distributions of 3,3 ’,4,4 ’,5-pexb in fecl 3 tetra-, penta-, hexa-, and hepta-xb. in fecl 3...
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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'-
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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
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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 )
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