON, Canada >98β-TBCO Wellington Laboratories, Guelph, ON, Canada >982,4-DBP Sigma-Aldrich, St.Louis, MO, USA 99.9

2,4,6-TBP Sigma-Aldrich, St.Louis, MO, USA 99.92,6-DBP Sigma-Aldrich, St.Louis, MO, USA 99.9

4´-PeBPO-BDE208 BOC Sciences (Shirley, NY, USA) 954-BP Sigma-Aldrich, St.Louis, MO, USA 99.9

anti-DP Wellington Laboratories, Guelph, ON, Canada >98ATE Wellington Laboratories, Guelph, ON, Canada >98

BADP Accustandard (New Haven, CT, USA) >98BATE Wellington Laboratories, Guelph, ON, Canada >98bBDPP Accustandard (New Haven, CT, USA) 92.0

BEH-TEBP Wellington Laboratories, Guelph, ON, Canada >98BTBPE Wellington Laboratories, Guelph, ON, Canada >98

CDP Accustandard (New Haven, CT, USA) Technical mixtureDBDPE Wellington Laboratories, Guelph, ON, Canada >98

DBHCTD Wellington Laboratories, Guelph, ON, Canada >98DBNPG Sigma-Aldrich, St.Louis, MO, USA 98

DBS DBS from MolMall Sarl (Lonay, Switzerland) nsDMP Accustandard (New Haven, CT, USA) Technical mixture

EHDPP Sigma-Aldrich, St.Louis, MO, USA 91.4EH-TBB Wellington Laboratories, Guelph, ON, Canada >98

HBB Wellington Laboratories, Guelph, ON, Canada >98

HBB (13C6) Wellington Laboratories, Guelph, ON, Canada Isotopic purity: >99

HEEHP-TEBP BOC Sciences (Shirley, NY, USA) 95IDP Accustandard (New Haven, CT, USA) Technical mixture

mDEP/dDEP Accustandard (New Haven, CT, USA) 97.6m-TCP Wellington Laboratories, Guelph, ON, Canada >97

OBTMPI Wellington Laboratories, Guelph, ON, Canada >98o-TCP Wellington Laboratories, Guelph, ON, Canada >98

PBB-Acr Sigma-Aldrich, St.Louis, MO, USA 98PBBBr Sigma-Aldrich, St.Louis, MO, USA nsPBCH BOC Sciences (Shirley, NY, USA) 95

PBDEs Sigma-Aldrich, St.Louis, MO, USAWellington Laboratories, Guelph, ON, Canada >98

PBDE-139(13C12)

Wellington Laboratories, Guelph, ON, Canada Isotopic purity: ≥99

PBEB Sigma-Aldrich, St.Louis, MO, USA 99.7PBP Sigma-Aldrich, St.Louis, MO, USA 96

PBPAE Sigma-Aldrich, St.Louis, MO, USA nsPBT Wellington Laboratories, Guelph, ON, Canada >98

p-TCP Wellington Laboratories, Guelph, ON, Canada >98RDP Accustandard (New Haven, CT, USA) 98.0

syn-DP Wellington Laboratories, Guelph, ON, Canada >98T2CPP Accustandard (New Haven, CT, USA) 99.9T3CPP Accustandard (New Haven, CT, USA) 86.0TBBPA Wellington Laboratories, Guelph, ON, Canada >98

S30

TBBPA-BAE Carbone Scientific (London, UK) 98.2TBBPA-BDBPE Sigma-Aldrich, St.Louis, MO, USA 98.2TBBPA-DHEE Sigma-Aldrich, St.Louis, MO, USA 98TBBP-DBPE BOC Sciences (Shirley, NY, USA) 98

TBCT Wellington Laboratories, Guelph, ON, Canada >98TBNPA Sigma-Aldrich, St.Louis, MO, USA nsTBOEP Sigma-Aldrich, St.Louis, MO, USA 94

TBP-DBPE Wellington Laboratories, Guelph, ON, Canada >98TBPP Chemos (Regenstauf, Germany) nsTBX Wellington Laboratories, Guelph, ON, Canada >98

TCBPA Sigma-Aldrich, St.Louis, MO, USA 98TCEP Sigma-Aldrich, St.Louis, MO, USA 97TCIPP Sigma-Aldrich, St.Louis, MO, USA 97.5

TDBP-TAZTO Sigma-Aldrich, St.Louis, MO, USA 97TDCIPP Sigma-Aldrich, St.Louis, MO, USA ns

TEBP-Anh Sigma-Aldrich, St.Louis, MO, USA 98TEHP Sigma-Aldrich, St.Louis, MO, USA 97TEP Sigma-Aldrich, St.Louis, MO, USA ≥99.8TiPP Accustandard (New Haven, CT, USA) 95.0

TiPPP Accustandard (New Haven, CT, USA) 98.3TMP Accustandard (New Haven, CT, USA) 98.5TNBP Sigma-Aldrich, St.Louis, MO, USA ≥99TPeP Accustandard (New Haven, CT, USA) 97.2TPHP Sigma-Aldrich, St.Louis, MO, USA ≥99

TPHP (D15) Wellington Laboratories, Guelph, ON, Canada Isotopic purity: >98

TPP Sigma-Aldrich, St.Louis, MO, USA 99TTBNPP BOC Sciences (Shirley, NY, USA) 98

TTBP-TAZ BOC Sciences (Shirley, NY, USA) 95V6 Accustandard (New Haven, CT, USA) Technical mixture

ns = not specified

S31

Table S6 Chosen SIM-ions/MRM-transitions for GC-MS analysis of PBDEs on each of the three instrument systems.GC-(EI)MS GC-(CI)MS GC-(EI)MS/MS

Compound No. of Br Ion 1 Ion 2 Ion 1 Ion 2 Parent ion 1 Product ion 1 CE Parent ion 2 Product ion 2 CEBDE3 1 247.9 249.9 79 81 248 141 19 248 115 19

7 2 168 327.8 79 81 248 141 12 327.9 168 1215 2 168 327.8 79 81 327.9 218.9 11 327.9 168 1117 3 247.9 407.8 79 81 407.8 247.9 23 407.8 246 2328 3 247.9 407.8 79 81 407.8 247.9 23 407.8 246 2347 4 325.8 485.7 79 81 485.7 326 22 483.7 324.1 2249 4 325.8 485.7 79 81 485.7 326 22 483.7 324.1 2266 4 325.8 485.7 79 81 485.7 326 23 483.7 324.1 2371 4 325.8 485.7 79 81 485.7 326 22 483.7 324.1 2277 4 485.7 483.7 79 81 485.7 326 23 483.7 324.1 2385 5 403.7 405.7 79 81 565.7 405.8 23 563.7 403.7 2399 5 403.7 405.7 79 81 565.7 405.8 25 563.7 403.7 25

100 5 403.7 405.7 79 81 565.7 405.8 22 563.7 403.7 22119 5 403.7 405.7 79 81 565.7 405.8 22 563.7 403.7 22126 5 563.6 565.6 79 81 565.7 405.8 22 563.7 403.7 22138 6 486.6 643.5 79 81 643.6 483.3 38 483.7 324.1 38153 6 483.6 643.5 79 81 643.6 488.8 38 483.7 374.9 38154 6 483.6 643.5 79 81 643.6 488.8 30 483.7 374.9 30156 6 483.6 643.5 79 81 643.6 483.3 38 483.7 324.1 38183 7 561.6 723.5 79 81 723.5 563.4 25 721.5 561.3 25184 7 561.6 723.5 79 81 723.5 563.4 22 721.5 561.3 22191 7 561.6 723.5 79 81 723.5 563.4 38 721.5 561.3 38196 8 639.6 801.4 79 81 801.7 641.5 17 643.6 483.5 17197 8 639.6 801.4 79 81 801.7 641.5 18 643.6 483.5 18206 9 719.5 881.4 79 81 879.8 719.6 8 561.7 454.9 8207 9 719.5 881.4 79 81 879.8 719.6 13 561.7 454.9 13209 10 799.5 959.4 79 81 799.4 639.5 40 639.6 530.7 40

S32

Table S7 Chosen SIM-ions/MRM-transitions for GC-MS analysis of detectable HFRs on each of the three instrument systems.a

GC-(EI)MS GC-(CI)MS GC-(EI)MS/MSCompound Ion 1 Ion 2 Ion 1 Ion 2 Parent ion 1 Product ion 1 CE Parent ion 2 Product ion 2 CE

24-DBP 251.8 249.7 251.7 78.9 251.8 142.8 10 142.8 117 2026-DBP 251.8 253.8 78.9 80.9 251.8 142.8 10 142.8 117 20

DBS nd nd 78.9 80.9 104 78.1 5 182.9 104.1 30DBNPG nd nd 78.9 80.9 213.8 133.1 10 132.9 93.1 40TBNPA 213.8 211.8 78.9 80.9 213.8 133 5 132.9 92.9 40246-TBP 329.7 331.6 329.6 331.6 331.7 221.8 30 nd nd nd

TBBPA-BAE nd nd nd nd nd nd nd nd nd ndATE 302.7 371.7 78.9 80.9 329.7 221.9 10 369.9 209.7 5

DBE-DBCH (α-) 266.8 186.9 78.9 80.9 266.8 105.2 40 186.9 105.2 5DBE-DBCH (β-) 266.8 186.9 78.9 80.9 266.8 105.2 40 186.9 105.2 5

TBX 421.7 340.7 80.9 78.9 421.6 342.6 10 342.7 261.7 30BATE 331.7 449.7 78.9 80.9 329.7 249.7 10 289.8 210.8 20TBCO

(α-) 348.9 346.6 78.9 80.9 186.9 105.1 30 266.8 105.2 40

TBCO(β-) 348.9 346.6 78.9 80.9 186.9 105.1 30 266.8 105.2 40

TBCT 441.6 362.7 78.9 80.9 439.5 360.4 30 360.6 281.7 40PBCH 270.8 352.7 78.9 80.9 352.6 191.9 50 432.6 191.7 40

DBHCTD 236.8 374.8 78.9 80.9 236.7 116.7 40 344.8 235.1 10PBT 485.6 406.6 78.9 80.9 485.5 406.9 20 406.6 246.9 30

PBEB 499.6 484.6 78.9 80.9 484.5 405.6 5 499.5 420.5 5PBPAE 460.5 527.6 80.9 78.9 369.6 289 30 489.4 407.5 10

TBP-DBPE 329.7 331.7 78.9 80.9 nd nd nd nd nd ndHBB 551.5 473.6 551.4 549.4 551.4 472.4 5 471.5 392.7 40

TEBP-Anh nd nd 463.5 461.5 419.4 231.6 50 463.4 419.7 50PBBBr 484.6 565.4 78.9 80.9 485.5 406.7 5 565.4 484.5 5TCBPA nd nd 365.8 363.8 350.7 187 10 365.7 350.8 10PBB-Acr 476.6 478.6 78.9 80.9 476.6 448.4 5 407.6 326.6 5EH-TBB 112 420.6 78.9 80.9 420.5 392.3 5 nd nd nd

HEEHP-TEBP 477.7 479.6 521.5 519.5 nd nd nd nd nd ndS33

TBBPA 528.7 543.7 541.5 543.2 528.6 276.5 30 543.5 528.8 10HBCDD

(α-) 238.9 318.9 560.6 562.6 158.9 117.2 5 238.9 131.2 20

HBCDD(β-) 238.9 318.9 560.6 562.6 158.9 117.2 5 238.9 131.2 20

HBCDD(γ-) 238.9 318.9 560.6 562.6 158.9 117.2 5 238.9 131.2 20

BTBPE 356.7 358.7 78.9 80.9 358.6 251.5 40 358.6 277.3 10TDBP-TAZTO 649.7 489.8 647.6 649.6 487.6 367.5 10 647.6 449.2 10

BEH-TEBP 112.1 464.6 78.9 80.9 464.5 329.3 50 384.5 384.5 0DP (syn-) 271.7 236.8 651.7 653.7 271.7 237 5 236.7 143 5DP (anti-) 271.7 236.8 651.7 653.7 271.7 237 5 236.7 143 5

TBBPA-DHEE 528.7 530.7 543.7 541.7 nd nd nd nd nd ndTBBPA-BDBPE 490.8 705.9 159.7 80.9 nd nd nd nd nd nd

OBTMPI 850.5 773.5 78.9 80.9 852.5 771.3 10 nd nd ndDBDPE nd nd 78.9 80.9 nd nd nd nd nd nd

TTBP-TAZ 737.6 985.5 78.9 80.9 nd nd nd nd nd ndPBP nd nd 407.5 408.5 487.4 405 50 nd nd nd

TBBP-DBPE nd nd nd nd nd nd nd nd nd nd4-BP nd nd nd nd nd nd nd nd nd nd

4’-PeBPO-BDE208 nd nd nd nd nd nd nd nd nd ndand = not detected

S34

Table S8 Chosen SIM-ions/MRM-transitions for GC-MS analysis of detectable OPFRs on each of the three instrument systems.a

GC-(EI)MS GC-(CI)MS GC-(EI)MSMSCompound Ion 1 Ion 2 Ion 1 Ion 2 Parent ion 1 Product ion 1 CE Parent ion 2 Product ion 2 CE

TPP 98.9 141 121.8 78.9 140.9 99.1 10 183 99.1 10TTBNPP 213.8 132.9 78.9 80.9 211.8 133 5 215.8 135 5

TNBP 99 155 135.9 208.9 210.9 99.1 10 155.3 99.1 40TCEP 249.0 204.9 220.8 222.8 248.9 124.9 5 204.8 117 5TCIPP 200.9 276.9 248.9 250.9 200.9 99.1 30 276.9 125 10T2CPP 124.9 276.9 248.9 250.9 200.9 99.1 30 276.9 125.1 10T3CPP 124.9 276.9 248.9 250.9 200.9 99.1 20 276.9 125.1 10TpeP 98.9 169 nd nd 168.8 99.1 50 239 99.1 50TPHP 343 245 nd nd 326 215 40 326 170.1 30

TDCIPP 190.8 380.9 318.7 316.7 380.7 159 5 nd nd ndTEHP 190.9 380.8 318.8 316.8 380.7 159 5 302.8 192.9 5

TBOEP 299.1 199 73 297 198.9 99 20 299 101.1 20EHDPP 251 362.1 284.9 105.9 251.2 77 5 nd nd ndTCP (o-) 165 368 nd nd 368.1 181.1 5 368.1 165.1 40TCP (m-) 165 368 nd nd 368.1 181.1 5 368.1 165.1 40TCP (p-) 165 368 nd nd 368.1 181.1 5 368.1 165.1 40TiPPP 118 452.2 nd nd 250.9 77.1 40 452.1 118.1 10

V6 322.9 546.9 518.8 520.8 322.7 216.9 20 500.5 314.9 20TBPP 479.2 494.2 nd nd 494 479.2 5 479.1 367.2 10RDP 273.1 418 nd nd 573 417.2 20 417.9 167.9 20IDP nd nd nd nd 250.9 77.1 30 nd nd nd

BADP nd nd nd nd nd nd nd nd nd ndBBDPP nd nd nd nd nd nd nd nd nd nd

CDP nd nd nd nd nd nd nd nd nd ndDMP nd nd nd nd nd nd nd nd nd ndTMP nd nd nd nd nd nd nd nd nd nd

mDEP/dDEP nd nd nd nd nd nd nd nd nd ndTEP nd nd nd nd nd nd nd nd nd ndTiPP nd nd nd nd nd nd nd nd nd nd

and = not detected

S35

Table S9 Spiking levels (ng mL-1) in pure solvent/extracts and environmental concentrations (dissolved phase) in water sample (ng L-1) during method development, detectability, matrix and clean-up experiments. Indices (a-e) indicate why a certain FR was not included in that particular experiment.

Method development Detectability Matrix

effect Clean-up Environmental concentrationg

BDE3 2000 -a -a -a -h

7 2000 -a -a -a -h

15 2000 -a -a -a -h

17 2000 -a -a -a -h

28 2000 -a -a -a -h

47 2000 -a -a -a -h

49 2000 -a -a -a -h

66 2000 -a -a -a -h

71 2000 -a -a -a -h

77 2000 100 100 600 < IDL85 2000 -a -a -a -h

99 2000 20 20 120 < IDL100 2000 20 20 120 < IDL119 2000 -a -a -a -h

126 2000 -a -a -a -h

138 2000 -a -a -a -h

153 2000 20 20 120f < IDL154 2000 -a -a -a -h

156 2000 -a -a -a -h

183 2000 100 100 600 < IDL184 2000 -a -a -a -h

191 2000 -a -a -a -h

196 2000 -a -a -a -h

197 2000 -a -a -a -h

206 2000 -a -a -a -h

207 2000 -a -a -a -h

209 2000 20 20 120f < IDL246-TBP 2000 20 20 1000f < IDL24-DBP 2000 800 800 24000f < IDL26-DBP 2000 800 800 24000f < IDL

4-BP 2000 -b -b -b -h

4'-PeBPO-BDE208 2000 -b -b -b -h

aDP 2000 20 20 1000 < IDLATE 2000 100 100 5000 < IDL

BATE 2000 100 100 5000 < IDLBEH-TEBP 2000 100 100 -c < IDL

BTBPE 2000 100 100 -c < IDLDBDPE 2000 -b -b -b -h

DBE-DBCH (α) 2000 -d -d -d -h

DBE-DBCH (β) 2000 400 400 8000 < IDLPBBBr 2000 100 100 5000 < IDL

S36

PBCH 2000 400 400 -c < IDLPBEB 2000 20 20 1000 < IDLPBP 2000 -b -b -b -h

PBPAE 2000 100 100 5000 < IDLPBT 2000 20 20 1000 < IDLsDP 2000 20 20 1000 < IDL

TBBPA 2000 400 400 -c < IDLTBBPA-BAE 2000 -e -e -e -h

TBBPA-BDBPE 2000 -c -c -c -h

TBBPA-DHEE 2000 -c -c -c -h

TBBP-DBPE 2000 -b -b -b -h

TBCO (α) 2000 20 20 -d < IDLTBCO (β) 2000 20 20 1000 < IDL

TBCT 2000 100 100 5000 < IDLTBNPA 2000 400 400 20000 < IDL

TBP-DBPE 2000 20 20 1000 < IDLTBX 2000 20 20 1000 < IDL

TCBPA 2000 -b -b -b -h

TDBP-TAZTO 2000 400 400 20000f < IDLTEBP-Anh 2000 -b -b -b -h

TTBP-TAZ 2000 100 100 5000f < IDLBADP 2000 -b -b -b -h

bBDPP* 2000 -b -b -b -h

CDP 2000 -b -b -b -h

DMP 2000 -b -b -b -h

EHDPP 2000 100 100 5000 < IDLIDP 2000 -b -b -b -h

mDEP/dDEP 2000 -b -b -b -h

RDP 2000 -c -c -c -h

T2CPP* 2000 -d -d -d -h

T3CPP* 2000 -d -d -d -h

TBOEP 2000 -c -c -c -h

TBPP 2000 100 100 5000 < IDLTCEP* 2000 -c -c -c -h

TCIPP* 2000 400 400 20000 100TCP (o) 2000 100 100 5000 < IDLTCP (m) 2000 400 400 -d -h

TCP (p) 2000 400 400 -d -h

TDCIPP* 2000 20 20 1000 5DBHCTD 2000 20 20 1000 < IDLDBNPG 2000 -b -b -b -h

DBS 2000 -b -b -b -h

EHTBB 2000 400 400 -c < IDLHBB 2000 20 20 1000 < IDL

HBCDD (α) 2000 20 20 1000f < IDLHBCDD (β) 2000 20 20 1000f < IDL

S37

HBCDD (γ) 2000 20 20 1000f < IDLHEEHP-TEBP 2000 -c -c -c -h

OBTMPI 2000 20 20 1000 < IDLPBB-Acr 2000 100 100 5000 < IDL

TEHP 2000 -c -c -c -h

TEP 2000 -b -b -b -h

TiPP 2000 -b -b -b -h

TiPPP 2000 100 100 5000 < IDLTMP 2000 -b -b -b -h

TNBP 2000 800 800 24000 < IDLTPeP 2000 800 800 -c < IDLTPHP 2000 -c -c -c -h

TPP 2000 400 400 20000 < IDLTTBNPP* 2000 800 800 24000f < IDL

V6* 2000 400 400 -c < IDLNot included in the experiment because: ait was considered adequate to include only a few representatives with different degree of bromination from the group of PBDEs, bit was not detected using the EI-MS instrument during the method development, cStandards were not available when the experiment was conducted, cit was considered adequate to include only one out of several isomers, emultiple peaks were detected in the standard during method development; fno result reported due to unresolved peak/retention time shift; genvironmental concentration (semi-quantitative) in a water sample used for detectability and matrix experiments; hnot included in the experiment; *halogenated OPFR.

S38

Table S10 Detectable and non-detectable FRs (n = 96 plus six isomers) at injection of 2 ul of 2000 ng µL-1

per compound on three different GC-MS systems operating in SCAN-mode: GC-(EI)MS/MS, GC-(EI)MS, and GC-(CI)MS.a

Compound GC-(EI)MS/MS

GC-(EI)MS

GC-(CI)MS Compound GC-

(EI)MS/MSGC-

(EI)MSGC-

(CI)MSBDE3 PBBBr

7 PBCH 15 PBEB 17 PBP ND 28 PBPAE 47 PBT 49 sDP 66 TBBPA 71 TBBPA-BAE MP MP MP

77 TBBPA-BDBPE

85 TBBPA-DHEE

99 TBBP-DBPE MP ND MP100 TBCO (α) 119 TBCO (β) 126 TBCT 138 TBNPA 153 TBP-DBPE 154 TBX 156 TCBPA ND

183 TDBP-TAZTO

184 TEBP-Anh ND 191 TTBP-TAZ ND 196 BADP ND ND ND197 bBDPP* ND ND ND206 CDP ND ND ND207 DMP ND ND ND209 EHDPP

246-TBP IDP ND ND24-DBP mDEP/dDEP ND ND ND26-DBP RDP ND

4-BP ND ND ND T2CPP* 4'-PeBPO-BDE208 ND ND ND T3CPP*

aDP TBOEP ATE TBPP ND

BATE TCEP* BEH-TEBP TCIPP*

BTBPE TCP (o) NDDBDPE ND ND TCP (m) ND

DBE-DBCH (α) TCP (p) NDDBE-DBCH (β) TDCIPP*

DBHCTD TEHP

S39

DBNPG ND TEP ND ND NDDBS ND TiPP ND ND ND

EHTBB TiPPP NDHBB TMP ND ND ND

HBCDD (α) TNBP HBCDD (β) TPeP NDHBCDD (γ) TPHP ND

HEEHP-TEBP TPP OBTMPI TTBNPP* PBB-Acr V6*

aLight grey with tick mark () = Detected; Dark grey = Not suitable; ND = Not detected; MP = Multiple chromatographical peaks; * = halogenated OPFR.

S40

Table S11 Instrumental detection limits (IDLs, ng/mL) of PBDEs, HFRs, and OPFRs on each of the three instrument systems. Injection volume was 2 µL.

EI-MS CI-MS EI-MS/MSBDE77 100 62 2BDE99 19 11 1BDE100 19 13 0BDE153 19 12 1BDE183 101 53 10BDE209 21 22 ndTBNPA 359 1706 69246-TBP 39 33 2PBCH 461 775 53TBCO 21 19 260BATE 96 23 5

DBE-DBCH 394 213 30TDBP-TAZTO 692 5089 8336

ATE 92 23 19TBX 18 5 1

TBCT 91 6 4PBT 18 5 2

TBP-DBPE 20 17 8PBB-Acr 102 27 7PBBBr 173 426 113PBEB 19 2 1HBB 19 4 2

HBCDD 348 nd 2PBPAE 103 72 8TBBPA 1057 93 74

DBHCTD 39 nd 9EH-TBB 392 70 40BTBPE 103 32 8

BEH-TEBP 103 20 17sDP 20 10 1aDP 20 6 2

OBTMPI 22 4 5TiPPP 12 nd 20TPeP 84 nd 203TPP 131 nd 83

TDCIPPa,b 13 14 5TCIPPa,b 264 67 95

TNBP 100 nd 185V6a 155 nd 84

EHDPP 12 nd 24TTBNPPa 285 33 167

TBPP 13 nd 26o-TCP 14 nd 21m-TCP 48 nd 66p-TCP 40 nd 87

aHalogenated OPFR; bHigh uncertainty in IDLs due to high background concentration; nd = not detected.

S41

Table S12 Ratios between peak areas obtained in GC-(CI)MS analysis of PBDEs (dissolved in pure solvent) using an ion source temperature of 250 °C and peak areas obtained at higher temperatures.

Temperature (°C) BDE77 BDE99 BDE100 BDE153 BDE183 BDE209260 1.00 0.99 1.01 0.99 0.98 1.03270 0.96 0.94 1.03 1.02 1.03 1.10280 1.03 1.04 0.97 1.03 1.03 1.10290 0.99 1.02 1.10 1.02 1.02 1.10300 0.97 0.99 0.83 1.02 1.03 1.08

Table S13 Correlation p-values between matrix effect and physico-chemical properties and other parameters.

Log Kowa Log Koab Log Kocc MWd Log SWe Log Hf Log VP

g Bph Retention time No. of Π-bonds

PBDEs 0.0032* 0.0020* 0.0016* 0.0044* 0.0045* 0.071 0.0015* 0.0044* 0.0061* -i

HFRs 0.24 0.68 0.69 0.62 0.92 0.82 0.65 0.84 0.67 0.10OPFRs 0.24 0.67 0.24 0.65 0.24 0.96 0.56 0.22 0.10 0.43

aKOW = octanol-water partition coefficient; bKOA = octanol-air partition coefficient; cKOC = organic carbon-water partition coefficient; dMW = molecular weight; eSW = water solubility; fH = Henry’s law constant; gVP = vapour pressure; hBp = boiling point; iNot possible to determine since all PBDEs have the same number of Π-bonds; * = Significant p-value (p < 0.05).

S42

Florisil Acidified silica AluminaF1 F2 F3 F4 F5 F1 F2 F3 F4 F5 F1

BDE77 94±3 nd nd nd nd 92±1 nd nd nd nd 99±0

BDE99 103±2 1±1 nd 2±2 nd 90±6 nd nd nd nd 98±1

BDE100 94±2 nd nd nd nd 107±2 nd nd nd nd 96±3

BDE183 102±1 1±0 nd nd nd 100±1 nd nd nd nd 99±0

TBNPA 89±1 1±0 nd nd nd nd 4±0 46±0 81±8 61±23 37±15

ATE 85±0 nd nd nd nd 3±1 1±0 nd nd nd 76±9

DBE-DBCH 86±3 nd nd nd nd 100±3 nd nd nd nd 87±9TBX 88±0 nd nd nd nd 110±4 nd nd nd nd 94±3

BATE 87±1 nd nd nd nd 100±2 nd nd nd nd 93±8TBCO 79±2 nd nd nd nd 104±9 nd nd nd nd 92±13TBCT 91±2 nd nd nd nd 108±4 nd nd nd nd 98±2

PBT 92±1 2±0 nd nd nd 112±5 2±0 1±0 nd 1±0 103±4

PBEB 87±1 nd nd nd nd 104±3 nd nd nd nd 103±4TBP-DBPE 74±1 nd nd nd nd 75±7 nd nd nd nd 110±15

PBPAE 76±2 nd nd nd nd 25±3 nd nd nd nd 100±14HBB 85±1 1±0 nd nd nd 102±1 1± 1± nd 1± 104±6

PBBBr 83±1 nd nd nd nd 89±4 nd nd nd nd 109±4PBB-Acr 90±1 1±0 nd nd nd nd nd nd 5±0 21±3 104±2DBHCTD 76±1 nd nd nd nd 81±7 nd nd nd nd 97±21

sDP 92±4 2±0 2±2 nd nd 95±0 2±

1 1±0 nd nd 107±8

aDP 93±5 2±0 1±0 nd 1±0 95±1 2±

0 1±0 1±0 1±0 111±6

OBTMPI 83±4 nd nd nd nd 88±1 nd nd nd nd 102±15TPP 1±1 nd nd nd nd nd nd nd nd nd 26±20

TNBP nd nd nd nd nd nd nd nd nd nd 41±26

TCIPP 3±2 6±5 2±0 1±0 1±0 1±0 1±

0 1±0 1±0 1±0 54±30

TDCIPP 55±13 6±4 2±

2 1±1 1±1 nd nd nd nd nd 89±30

EHDPP 47±20 13±5 3±

3 2±1 1±1 nd nd nd nd nd 93±27

oTCP 68±8 5±3 2±1 1±0 nd nd nd nd nd nd 86±13

TiPPP 75±3 3±2 1±1 nd nd nd nd nd nd nd 92±7

TBPP 73±12 4±2 2±

1 1±0 nd nd nd nd nd nd 93±5

Table S14 Average recoveries and standard deviations (n = 2) of individual fractions for target FRs obtained with the three different clean-up methods.a

aF1 = 1st fraction, F2 = 2nd fraction, etc.

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Figure S1 Quantile-quantile (Q-Q) plot of matrix effect values (two outliers excluded). If normally distributed, data points should form a straight line. Insert: Box plot of matrix effect values indicating two outliers (values outside the whiskers). The six data points represent the three highest and lowest matrix effect values, corresponding to FRs: 1 = V6; 2 = TBBPA; 3 = 2,4,6-TBP; 4 = DBHCTD; 5 = TDBP-TAZTO; 6 = PBBBr.

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6

54

3

2

1

BDE

77BD

E10

0BD

E99

BDE

153

BDE

183

BDE

209

26D

BPTB

NPA

246-

TBP

ATE

DBE

-DB

CH TBX

BAT

ETB

COTB

CTPB

CH

PBT

PBE

BTB

P-D

BPE

PBPA

EH

BBPB

BBr

PBB

-Acr

DBH

CTD

EHT

BBTB

BPA

BTBP

ETD

BP-

TA

ZTO

BEH

TBP

sDP

aDP

OBT

MPI

TPP

TTBN

PPTN

BP

TCIP

PTP

ePTD

CIP

PEH

DPP

oTCP

mT

CPpT

CPTi

PPP V6

TBPP

0.0

0.5

1.0

1.5

2.0M

atri

x ef

fect

2.4 5.0 2.1 19.2

Figure S2 Matrix effect, calculated with equation 2, for individual FRs when analyzing a spiked river extract without any clean-up. Matrix effect ≥ 1.1 means enhancement, ≤ 0.9 means suppression, and a value close to 1 (red line) means no matrix enhancement or suppression.

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References

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