by SENS and SWICO - Ecotic

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PCB’s in Small Capacitors from Waste Electrical and Electronic EquipmentsTable 6 Identifi ed individual substances and substance classes in the capacitor samplesN° Origin of Capacitors Possible Compounds / Substance ClassesLarge Household Appliances (LHA), Small Household Appliances (SHA)1 LHA mixture naphthalene, hydrocarbons, chlorinated naphthalene, phthalates2 Dishwashers naphthalene, hydrocarbons, biphenyls, chlorinated naphthalene,phthalates3 SHA mixture, without microwavedeviceshydrocarbons, methyl-naphthalene, chlorinated naphthalene4 Microwave devices biphenyls (for ex. ethyl methyl), phthalates5 Cooling and freezing appliances naphthalene, benzyl-methylbenzene, hydrocarbons, biphenyls,triphenyl phosphate, phthalates, phosphoric acid ester6 Ballasts in fl uorescent tube lamps phthalatesIT (Information Technology) / CE (Consumer Electronics) / UPS (uninterruptible power supply systems)7 IT / CE: capacitors < 1 cm hydroxybutyric acid, chloro-butyrophenon, phthalates, fatty acid,fatty acid ester, hexabrome benzene8 IT / CE: capacitors 1 –2.5 cm dimethylacetamide, hydroxybenzoic acid, benzyl alcohol, dimehylbenzylalcohol, dibenzoyloxy-heptane-diamide, benzoic acid ester,chlorinated naphthalene, carbonic acids, fatty acid ester, hexabromebenzene, phthalates, phosphoric acid ester9 IT / CE: capacitors > 2.5 cm Dimethyl acetamide, hydroxybutyric acid, methyl pirrolidon, benzoicacid chlorethyl ester, benzoic acid ester, tetrabutyl ammonium cyanide,butoxyethoxy-ethyl acetate, biphenyls, chlorinated naphthalene,phthalates10 UPS hydrocarbons3.4 GC-ECD / FID Fingerprint AnalysisBulk sample N° 4 “microwave devices” was submittedto a differentiated analysis, in order to enable, as muchas possible, more precise statements on the di-electrodesand electrolytes used after the PCB prohibition.The samples were prepared so as to allow individualidentifi cations within the substance classes, includingquantifi cation. Table 7 displays the results.Two signifi cant substance groups could be traced witha fi ngerprint measure by GC-ECD / FID: a technical mixtureof alkylated biphenyls and a technical mixture ofphthalates within DINP and DIDP range (di-isononylphthalate and di-isodecyl phthalate). The identifi cationof individual substances was not obvious and led toprobabilities in the laboratory report. But these areclearly technical mixtures as used in typical products forhigh-tension capacitors in microwave ovens (see paragraph4.3). With that, the results of the GC-MS full scananalysis could be asserted. The quantifi cation of thesemain components revealed that especially a very highamount of substituted biphenyls (18%) is found in capacitorsfrom microwave devices. In opposition, theamount of phthalates is situated in the per thousandrange.Table 7 Quantifi cation of main components in capacitors from microwave devices (bulk sample Nº 4)Substance Group [ mg/kg ]Sum of biphenyls: (substituted by 4 methyl groups at most) 180’000Sum of DINP (di-isononyl phthalates) and DIDP (di-isodecyl phthalates) 2’15012
4 Discussion on the Results4.1 Uncertainties with the Sample PreparationThe varying results from the different laboratories on thesame bulk sample for the PCB content approximate factor10 with regard to N° 1 “mixture of large householdappliances” and N° 6 “ballasts in fl uorescent tubelamps”. Even with a complex matrix, such as shreddedold capacitors, this is, on principle, not acceptable. Anoverall survey was therefore set to clarify the causes ofthe differences and fi nd out which results were the mostreliable. Even an experienced PCB analyst could notfi n d a concluding answer to the two questions as,among others, gaps occurred in the specifi cations formethods and quality assurance systems of the laboratories.Potential sources of error with reconditioning andsplitting were identifi ed in the three laboratories. Insuffi -cient extraction yield may have caused the low values,while too high values can result from the unsatisfactorysplitting of congeners, if, according to the standard,they are multiplied with the factor following LAGA. All inall, we must assume that the real PCB contents aresituated in the middle of the ranges given by Table 5.The values derived for interpretation were calculated onthe basis of these ranges. Anyway, for deriving conclusions,the analytical uncertainties are of minor signifi -cance.For plausibility considerations and comparisons withanalyses dating back about 20 years (BUWAL 1994), thenumber of PCB-containing capacitors was estimatedfrom the PCB contents in Table 5. By assuming a PCBshare of 40 % in PCB-containing capacitors (KTAG1998) and an average weight for small capacitors reckonedaccording to the corresponding device category,we come to the absolute and percentual shares from themeasured PCB contents of Table 8. It is a rough estimate,as these assumptions are not suffi c iently securedstatistically. In spite of this reservation, these results allowa comparison with studies performed in 1988 (BU-WAL 1994). The decrease is signifi cant for all the devicecategories. Moreover, both studies reveal that the highestshares in PCB-containing capacitors originate fromdevice categories averaging the longest service life.Also this result is plausible.Table 8 Calculated number of PCB-containing capacitors, compared with 1988N° Origin of Capacitors AverageWeight[g]Number ofCapacitors,RandomSample[ – ]Large Household Appliances (LHA), Small Household Appliances (SHA)Number ofPCB-ContainingCapacitors[ – ]Share1 LHA mixture 150 2’767 10–114 0.4–4.1 8.42 Dishwashers 150 147 < 1 < 0.1 4.23 SHA mixture, without microwave devices[ % ]ComparisonBUWAL 1994 7[ % ]80 163 < 1 < 0.1 1.44 Microwave devices 225 222 < 1 < 0.1 –5 Cooling and freezing appliances 100 1’480 < 1 < 0.1 0.56 Ballasts in fl uorescent tube lamps 120 825 51–511 6.2–61.9 68.5IT (Information Technology) / CE (Consumer Electronics) / UPS (uninterruptible power supply systems)7 IT / CE: capacitors < 1 cm 10 2’100 < 1 < 0.18 IT / CE: capacitors 1–2.5 cm 20 16’100 3 < 0.19 IT / CE: capacitors > 2.5 cm 40 3’125 8–15 0.3–0.510 UPS 500 534 < 1 < 0.1 –2.57Specimens of 1988, share calculated from subcategories13
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