3,3',4,4',5-PeXB

0

1

PCB-126 MonoBr DiBr

X

X

X

X

X

Br0Cl5

Br1Cl4

Br2Cl3

Distributions of 3,3’,4,4’,5-PeXB in FeCl3

tetra-XB penta-XB hexa-XB hepta-XB

3,3',4,4',5- 3,3',4,4',5,5'-

2,3,3',4,4',5,5'-3,3',4,4'-

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

XX

XX

X

X

X

XX

X

X

X

X

X

X

X

X

X

tetra-, penta-, hexa-, and hepta-XB. in FeCl 3

32 36 40 44 48

0

71442Br2T3CB

32 36 40 44 48

0

1382993 BrT4CB

32 36 40 44 48

0

5678926

P5CB

32 36 40 44 48Retention Time (min)

0

1578810

13C-P5CB

#126

MBr-#126

DiBr-#126

#126#1

05

#114

#123

#118

32 36 40 44 48

0

71442Br2T3CB

32 36 40 44 48

0

1382993 BrT4CB

32 36 40 44 48

0

5678926

P5CB

32 36 40 44 48Retention Time (min)

0

1578810

13C-P5CB

#126

MBr-#126

DiBr-#126

#126#1

05

#114

#123

#118

28 32 36 40 44 48 52

0

160936

BrH6CB

28 32 36 40 44 48 52

0

2691689BrP5CB

28 32 36 40 44 48 52

0

2250853BrT4CB

28 32 36 40 44 48 52Retention Time (min)

1093

83433 BrT3CB

MBr-#126

MBr-#169

MBr-#189

28 32 36 40 44 48 52

0

160936

BrH6CB

28 32 36 40 44 48 52

0

2691689BrP5CB

28 32 36 40 44 48 52

0

2250853BrT4CB

28 32 36 40 44 48 52Retention Time (min)

1093

83433 BrT3CB

MBr-#126

MBr-#169

MBr-#189

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

XX

XX

X

X

X

XX

X

X

X

X

X

X

X

X

X

Etching liquid

Etching waste

Steel plantconverter dust

iron powder

Recycle plant

FeCl3

FeCl2

Cl2Etching plant

Fe

Cu

water treatment

Ni

Coagulant

printed circuit board etching plant

13C coPCB

PCB-126

Co-PCB

FeCl3STD

PeCB

13C coPCB

PCB-126

Co-PCB

FeCl3STD

PeCB

Co-PCB

0.0

100.0

#81

#77

#126

#169

TEQ(%)/L

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

ClCl

Cl

Cl

Cl

Cl

Cl

#169

#169

HxCB

FeCl3

STD

DETECTION OF POLY HALOGENATED BIPHENYLS IN THE FeCl3 MANUFACTURING PROCESS

Nakano T, Matsumura C, Tsurukawa M, and Moriguchi Y

Hyogo Prefectural Institute of Public Health and Environmental Sciences, 3-1-27 Yukihira-cho, Suma-ku, Kobe, 654-0037 Japan

(A)

(B)

(C)

Fe

Cu

Cu

Br

Pb

Fe

Fe

Zn

Ni

Mn Cr

Fe

Zn Ni

Mn

Fe F

e

Zn Ni

Mn

CuCuP

b Cr

(A)

(B)

(C)

Fe

Cu

Cu

Br

Pb

Fe

Fe

Zn

Ni

Mn Cr

Fe

Zn Ni

Mn

Fe F

e

Zn Ni

Mn

CuCuP

b Cr

Etching

FeCl2

FeCl3

raw w

ater

warm

ing b

ath

con

tact oxid

ation

nitrificatio

n

den

itrification

re-aeratio

n

rapid

ly-stirrin

g

slowly

-stirring

coag

ulatio

n bath

neu

tralization

sterilization

bath

0

40

80

120

160

effluen

tb

ath

H3PO4

NaOHH2SO4

NaOH

NaOH

MeOH

FeCl3

NaOHH2SO4

NaOHH2SO4

sodium hypochlorite

NaClO

[Al2(OH)nCl6-n]m

12.5m3 224m3

24m3

PCB （pg-TEQ/L）

distrib

utio

n

bath

material

tank

50-120m3

ferrous chlorideiron dissolution tank2HCl+Fe FeCl2+H2

2FeCl3+Fe 3FeCl2

waste HClsteel mill

HCl+FeCl2

Etching waste liquidFeCl2+FeCl3

Print circuit board

scrap ironsteel sheet , press scrap

den

sity con

trol

filtration

filtrate tank

chlorination2FeCl2+Cl2 2FeCl3

pro

du

ct tank

ferric chloride (FeCl3) manufacturing flow

Cl2 gas

Cu

-recovery

water treatment

Etching liquid

Figure 1 GC/MS chromatogram in contaminated FeCl3

Co-PXB: #126,#169,#189 （ monobromo substituted ）

Figure 2 GC/MS chromatogram in contaminated FeCl3

Co-PXB: #126 （ PeCB, MBrTeCB, DiBrTrCB ）

Figure 3 Fluorescent X-ray analysis of liquid samples (A) used etching waste, (B) FeCl2, (C) FeCl3

Figure 4 PBrDPE in strongly acidic solution in presence of HCl, FeCl2 and CuCl2.

Figure 5 TEQ contributions (%) of co-PCB in FeCl3

Figure 6 Distributions of 3, 3’, 4, 4’, 5-PeXB in FeCl3. Figure 7 tetra-, penta-, hexa-, and hepta-XB. in FeCl3

Unique distributions of major PCB congeners from 3,3’-dichloro benzidine related sites.

PCB concentrations in waste water treatment system.

FeCl3 manufacturing process.

Figure GC/MS chromatogram in contaminated FeCl3 (Co-PCB: #126)

Figure GC/MS chromatogram in contaminated FeCl3 (Co-PCB: #169 ）

FeCl3 manufacturing process and metal recovery process .

FeCl3 as coagulant

Coprecipitation involves removal of two or more constituents by a precipitation reaction. Coprecipitation of element with Fe(OH)3 is an effective treatment process:

FeCl3 + 3H2O = Fe(OH)3 + 3H+ + 3Cl-

FeCl3 as etching liquid

Ferric Chloride (FeCl3) is used to etch away copper that isn't protected by the remaining photoresist coating on the PC board (Printed circuit board). To recover copper and nickel from a spent FeCl3 etching solution, these chemicals are recycled.

Introduction

In recent years it was found that several organic and inorganic food and feed additives can be contaminated with PCDD/PCDF and other persistent organic pollutants. One known example is the PCDD/PCDF contamination of chicken from contaminated ball clay used as food additives. Recently the EU have enacted a law with limits for PCDD/PCDF and PCB concentration for food and feed including food additives. Currently inorganic food/feed additives are screened and evaluated in this respect in the EU. In Japan a research project was performed evaluating POPs in FeCl3. FeCl3 is used partly as food/feed additive but a much larger share of FeCl3 is used for purification of water. A common used waste water treatment step using FeCl3 is coagulation following by a sedimentation step. A part of the FeCl3 is produced from recycled materials. One of the recycling processes use the Fe recovered from etching liquid of printed circuit board from and waste acids from steel mills.The aim of this study was to evaluate if the FeCl3 used for water treatment can be contaminated with persistent organic pollutants. This first study revealed that FeCl3 can be highly contaminated with dioxin-like PCBs and chlorinated-brominated PXBs calling for further investigations and possibly actions on international level.

Materials and MethodsGC/MS analysis : The analysis was carried out using a HP 6890 gas chromatograph connected to a JMS-800D mass spectrometer (JEOL Ltd. Japan) operating at a resolution >10 000. Co-PCB, Co-PXB and PXDF were analyzed using　HT8-PCB column. Temperature program used for congener specific separation of the PCB, PXB and PXDF on HT8-PCB column: 120C, 20C/min. to 180C, 2C/min. to 260C. 5C/min. to 300C, 5 min. isothermal. Monitoring ions for GC/MS analysis are listed in Table.

Standards: Commercially-available native/labeled standards were obtained from CIL as authentic standard/mixtures for crosschecking the assignment. , 4’-bromo- 3, 3’, 4, 5-tetrachloro biphenyl was obtained from CIL for a PXB standard.

Results and Conclusion

- Some lots of FeCl3 produced and used for water purification were found to be highly contaminated with PCBs (ng-TEQ/L) and chlorinated-brominated PXBs. The contaminated lots of FeCl3 stem from a process using partly FeCl3 as a recyling product from etching of printed circuit boards.

- As PCB contaminants mainly the toxic coplanar PCB congeners having dioxin-like properties and assigned TEQ values were found (#126 > #169 > #189).

- In addition to the chlorinated PCBs also monobrominated-polychlorinated s of Co-PCB #126, #169 and #189 were detected in slightly lower concentrations (Figure 7).

- Possible pathways for the formation of the PCBs are proposed: either from brominated flame retardant contamination from the etching process (e.g. PBDE; Figure 4) or formation from certain aromatic organics forming PCBs during the chlorination steps in the process of FeCl3.

- The finding of highly dioxin-like PCB contaminated FeCl3 used for waste purification is alarming and need to be highlighted and investigated as possible contamination source for drinking water and waste water sludge. Since the FeCl3 is used worldwide in water purification, investigations should be initiated with an international perspective.

HCl, FeCl2, CuCl2 PBrDPE

References1. Grabda M, Oleszek-Kudlak S, Shibata E, Nakamura T, Organohalogen Comp 2006; 68:1983.

BrPeCDF: 417.7706, 419.7679PeBrBiphenyl: 547.6268, 549.6247

BrTeCDF : 383.8096, 385.8070TeBr4MCB: 501.6792, 503.6771

BrTrCDF : 349.8487, 351.8460TrBrDiCB: 457.7297, 459.7274

BrHxCB: 437.7523, 439.7496DiBrTrCB : 413.7800, 415.777

BrPeCB: 403.7913, 405.7886MBrTeCB : 367.8329, 369.8303

BrTeCB: 367.8329, 369.830313C-PeCB: 337.920, 339.9178

BrTrCB: 333.8718, 335.8694PeCB: 325.8805, 327.8775

Monitoring ions of PXB/PXDF

NO2 O2N

Cl Cl

+ HN

Cl

HN

Cl

H2N

Cl

NH2

Cl

H2SO4

H2N

Cl

NH2

Cl

2HCl

Cl Cl

H2SO4

HCl

PRODUCT

Cl Cl

Cl Cl

Cl

Cl Cl

Cl

ClCl

Cl Cl

Cl

Cl Cl

Cl

Cl

Cl Cl

Cl

Cl

Cl Cl

Cl Cl

OH

Br

Br

Br

Br

Br

Br

O

Br

Br

Br

Br

Br

Br

X

X

X

X

X

X

O

X

X

X

X

X

X X

X

X

X

X

HCl, FeCl2, CuCl2( Cl >> Br )

OH

Br

Br

Br

Br

Br

Br

O

Br

Br

Br

Br

Br

Br

X

X

X

X

X

X

O

X

X

X

X

X

X X

X

X

X

X

HCl, FeCl2, CuCl2( Cl >> Br )