1. Management of Flame- Retardant Plastic Waste: PBDE Monitoring
Dr. Asmuwahyu, Enviplast, BBKK-UNDP Team and B4T-UNDP Team , Presented at Electronic Industrial Waste Management and Waste as Industrial Resource. 8-9 January 2018

2. Polybrominated Diphenyl Ether, PBDE
A group of chemical substance containing brom, added to product including EEE- plastics as flame retardant.
Toxic, persistent, bioaccumulative , and endocrine-disrupting chmicals
PBDE levels in environment increasing , widespread in world, positively detected also in surface soils from various location at Surabaya- Indonesia ((Ilyas M, et al 2011). Source: Chemosphere 83 (2011)
In 2009, commercialPenta and Octa-BDE, as Persistent Organic Pollutant, added to Stockholm Convention, and ratification has been signed by Indonesian government. In 2017 by Technical Meeting of Stockholm Conv. Deca-BDE considered as POP

3. Approximate quantity of PBDE compared to Non Halogenated Flame Retardant
Type
Quamtity (weight %)
Halogenated (PBDE),
12-18
Alumunium hydroxide 60
Magnesium hydroxide
Melamin cyanuric
40-50
Recorsenol bis (diphenyl phosphat)
15-30

4. UL 94 Compliance: Test of Fire Standard for EEE
Criteria condition
V-0
V-1
V-2
Time after flame for every specimen t1 ....
10 sec
30 sec
Totak time for five speciments
50 sec
250 sec
Tima after flame dan afterglow for evry specimen after exposing to flame 2nd time
60 sec
Is after flame or after glow reach to the clamp ? no
Cotton burnt ?

5. Composition comercial Penta BDE
Catagories PBDE
TriBDE
TetraBDE
Penta BDE
HexaBDE
HeptaBDE
Content
Traces (BDE-17 and BDE 28
Major
(BDE-47)
Major (BDE-99)
Minor BDE 100 and 85
Minor (BDE 153) traces (BDE 154
Traces (BDE-183
Reported content
0.53 %
33 %
58 % 8%
0.5 %
Source:. La Guardia, M.J., Hale R.C. and Harvey, E. (2006) Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the widely used Penta-, Octa- and Deca-PBDE Technical Flame-Retardant Mixtures. Environ. Sci. Technol. 40(20) :

6. Composition of commercial OctaBDE
Catagories of PBDE
Hexa-BDE
Hepta-BDE
Octa-BDE
Nona-BDE
Deca-BDE
Content
MInor
Major (BDE-183), traces (BDE-180 and 171)
Major (BDE-197) Minor (BDE-203 and 196)
Minor (BDE-206 and 207)
Traces (BDE-209)
11%
43 %
35 %
10 %
<1 %
Source: La Guardia, M.J., Hale R.C. and Harvey, E. (2006) Detailed Polybrominated Diphenyl Ether (PBDE) Congener Composition of the widely used Penta-, Octa- and Deca-PBDE Technical Flame-Retardant Mixtures. Environ. Sci. Technol. 40(20) :

7. Source of PBDE to the Environment
Electrical and electronic Waste : e –waste, WEEE
Non e-waste: example Polyurethan foam use in matras, furniture, upholstery in vehicle.
End of live Treatment of product containing PBDE: antimony recovery from plastic containing PBDE.

8. Release of PBDE into Environment, Need of Monitoring.
Concern with release of PBDE into environment
Leaching from landfills: Given high octanol-water partition coefficient, it is considered very unlikely that significant amounts of PBDE will be water leached from soil in landfills. However, Norwegian and Canadian screening studies have measured concentrations of PentaBDE in the leaching water from landfills (Fjeld et al. 2003, Danon-Schaffer et al 2014).
Open burning of e-waste , incineration (Danish EPA, 1999 , UNEP/POPS/POPRC.3/20/Add.1)
PBDE entering disposal of end-of-life phase from various EEE waste.

9. Monitoring DecaBDE in Recycle from WEEE
Although, production and use of Penta and OctaBDE has officially stopped (in 2004) and DecaBDE later-on is restricted (REACH, 2017).
DecaBDE debrominate under various condition . It is necessary that article containing Deca BDE , including its recycled should be monitored for its possible debromination result. .

10. IEC 62321-6. Determination of PBB and PBDE in polymer and electronic
Determination of certain substance in electrotechnical product-part 6 Determination of polybrominated biphenyl and polybrominated diphenyl ether and electronics by GC-MS, IAMS (Ion Attachement-MS) and HPLC-UV.
The method has specially been optimized for the concentration range between 100 ppm and 1000 ppm due to the requirement of RoHS Compliance.

11. Brominated screening, by BBKK using ATR FTIR methodNo
Nama sampel
Material
Brominated (%)
Mainan Anak 1
Ring plastic PE
0.039 2
Funny Blok MBS PP
0.159 3
Mix Brick Toys (Building Block) merk Doll
ABS
0.005 4
Betty Dolls
PVC
0.836 5
Gasing Petarung (Tor Blade)
a. bagian pelapis transparan
0.017
b. bagian tarikan
0.144 6
Magic cube
Kopolimer PPE
0.415 7
Rubiks
0.125 8
Cube merk Dispor
Kopolimer Styrene acrylonitril
0.089 9
Hand spinner
Pemutar
tidak terdeteksi (tt)

12. Example of Brominated screening on several toys suspected from WEEE by BBKK-Ministry of IndustryNo
Toys
Material
Est % brom* 1
Colored Rings PE
0.04 2
Doll
PVC
0.84 3
Rubic
ABS
SA white
Colored
0.13
Non
0.47 4.
Car remote control SA
PPE
0.61 5
Spinner
0.41

13. Screening analysis by BBKK on EEE produced before 2009.No
Sample
Materials
Screening Brom content 1
TV casing
HIPS/ABS
Non 2
Computer Monitor casing
ABS 3
Motor casing PP
0.2 % 4
Mixer casing
PBT 5
Carpet PU
3.2 % 6
Cable PE
1.9 %

14. Selectivity, Sensitivity and Limit of Detection on PBDE analysis.
Analysis PBDE by
Advantage
Drawback
GC-ECD
Purchase cost
Easy of use
Maintenance cost
Selectivity depends on retention time
Sensitivity depends on Brom content
GC-EILRMS
Good PBDE in EEE.Moderate selectivity
High Limit of Detection
,>5ppm
GC-NCILRMS
Good PBDE in EEE and WEEE
Good sleectivity
Better Limit of Detection than EILFMS
GC-HRMS (Tandem)
Very good selectivity and sensitivity, very good for PBDE ini environmental and tsuue
High purchase cost.
Very loww Limit of Detection. around 0.1 ppb

15. Sensistivity of MS determination for PBDE
For analysis of PBDE in plastic, Low Resolution MS is sensitive enough to detect the present of PBDE at level more than 5 ppm. Scaning can be done from 400 to 1000 m/z or using Selected Ion Monitoring to improve detection limit.
For analysis of PBDE in an environment compartment or in tissue samples needs more sensitive MS.. Single Ion Reaction Mode, SRM with needs Tandem MS. Monitoring at least 2 most abundant isotop cluster of the precursor, molecular Ion. With this technique , level of around 10 pg/g or 0.01ppb can be achieved

16. PBDE analysis at B4T- –Ministry of Industry , with GC-MS

17. SIM Selected Ion Monitoring PBDE for Quantitative analysis GCMS
PBDE , based on GC retention
Ion specific quantificatioIon
Ion Confirmation
Tetrabromodiphenylether
486.71
483.71
Pentabromodiphenylether
583.62
565.62
Pentabromodipnenylether, higher brom isotop mass
586.62
Hexabromodiphenylether (M-2Br)
483.69
481.69
Heptabromodiphenylether (M-2BR)
581.60
583.60
Octaromodiphenylether (M-2Br)
64151
639.51
Nonabromodiphenylether (M-2Br)
719.42
721.42
Decabromodiphenylether (M-2Br)
799.33
797.33

18. PBDE in EEE and related waste , WEEE,
PBDE, used mainly in plastic consumed by Electrical and Electronic Equipment (EEE) .). Waste of EEE possibly sent to recycling facility due to high demand plastic materials. The recycled plastic containing PBDE than used to produce article in which no flame retardancy is required for example toys Based on FTIR Screening , almost 90 % of sample of imported toys from China contains Bromine functionality group (report 2017 BBKK-UNDP Team , BBPI -ministry of Industry) !

19. WEEE plastic in Recycling ?
Polymer of used EEE, produced befor 2005, may contain PBDE, for example CRT (Cathode Ray tube) TV housing and Computers.
Imported used EEE need to be monitored
The polymer fraction from recycling of WEEE, which is relevant to TV or Computer Monitor casing are mainly ABS or HIPS but also as mixed plastic fraction.
PBDE –or halogenated monitoring: Bromine screening must be performed.
Confirmation analysis by GCMS needs to be considered if neccessary

20. By systematic Monitoring , Limit the use of WEEE in:
Food packaging, food container
Kitchen equipment
Water pipe for drinking water.
Silo, sorage and piping for food .
Polymer part with direct contact for food .
freezer imterior.
Toys
Labelling system for an article:
No halogen Confirmed made from recycled WEEE
set up an electrical and electronic waste standard management
Certification for WEEE recycler? .

21. www.enviplast.com | info@enviplast.com
Thank You for Saving My Life and Our World |