Management of Flame Retardant Plastic Waste PBDE Monitoring

Management of Flame. Retardant Plastic Waste: PBDE Monitoring

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) 783 -791 • In 2009, commercial. Penta 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

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

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

Composition comercial Penta BDE Catagories PBDE Tri. BDE Tetra. BDE Penta BDE Hexa. BDE Hepta. BDE 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) : 6247 -6254

Composition of commercial Octa. BDE 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) : 6247 -6254

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.

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 Penta. BDE 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.

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

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 Ro. HS Compliance.

Brominated screening, by BBKK using ATR FTIR method Brominated No Nama sampel Material (%) Mainan Anak 1 Ring plastic PE 0. 039 2 Funny Blok MBS PP 0. 159 Mix Brick Toys (Building Block) merk 3 Doll ABS 0. 005 4 Betty Dolls PVC 0. 836 5 Gasing Petarung (Tor Blade) a. bagian pelapis transparan PVC 0. 017 b. bagian tarikan ABS 0. 144 6 Magic cube Kopolimer PPE 0. 415 7 Rubiks ABS 0. 125 Kopolimer Styrene 8 Cube merk Dispor acrylonitril 9 Hand spinner 0. 089 tidak Pemutar ABS terdeteksi (tt)

Example of Brominated screening on several toys suspected from WEEE by BBKK-Ministry of Industry No 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 SA control PPE 0. 47 0. 61 5 Spinner 0. 41 SA

Screening analysis by BBKK on EEE produced before 2009. No Sample Materials Screening Brom content 1 TV casing HIPS/ABS Non 2 Computer Monitor ABS casing Non 3 Motor casing PP 0. 2 % 4 Mixer casing PBT Non 5 Carpet PU 3. 2 % 6 Cable PE 1. 9 %

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 , >5 ppm 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

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. 01 ppb can be achieved

PBDE analysis at B 4 T- –Ministry of Industry , with GC-MS

SIM Selected Ion Monitoring PBDE for Quantitative analysis GCMS PBDE , based on GC retention Ion specific quantificatio. Ion Confirmation Tetrabromodiphenylether 486. 71 483. 71 Pentabromodiphenylether 583. 62 565. 62 Pentabromodipnenylether, higher brom isotop mass 586. 62 583. 62 Hexabromodiphenylether (M-2 Br) 483. 69 481. 69 Heptabromodiphenylether (M-2 BR) 581. 60 583. 60 Octaromodiphenylether (M-2 Br) 64151 639. 51 Nonabromodiphenylether (M-2 Br) 719. 42 721. 42 Decabromodiphenylether (M-2 Br) 799. 33 797. 33

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) !

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

• • 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? .

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