Emissions from Fires in Electrical and Electronics Waste

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Emissions from Fires in Electrical

and Electronics Waste

SP Fire Technology SP REPORT 2005:42

SP Swedish National T

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Emissions from Fires in Electrical

and Electronics Waste

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Abstract

To assess the emissions to air and water from a fire in electrical and electronics waste, four medium-scale fire experiments were performed. Each test involved 242 kg of waste. Two different ventilation conditions were studied. In two of the tests, water was applied. Extensive gas sampling and gas analyses were performed during the tests. This included analyses for inorganic gases, volatile organic compounds (VOC), polycyclic aromatic hydrocarbons (PAH), polychlorinated dibenzodioxins and furans (PCDD/ PCDF), polybrominated dibenzodioxins and furans (PBDD/PBDF), brominated flame retardants, particles, and metals. After the tests with water application, the run-off water was analysed for the same types of species, and also some common water quality parameters. The report presents both time-resolved and integrated results from these analyses. The application of water affected the result in that way that the yield of organic species increased. The yield of particles, however, decreased.

Key words: electrical and electronics waste, fire, gas analyses, extinguishing water,

PCDD/F, PBDD/F, PAH, metals, brominated flame retardants

SP Sveriges Provnings- och SP Swedish National Testing and Forskningsinstitut Research Institute

SP Rapport 2005:42 SP Report 2005:42 ISBN 91-85303-74-7 ISSN 0284-5172 Borås 2005 Postal address: Box 857,

SE-501 15 BORÅS, Sweden

Telephone: +46 33 16 50 00 Telefax: +46 33 13 55 02

E-mail: info@sp.se

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Preface

This work was sponsored by the Swedish Rescue Services Agency (Räddningsverket, HNR 55).

The technicians at SP Fire Technology are acknowledged for their efficient manner of performing the fire tests. Thanks to Lars Rosell, Kristofer Gustafsson, and Stefan Österberg who assisted with the gas sampling and measurements. The City of Borås, and El-Kretsen assisted both with information and help to obtain the electrical and electronics waste used as fuel in the fire tests. For this assistance these organizations are gratefully acknowledged.

A reference group was connected to the project. The members of the reference group were:

Ann Lundström, Environmental authorities of the City of Göteborg (Miljöförvaltningen, Göteborg)

Ingela Höök, The County Administration of Västra Götaland (Länsstyrelsen i Västra Götalands län)

Måns Krook, The fire department of Malmö (Malmö Brandkår)

Niklas Johansson, Swedish Environmental Protection Agency (Naturvårdsverket) Peter Andersson, The Swedish Fire Protection Association (Svenska

brandförsvarsföreningen)

The work presented in this report was part of a research project concerning also the spread of emissions to air, soil, and water. Within this project also the following reports were produced:

Lönnermark, A., Andersson-Sköld, Y., Axelsson, J., Haeger-Eugensson, M., Palm Cousins, A., Rosén, B., and Stripple, H., "Emissioner från bränder - Metoder, modeller och mätningar", Räddningsverket, P20-470/07, Karlstad, 2007 (in Swedish).

Lönnermark, A., and Blomqvist, P., "Emissions from Fires in Electrical and Electronics Waste", SP Swedish National Testing and Research Institute, SP REPORT 2005:42, Borås, Sweden, 2005.

Lönnermark, A., Stripple, H., and Blomqvist, P., "Modellering av emissioner från bränder", SP Sveriges Provnings- och Forskningsinstitut, SP Rapport 2006:53, Borås, 2006 (in Swedish).

Haeger-Eugensson, M., Tang, L., Chen, D., Axelsson, J., and Lönnermark, A., "Spridning till luft från bränder", IVL Svenska Miljöinstitutet, IVL rapport B-1702, Göteborg, 2006 (in Swedish).

Rosén, B., Andersson-Sköld, Y., and Starzec, P., "Emissioner från bränder - Spridning till mark och vatten", Statens geotekniska institut, SGI Varia nr 568, Linköping, 2006 (in Swedish).

The Swedish Rescue Services Agency is acknowledged for their financial support and the reference group and the project members for the work during the project.

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Sammanfattning

Allt fler material och produkter blir förbjudna att lägga på deponier. I stället skall de återanvändas eller återvinnas på något sätt. Detta innebär att det skapas många mellanlager där använda produkter samlas i väntan på att transporteras till nästa steg i återvinningskedjan. Sådana lager innebär en brandrisk och detta kan också innebära en hälso- och miljörisk beroende på vilka ämnen som produceras i branden.

I det aktuella arbetet har bränder i avfall i form av elektrisk och elektronisk utrustning (EE-avfall) studerats. Fyra brandförsök med EE-avfall har genomförts. Varje försök bestod av 242 kg avfall placerat i en stålbur med en sammansättning representativ för vad som samlas in av återvinningsföretag. I ett av försöken begränsades ventilationen genom att sidorna i buren täcktes med plåtar. Under två av försöken begöts branden med vatten under samplingsperioden.

De ämnen som analyser utfördes för var oorganiska gaser, flyktiga organiska ämnen (VOC), polycykliska aromatiska kolväten (PAH), polyklorerade dibensodioxiner och dibensofuraner (PCDD/PCDF), polybromerade dibensodioxiner och dibensofuraner (PBDD/PBDF), bromerade flamskyddsmedel, partiklar och metaller och några andra utvalda grundämnen. Både brandgaserna och släckvattnet analyserades. Denna rapport innehåller resultaten från dessa analyser. Resultaten visar bland annat att

vattenbegjutningen ökar utbytet av organiska ämnen medan utbytet av partiklar i brandgasen minskade.

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1 Introduction

Since the first of July 2001 a company that sells electrical or electronics (EE) products in Sweden has the responsibility to ensure that the products are taken care of when they are taken out of use [1-3]. Many producers or trade organisations have joined the

organisation El-Kretsen, which takes care of collecting and recycling such waste. The waste is then sorted and dismantled so that environmentally hazardous components or materials are destroyed or safely contained while other materials are reused in some way. The distribution of different types of EE-waste collected for material re-cycling is presented in Table 1.1. This distribution of waste was principally used in the fire tests described in the report.

Table 1.1 Composition of EE-waste collected for material re-cycling [4].

Item Percentage Comments

Vacuum cleaner 3.8 a)

Micro wave 2.91 a)

Sewing machine 0.62 -

Small and medium-sized household appliance

3.99 a) b)

high-pressure wash appliance 0.02 -

Electric hand tools 0.42 -

Electric apparatuses for cutting grass 0.41 a)

Computers (desk tops) 5.66 a)

Lap tops 0.14 -

Monitors 9.66 a)

Printers 3.27 a)

Copy machines 4.06 -

Scanners 0.18 -

Other office machines 2.29 -

Fax machines 0.55 -

Telephones, cord connected 0.74 -

Telephone switchboards 0.66 -

Mobile phones 0.23 -

Cordless telephones 0.36 -

Modems 0.09 -

Small transformers, battery chargers 0.06 -

Television sets 34.9 a)

Other appliances (radio, video, CD etc.) 9.05 a)

Car radio 0.32 - Cameras 0.23 - Battery clocks/watches 0.06 - Video games 0.12 - Other games 0.15 - Armatures 5.04 -

Medical and laboratory equipment 0.15 - Other products included in the producer

responsibility

10.34 -

Total 100.54 a) These items are specified separately in the lists for each test.

b) The items within this group used in the tests included coffee maker, electric kettle, toasters and electric whisk.

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This means that a large amount of EE-waste is collected and stored at different places, both at special recycling stations and at dismantling companies. Large amount of stored goods means a large fire risk. In the case of EE-waste it can also mean a special

environmental risk due to the components of the waste. To assess to what extent species hazardous to the environment are produced and spread during a fire in EE-waste, a series of fire tests with EE-waste was performed. The waste used in these tests is described in the next section.

In a connected test series, the emissions from tyres fires were also investigated. However, the results from those tests are presented in a separate report [5].

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2 Commodities and experimental set-up

In total 15 of El-Kretsen´s cages with a total weight of EE-waste of 5100 kg was delivered to SP. From this EE-waste, representative and a similar mix of waste was selected for four different fire tests. The waste used in the four tests is described in Table 2.1.

Table 2.1 EE-waste used in each test (kg).

Item Test T1 Test T2 Test T3 Test T4

3 Vacuum cleaners (incl. one cordless) 14.64 14.09 15.93 15.14

1 Micro wave 16.64 16.72 15.07 12.70

5 Coffee machines/Electric kettles 4.34 6.02 5.99 5.44

1 Toaster 0.94 1.70 1.57 1.33

2 Electric mixers 1.88 2.23 2.21 2.07

1 Electric apparatus for cutting grass 1.74 3.29 1.42 1.30

2 Computers (desk tops) 18.37 18.16 20.03 19.13

1 Lap tops (L) / Scanners (S) 8.52 L 3.09 L 3.59 S 5.74 S

2 Monitors 31.30 31.18 31.69 33.66

2 Printers 12.60 12.76 11.59 12.29

2 keyboards 1.99 3.34 2.68 2.50

1 video recorder 3.65 4.71 5.96 6.62

2 DVD/CD players 8.93 7.12 7.25 8.33

3 portable Radio/CD players 7.93 8.08 8.10 8.16

1 Speaker 2.07 2.10 4.25 4.31

2 Telephones, cord connected 1.74 2.20 2.18 1.77

3 Television sets 105.13 105.63 102.89 101.91

Total 242.4 242.4 242.4 242.4

After having weighed all the items to be used in the fire tests (see Table 2.1), the waste was placed in cages from El-Kretsen (see Figure 2.1). The waste was placed in a similar way in the cage in each test. Each cage had a combustible board as base. The weight of the board (excluding the piece removed to allow the ignition flame from the burner to enter the cage) was approximately 12 kg. This weight is not included in the total weight given in Table 2.1. The inner dimensions of the cages were 152 cm × 109 cm × 106.5 cm. The total height was 120.5 cm.

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In each test the cage with EE-waste was placed on a square metal plate with 2 m long sides. The plate had a 3 cm high rim along the sides. The purpose of the plate was to collect melting plastic. During the tests with extinguishment, the plate also collected the water, but to decrease the effect on the load cells, holes were drilled during the first test with extinguishment (Test 2) near the four corners of the square (where it was noticed that much water was collected) and the water was then collected in steel pans beneath these holes. The 2 m by 2 m square plate was placed on a stand connected to load cells (see Figure 2.2). There was a square hole (22 cm × 22 cm) in the metal plate under which a square propane burner (17 cm × 17 cm) was positioned. The heat release rate of the ignition burner was approximately 25 kW.

Load cell Burner 0. 25 0. 25

Figure 2.2 The experimental set-up with the cage with EE-waste on metal plate placed on load cells. The waste was ignited with help of a propane burner. In case of extinguishment, the water was collected in a concrete pool. The symbol × represents thermocouples.

The gas temperature was measured at three different heights along the vertical centreline of the cage. The thermocouples (type K, 0.25 mm) were positioned at the top level of the cage and 0.25 m and 0.5 m, respectively, below this level (see Figure 2.2).

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3 Experimental procedure

Four different tests were performed. In two tests water application was used. The water application is described in the result section. In one test the sides of the cage were covered with steel plates to limit the access of air. The front was not fully covered to still have visual access (see Figure A3.6 in Appendix 3). The test series was run in the following way:

Test T1: No water application; no steel plates

Test T2: Water application; no steel plates

Test T3: No water application; steel plates

Test T4: Water application; no steel plates (repetition of Test T2)

Each test started with background measurements of the time resolved parameters for two minutes. After this period the gas burner was ignited (time zero) and was allowed to burn for two minutes. After the gas burner had been switched off the hole in the steal pan was covered by the Promatect® H board to prevent air from flowing into the cage through this hole. At this time, the accumulation sampling was started, provided the test did not include water application. In the case with water application, the accumulation sampling was started when the water application was started. The time at which the accumulation sampling was ended depended on the type of species to be analysed and how much had been collected. The exact times are presented in Table 3.1.

Table 3.1 Events during the fire tests.

T1 T2 T3 T4 Burner on 0:00 0:00 0:00 0:00 Burner off 2:00 2:00 2:00 2:00 Soot sampling on 2:00 6:00 2:00 6:00 TENAX on 2:00 6:00 2:00 6:00 Dioxins on 2:00 6:00 2:00 6:00 Hg on 2:00 6:00 2:00 6:00

Soot sampling off 28:00 26:00 48:00 26:00

TENAX off 28:00 26:00 32:00 26:00

Dioxins off 28:00 26:00 32:00 26:00

Hg off 28:00 26:00 32:00 26:00

Between each test a propane gas burner (2.5 to 3 MW) was used to heat the system during ten minutes to avoid memory effects from the previous test. Photos of the set-up and from the tests can be found in Appendix 3.

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4 Measurement, sampling and analysis

methods

4.1 Gas analysis

4.1.1 Collection of smoke gases and HRR measurement

The fire gases were collected by a hood connected to SP’s industry calorimeter [6, 7], and guided through a duct were the flow rate and gas temperature were measured and the gases were analysed. The flow rate was measured using a bidirectional probe [8].

Gas sample Gas analysis Gas analysis Data logger 8 m 6 m Ø 1 m Measurement station a) 2.05 0.47 0.73 0.27 0.145 0.28 0.535 ELPI Particles total FTIR, Tenax O₂, CO, CO₂ Hg p,T Laser Gas flow Dioxins, PAH, BFR

BFR = Brominated flame retardants

b)

Figure 4.1 Experimental set-up in the SP fire hall with a) the hood system and b) details on the measurement station. (Dimensions in m)

The industry calorimeter is used to measure the heat release rate (HRR) from fires and is based on the oxygen consumption method [9, 10]. At the measurement station in the duct the concentrations of O2, CO2, and CO were measured. Further, at this station the extra

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4.1.2 Analysis of the smoke gases

The smoke gases were analysed for inorganic gases (e.g. CO, HCl etc.), volatile organic compounds (VOC), polycyclic aromatic hydrocarbons (PAH), polychlorinated

dibenzodioxins/furans (PCDD/PCDF), polybrominated dibenzodioxins/furans (PCDD/PCDF), and some selected brominated flame retardants. The flame retardants analysed were: polybrominated diphenylethers (PBDE), tetrabromobisphenol-A

(TBBPA) and 2,4,6-Tribromfenol.The amount and the size distribution of particles in the smoke gases and the metals on the particles were also analysed.

Many smaller species can be analysed using FTIR spectroscopy, which gives time resolved concentration information. This method was used for CO2, CO, HCl, HBr, HF,

SO2, NH3, HCN, and NOX (=NO+NO2). The instrument used was a BOMEM MB 100

with a 0.922 L gas cell with a path-length of 4.8 m. The spectral resolution of the instrument was 4 cm−1. Four averaged spectra were collected per minute. Further details of this instrument have been presented elsewhere [11]. The applicability of the FTIR technique for measurements of fire gases has previously been examined in a European research project [12] and proved to be valid.

Measurements of VOC species were conducted by adsorption of fire gases on Tenax (~200 mg) adsorbent tubes (Perkin Elmer). Two adsorbent lines in parallel were used, with different sampling flows. The sampling flows are low with this method, generally below 100 mL/min. To minimize the risk for losses in sampling, each line had a backup sampling tube. The definition of VOC species using this method includes a range of non-polar or slightly non-polar small-medium sized hydrocarbon species with a molecular weight of approximately 75–200 amu. The adsorbents were subsequently analysed by thermal desorption and high resolution gas chromatography (HRGC). The GC column was split for both FID (flame ionisation detector) and MS (mass selective detector) detection. Individual species were identified from the MS data, and quantified from the FID data. The higher molecular weight hydrocarbons (PAH, PCDD/ PCDF, etc.) were collected using a large sampling-volume system. The sampling flow normally collected with this system was 20 L/min. The sampling system consisted of a heated fibreglass filter, a water-cooled condenser with a condensate bottle, and a large adsorbent cartridge containing XAD-2 (~50 g). Further, all parts of the sampling system in contact with sample gases were made of quartz glass, and thoroughly cleaned at the chemical

laboratory prior to use. Organic species with a high boiling point tend to be adsorbed on particles in smoke gases. Hence, it is important that the sampling method used collects a representative sample concerning particle size distribution. This was considered in the tests presented here. The diameter of the sample-probe tip was, together with the

sampling flow, adjusted to obtain a sampling speed in the orifice of the tip that was equal to that of the gas speed in the fire gas duct. In this manner iso-kinetic sampling was achieved.

The analysis methodology used for the larger hydrocarbons was in all cases based on high-resolution gas chromatography (HRGC) and mass fragmentography. The

quantification procedure was carried out using internal standards, which implies that the results are compensated for losses due to sample preparation. PAH: The samples were prepared by using modified US EPA3580 “Waste dilution” method. The determination of PAH was performed using the modified US EPA 8270. Twenty-one different PAH species (128–300 amu) were determined using this method. PCDD/ PCDF: Six specific PCDD isomers and nine specific PCDF isomers were quantified from their MS

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was determined from the specific mass number. Extraction and analysis was conducted in accordance with EN 1948. PBDD/ PBDF: five specific PBDD isomers and five specific PBDF isomers were quantified. Brominated flame retardants: eight specific

Polybrominated diphenylethers (PBDE), including deka-BDE, were quantified. Further were TBBP-A and 2, 4, 6-tribromo phenol quantified.

The real-time particle production and particle size distribution was measured using an ELPI (electrical low-pressure impactor). In the ELPI, the particles were charged using a Corona charger before they reached the low-pressure impactor, which has a number of electrically isolated collection stages. The total amount of particles was determined by weighing the amount collected on a quartz fibre filter. The collected particulate matter was analysed for metals and halogens.

4.2 Analysis of extinguishing water

In the tests with extinguishment, representative samples were taken from the collected water. Metals and some other elements were analysed using ICP-MS screening analysis. The water samples were analysed for volatile organic compounds, VOC, and less volatile organics, semi-VOC. The samples were extracted in two different ways: a) For analysis of semi-VOC, a specific amount of the sample was extracted with hexane. The extract was analysed with GC-MS. b) For analysis of VOC, part of the sample was heated in an airtight ampoule. Sample was taken from the gas phase and analysed with GC-MS. PAHs and brominated flame retardants were analysed with GC/MS. Dioxins and furans were analysed according to method SS-EN-1948-2/3:1996 (final analyses performed with gas chromatography and high resolution mass spectroscopy (HRGC/HRMS)).

4.3 Analysis of fire debris

Included in the main analyses was analysis of the fire debris of test T1 and T4 for the content of PCDD/PCDF. These were analysed according to method SS-EN-1948-2/3:1996 (final analyses performed with gas chromatography and high resolution mass spectroscopy (HRGC/HRMS)). Later the fire debris for all tests were analysed and then (in addition to PCDD/PCDF) also PAH, PBDD/PBDF, brominated flame retardants and metals were included in the analyses. The results from these analyses are reported elsewhere [13].

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5 Results

5.1 Heat release rate and temperature

The time resolved results of the HRR and the gas temperatures are given in Appendix 2. The maximum HRR and peak temperatures are summarized in Table 5.1.

Table 5.1 Maximum HRR and maximum gas temperatures at different heights; height 0 corresponds to a height 1 m above the steel plate.

Test HRRmax [kW] Tmax,-50cm [ºC] Tmax,-25cm [ºC] Tmax,0cm [ºC]

T1 1950 1127 1144 1270 T2 1824 1187 1227 1197 T3 1622 1012 937 959 T4 1718 1081 1094 1222

5.2 Mass loss

The mass loss was registered by load cells during the tests and for the tests without extinguishment (T1 and T3), the evaluation is straight forward. The consumed mass during a certain time period could be taken directly from the difference in the load cell signal. The application of water/foam complicates the situation, and average values of the heat of combustion for the EE-waste were used to estimate the mass loss during the time periods of water application. These estimated mass losses are associated with a larger uncertainty than the cases without water application, but they are assumed to be sufficiently accurate to provide interesting information for the calculation of yield (see below). The calculated and estimated mass losses for different time periods are summarized in Table 5.2.

Table 5.2 Mass loss (in kg) for different time periods during the tests. The time periods (in min) within the parenthesis are given from ignition.

Tests T1 70.9 (2-40) 57.3 (2-28) 42.3 (6-28) T2 13.2 (2-6) 14.6 (6-26)a) 15.3 (6-33)a) T3 62.1 (2-50) 60.9 (2-48) 51.7 (2-32) 35.1 (6-28) T4 15.1 (2-6) 19.7 (6-26)a) 20.0 (6-28)a) a) Water application.

5.3 Gas analyses

In many cases it is the concentration of different species that are of interest. However, since the concentrations in a real fire depend on a number of parameter, e.g. position, size of fire, topology, wind, etc., it is not a very good parameter to use to compare the results from different tests and different commodities. Instead a more useful parameter is yield, defined as: tot x x

m

Y

Δ

=

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where mx is the mass produced of species x and Δmtot is the mass of combustible material

consumed. The yield can then be used to compare the production of various species from different material or different set-ups. It can also be used in emission modelling for fires.

5.3.1 Inorganic gases

The inorganic gases carbon monoxide (CO), carbon dioxide (CO2), hydrogen chloride

(HCl), and hydrogen cyanide (HCN) were analysed with FTIR spectroscopy. The results from these analyses are presented as yields in Table 5.3. The concentrations of CO2 and

CO were also analysed with NDIR instruments. The measured concentrations of CO2

with the two different methods are compared in Figure 5.1. The results from the two instruments were in close agreement providing some validation of the FTIR

methodology. 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0 10 20 30 40 50 Time (min) CO 2 (% ) NDIR FTIR

Figure 5.1 Comparison between CO2-concentration measured during T1 with

NDIR-instrument and FTIR spectrometer, respectively.

Table 5.3 Yield of inorganic gases measured with FTIR

Test Time perioda) (min) YCO2 (g/kg) YCO (g/kg) YHCN (g/kg) YHCl (g/kg) 1 2 – 40 1890 85.9 2.24 6.83 1 2 – 28 1814 84.7 2.77 8.44 1 6 – 28 1911 84.9 2.45 9.33 2 2 – 6 1747 88.6 3.98 16.8 2 6 – 26 2002 125 3.43 27.2 2 6 – 33 b) 2009 125 3.27 26.0 3 2 – 50 1898 86.4 2.46 12.7 3 2 – 48 1902 86.2 2.51 12.9 3 2 – 32 1877 81.7 2.96 15.2 3 6 – 28 1969 81.3 2.87 14.2 4 2 – 6 1550 97.7 6.04 5.68 4 6 – 26b) 1829 128 4.85 10.1 4 6 – 28 b) 1822 127 4.77 10.0 a) From ignition

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In Table 5.3 the yields of CO2, CO, HCN and HCl are presented for different time

periods. The time periods were chosen both to correlate with sampling periods for other species (see below) and to represent periods with or without water application. Some selected time periods are also representative for the entire test. The time-resolved results from the FTIR measurements are presented in Appendix 2.

HBr was not detected by the FTIR, but was trapped and detected (as Br–) in the soot filter before the FTIR. This has been converted into a total production of HBr and is presented in Table 5.4 together with the HCl (detected as chloride) found on the filter.

Table 5.4 Yield of chloride and bromide (presented as HCl and HBr, respectively) trapped on the soot filter before the FTIR.

Test Time perioda) (min) YHCl (g/kg) YHBr (g/kg) T1 2 – 40 3.7 0.69 T2 2 – 33 8.9 4.9 T3 2 – 50 6.1 0.97 T4 2 – 28 5.0 2.7 a) From ignition

5.3.2 VOC

In Table 5.5, the yields of different VOC species are presented. Sampling was performed during a specific time period in each test and the results are averages for this time period.

Table 5.5 Yield of VOC [g/kg].

Analysis T1 T2 T3 T4

Time period [min] 2-28 6-26 2-32 6-26

Benzene 4.1 10.1 4.2 9.9 Toluene 0.9 4.0 1.2 4.5 Phenyl ethyn 0.8 1.4 1.0 1.5 Styrene 1.5 14.1 2.2 12.5 Phenol 0.4 3.1 0.5 3.0 Benzonitrile 0.4 0.6 0.5 0.8 Indene 0.2 0.8 0.3 0.9 Biphenyl 0.3 0.6 0.4 0.4 Total VOCa) 11.5 51.8 13.5 49.2

a) Naphthalene is reported together with the PAHs and is not included in the VOC data. Note that not all VOC species included in total VOC were identified.

The production of VOC is increased during the water application, by a factor of between four and five.

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5.3.3 PAH

Selected PAHs, both carcinogenic and others, were analysed for and the results are presented as yields in Table 5.6. The sampling of higher molecular weight hydrocarbons (PAH, PCDD/ PCDF, etc.) failed in T2 and there is thus no data available on these compounds for this test.

Table 5.6 Yield of PAHs [mg/kg]. Note that no data is available for test T2.

Analysis T1 T3 T4

Time period [min] 2-28 2-32 6-26

Benz(a)anthracene 33 46 100 Benzo(a)pyrene 1.2 21 54 Benzo(b)fluoranthene 57 51 87 Benzo(k)fluoranthene 46 43 75 Chrysene/Triphenylene 91 72 150 Dibenz(a,h)anthracene 7.8 9.1 17 Indeno(1,2,3-cd)pyrene 30 24 38 PAH, total carcinogenic 270 270 540 Acenaphtene 1.5 0.9 8.3 Acenaphthylene 94 150 664 Anthracene 310 45 141 Benzo(ghi)perylene 16 15 25 Phenanthrene 310 390 1040 Fluoranthene 190 140 303 Fluorene 52 45 158 Naphtalene 730 550 1740 Pyrene 97 75 170

PAH, total others 1800 1400 4150 PAH, totalt incl

naphtalene 2100 1700 4690 PAH, totalt excl

naphtalene 1300 1100 2950 PAH 0 200 400 600 800 1000 1200 Be nz (a )ant hr acene Be nz o (a )pyr e ne B e n zo( b) flu o ra nt hen e Be nzo( k) fluo ra nt hene C h ry se n e /T riph enyl ene D iben z( a, h) a n th ra ce ne In d e n o (1, 2, 3-cd )p yr ene A ce nap ht ene A cen aph th yl en e A n th ra cene B enzo( ghi )per yl e n e P hen ant re ne Fl uor ant he ne Fl uor e ne Py re ne P A H yi e ld [ m g/ k g ] T1 T3 T4

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It is clear from the results that the water application increased the yield of PAH with a factor between two and three.

Background sampling was performed after the test T4. Gases were sampled from the duct during a time period of 25 min. The amounts of PAHs found from the background sampling were negligible compared to the amounts found in the fire tests.

5.3.4 Dioxins and furans

A selected number of PCDD/PCDF congeners were analysed for. In Table 5.7 the results are presented as yields both for the individual congeners and as total toxic equivalences.

Table 5.7 Yield of PCDD/PCDF [μg/kg]. Note that no data is available for test T2.

Analysis T1 T3 T4 2378 TCDD 0.066 0.026 0.705 12378 PeCDD 0.037 0.026 0.456 123478 HxCDD 0.061 0.099 0.241 123678 HxCDD 0.084 0.039 0.278 123789 HxCDD 0.085 0.036 0.303 1234678 HpCDD 0.25 0.039 0.871 OCDD 0.27 0.062 0.664 2378 TCDF 0.57 1.20 17.0 12378 PeCDF 0.28 0.60 9.54 23478 PeCDF 1.27 2.40 19.1 123478 HxCDF 0.55 0.50 9.96 123678 HxCDF 0.36 0.41 9.13 123789 HxCDF 0.19 0.15 4.98 234678 HxCDF 0.51 0.39 13.7 1234678 HpCDF 1.05 0.75 17.0 1234789 HpCDF 0.39 0.21 7.47 OCDF 0.84 0.38 11.2 TCDD-ekv I-TEQ Lower Bound 0.99 1.56 16.6 TCDD-ekv I-TEQ Upper Bound 0.99 1.56 16.6 TCDD-ekv Nordic 0.99 1.52 16.6 TCDD-ekv Eadon 0.84 1.47 17.0

Also the yields of PCDD/PCDF increased from water application (T4) as can be seen from Table 5.7. In Figure 5.3, the data in Table 5.7 is presented graphically. In Figure 5.4 the same data is presented with a logarithmic scale.

The individual congeners can be assigned a toxic equivalence factor (TEF) according to the relative toxicity of the individual compound to the reference compound 2,3,7,8-TCDD. In Figure 5.5 the data from Table 5.7 is presented as individual toxic equivalences using TEFs according to WHO [14].

The analysed PBDD/PBDF are presented in Table 5.8 both as individual congeners and as a total sum (not toxic equivalence). Analysis of PBDD/PBDF were made in test T1 and test T4.

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PCDD/PCDF 0 5000 10000 15000 20000 25000 2378 TC DD 123 78 P eCD D 12 3478 HxC D D 12 3678 HxC D D 12 3789 HxC D D 12 3467 8 H pCD D OCDD 123 78 Pe CD F 234 78 Pe CD F 123 478 HxC D F 123 678 HxC D F 123 789 HxC D F 234 678 HxC D F 123 4678 Hp CD F OCDF Yield of PC DD/PC D F [ ng/kg] T1 T3 T4

Figure 5.3 Yield of PCDD/PCDF in the fire gases.

PCDD/PCDF 1 10 100 1000 10000 100000 237 8 TC D D 12 37 8 Pe C D D 12 34 78 HxC D D 12 36 78 HxC D D 12 37 89 HxC D D 123 46 78 Hp C D D OCDD 12 378 Pe CD F 23 478 Pe CD F 12 347 8 H xC D F 12 367 8 H xC D F 12 378 9 H xC D F 23 467 8 H xC D F 123 46 78 Hp CD F OC DF Yield of PCDD /P C D F [ng/kg] T1 T3 T4

Figure 5.4 Yield of PCDD/PCDF in the fire gases (note the logarithmic scale).

PCDD/PCDF, toxic equivalence 0.001 0.01 0.1 1 10 100 1000 10000 237 8 TC D D 12 378 Pe CD D 12 347 8 H xC D D 12 367 8 H xC D D 12 378 9 H xC D D 123 46 78 Hp CD D OCDD 12 378 Pe CD F 23 478 Pe CD F 12 347 8 H xC D F 12 367 8 H xC D F 12 378 9 H xC D F 23 467 8 H xC D F 123 467 8 H pCD F OC DF Yiel d of P C DD/PCDF [ ng TEQ/ kg] T1 T3 T4

Figure 5.5 Yield of PCDD/PCDF in the fire gases expressed as toxic equivalence for each congener with toxic equivalence factors according to WHO (note the

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Table 5.8 Yield of PBDD/PBDF [μg/kg]. Analysis T1 T4 2378 TBDD 2.24 24 2378 TBDF 5.53 178 12378 PeBDD <1.5 15 12378 PeBDF 2.54 54 23478 PeBDF 2.54 50 123478/123678HxBDD 2.09 22 123789 HxBDD <1.5 16 123478 HxBDF 2.84 66 1234678 HpBDF 10.01 278 Total PBDD/PBDF 27.8 703

As in the case for PCDD/PCDF, the total yield of the selected PBDD/PBDF congeners analysed increased with the water application (T4).

The analysis of the background sample taken after Test 4 showed that both chlorinated dioxins and chlorinated furans were present in the sample, but the amounts were negligible compared to the amounts found in the fire tests. There was no background analysis made on brominated dioxins/furans.

5.3.5 Brominated flame retardants

Some selected brominated flame retardants were analysed for. The results are presented in Table 5.9.

Table 5.9 Yield of brominated flame retardants [μg/kg]. Note that no data is available for test T2. Analysis T1 T3 T4 TBDE#47 22.4 3.8 4980 PeBDE#100 2.5 <1.5 581 PeBDE#99 16.4 2.4 7467 PeBDE#85 <1.5 2.2 266 HxBDE#154 4.0 <1.5 373 HxBDE#153 4.9 <1.5 664 HxBDE#138 <1.5 <1.5 83 DekaBDE#209 74.7 24.0 1203 TBBP A <1.5 2.2 1659 2,4,6-Tribromo phenol <1.5 14.2 3692

Brominated flame retardants were found from all tests where these species were analysed for. However, in test T4 with water application the yields found were extremely high if compared with the two tests without water application.

5.3.6 Particles

The smoke or particle production was measured with three different methods: a manual gravimetric method, ELPI, and a laser light extinction method. These methods are somewhat different in what they measure, but the parameter measured will be called “particles” for all three methods. The total amount of particles measured with the manual gravimetric method is presented in Table 5.10, where the yield is also given. The time

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resolved production of particles was measured with an ELPI. The particle concentration as function of time and the particle size distribution at different times are presented in Appendix 2. In Table 5.11 the concentration values from the ELPI have been integrated over the same time period as was used for the soot sampling with the manual gravimetric method. These values can be compared to the total amount measured with the gravimetric method and presented in Table 5.10. In both cases the amount of particles is lower in the test with water application. However, the magnitudes of the results differ between the methods. To extend the comparison of the different methods, the results are compared to the laser light extinction method in Table 5.12. The laser method gives the total amount of particles (smoke) in m2. This parameter then has to be converted into kg. The

conversion factor depends on the burning material, but Choi et al. summarized conversion factors for different materials showing that for several material a value of 8000 m2/kg is a representative value [15]. This value has been used to get the calculated results presented here. The calculations of the ELPI results include an assumed density of the particles of 2 g/cm3.

Table 5.10 Total amount and yield of particles measured with manual gravimetric method.

Test id Start Stop Amount on filters [mg] Concentration [mg/m3n] Total amount [g] Yield [g/kg] T1 2:00 28:00 214.3 172.4 6083 106 T2 6:00 26:00 1.7 1.8 47.16 3.23 T3 2:00 48:00 20.7 9.8 612.5 10.1 T4 6:00 26:00 3.1 3.3 90.40 4.59

Table 5.11 Total amount of particles measured with the ELPIa) (g).

Test id ELPI

T1 2870 T2 - T3 3390 T4 893

a) Integrated over the same time periods as for the gravimetric method (see Table 5.10). The stages 1 to 10 of the ELPI have been included in the evaluation. The D50%-value (i.e. 50 % collection

efficiency of this aerodynamic diameter for this stage) of stage 10 was 2.41 μm. The higher stages (larger diameters) were excluded since the uncertainty is large due to a smaller amount of particles collected on these stages.

Table 5.12 Comparison of yields of particles based on three different methods (g/kg).

Test id MGMa) ELPI Laser

T1 106 50.1 107

T2 3.23 - 46.7

T3 10.1 55.6 69.7

T4 4.59 45.3 74.4

a) Manual gravimetric method.

The comparison in Table 5.12 indicate that the laser and the ELPI show similar values while the manual gravimetric method gives very low values in the tests T2, T3, and T4. There is, however, no indication that there was anything special happening during the sampling of particles during these tests. Therefore, it has not been possible to relate the differences to differences in measuring techniques or problems during sampling or analysis. In general the manual gravimetric method is supposed to be more accurate than

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the other two methods. The main conclusion that can be drawn from all three methods is that the particle concentration is lower in the tests with water application.

5.3.7 Metals

The filters used to measure the total amount of particles were analysed for metals and halogens. The results from these analyses are given in Table 5.13, both as concentration on the particles and as total yield.

Table 5.13 Metals and halogens on particles (the five highest yields presented in bold).

Metal T1 T2 T3 T4 Yield on particle [mg/kg particle] Yield [μg/kg fuel] Yield on particle [mg/kg particle] Yield [μg/kg fuel] Yield on particle [mg/kg particle] Yield [μg/kg fuel] Yield on particle [mg/kg particle] Yield [μg/kg fuel] As 3.36 356 <38 <80 2.37 23.9 <7 <30 Ba 33.1 3510 1290 4180 145 1460 1190 5480 Cd 74.7 7910 135 437 48.3 488 116 533 Co 1.31 138 33.5 108 11.6 117 4.52 20.7 Cr 93.3 9890 3120 10070 918 9270 265 1210 Cu 1120 119000 2060 6650 676 6830 1520 6960 Mo 10.3 1090 482 1560 116 1170 <97 <440 Ni 65.3 6920 2350 7600 676 6830 152 697 Pb 2330 247000 3060 9880 1590 16100 2420 14510 Sb 1690 179000 3530 11400 1980 20000 3160 29600 Se 25.7 2720 94.1 304 23.7 239 41.9 192 Tl 0.887 94.0 21.8 70.3 3.29 33.2 11.0 50.3 V 0.65 69.2 <60 <190 <5 <50 <30 <150 Zn 3790 402000 7650 24700 3720 37600 4520 20730 Hg 4.48 475 5.29 17.1 1.26 12.7 0.968 4.44 Be <0.005 <0.5 <0.6 <1.9 <0.05 <0.5 <0.3 <1.5 Ga 0.416 44.1 11.9 79.2 1.36 13.5 10.3 96.5 Ge <0.1 <15 <20 <57 <1 <15 <10 <44 Rb 0.205 21.7 3.27 10.6 0.565 5.71 <2 <7 Y 2.98 316 11.8 38.2 2.07 20.9 6.08 27.9 Zr 0.504 53.5 39.2 127 3.53 35.7 17.0 78.2 Ag 1.10 117 <30 <295 <2 <24 <16 <74 Sn 25.1 2660 470 1520 142 1440 191 877 Te <0.09 <10 <10 <38 <1 <10 <6 <30 Ce 0.0478 5.07 1.29 4.17 0.138 1.39 0.608 2.79 Nd 0.0173 1.84 <1 <4 <0.1 <1 <1 <3 Re <0.01 <1 <1 <4 <0.1 <1 <1 <3 Au <0.1 <10 <10 <40 <1 <10 <6 <30 Bi <0.1 <10 <10 <40 4.81 48.6 <6 <30 Br 12100 1290000 - - - - 194000 888000 I <10 <1500 - - - - <1000 <4400 Cl 2750 292000 - - - - 41900 192000 F 4670 495000 - - - - 106000 489000

Since it was assumed that some mercury could exist in the gas phase, charcoal filters were used to trap gaseous mercury. The results of the analysis of these filters are

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presented in Table 5.14. The results are comparable to the mercury yield on the particles. For the tests without water application (T1 and T3) the amount of mercury on particles was higher than the gaseous mercury, but for the tests with water application (T2 and T4) the opposite was true. The five metals with the highest yield for each test are highlighted (written with bold text) in the table.

Table 5.14 Mercury, Hg, in the gases, trapped on charcoal filters.

Test Yield Hg [μg/kg] T1 289 T2 36 T3 9.3 T4 15

5.4 Water application

5.4.1 Extinguishment

A water applicator with nine nozzles was used for the water application. The nozzles were positioned in three rows with three nozzles in each row. The distance between the rows and between the nozzles in each row was 45 cm. The applicator was placed so that the openings of the nozzles were situated 20 cm above the top of the cage. A total water flow of 5 L/min was used. A calibration tests showed that the water density on a plane 20 cm beneath the nozzles was approximately 2 L/m2/min. The water flow rate was chosen to affect the fire but not to extinguish it. The reason for this strategy was to be able to collect extinguishing water that has been affected by the combustion. The water density is also representative of what can be expected when fighting a fire from a distance.

In test T2 approximately 150 L water were used during the water applicator phase and 6.7 L for the manual extinguishment. The corresponding values for T4 were 150 L and 8.1 L, respectively. The value 150 L is based on the calibration values (5 L/min). The high temperature in the beginning of the water application phase made the water vaporize in the nozzle. This fact, together with the low flow rate, made the adjustment of the flow rate difficult. A check with a total flow meter indicate that the total flow was lower, but approximately the same for both tests.

After test T2, 82.6 L water was collected for analysis; after test T4, 35.8 L was collected for analysis. A large amount of water was vaporized, but some of the water was also trapped in partly consumed waste and this can be one of the explanations for the difference in amount of collected extinguishing water after the tests. Analyses were performed on samples of the collected water and the results from these analyses are presented in Section 5.4.2.

5.4.2 Water analyses

Water was applied during a selected time period in the tests T2 and T4. The results of the analysis of the run-off water from these tests are presented in this section. Some common water parameters are presented in Table 5.15. In Table 5.16, Table 5.17, Table 5.18,

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Table 5.19, and Table 5.20 the results from the analyses of VOC and semi-VOC, PAH, and PCDD/PCDF, brominated flame retardants, and metals, respectively, are given.

Table 5.15 Analyses of various common water parameters.

Analysis T2 T4 Particle matters [mg/L] 72 220 pH, 25 ºC 4.1 5.0 Conductivity, 25 ºC [mS/m] 280 207 BOD7 [mg/L] 350 350 COD(Cr) [mg/L] 880 1000 TOC [mg/L] 320 330 Nitrogen, total N [mg/L] 23 24 Phosfor, total P [mg/L] 0.84 0.45 AOX [μg/L] 1600 670 EOX [μg/L] 47 < 1

Table 5.16 VOC and semi-VOC in the runoff water [μg/L].

Analysis T2 T4 Chlorobenzene <1 <1 Dichlorobenzenes <2 <2 Trichlorobenzenes <2 <2 Tetrachlorobenzenes <2 <2 Pentachlorobenzene <1 <1 Hexachlorobenzenes <1 <1 Benzene <10 (traces) <10 Toluene 5.5 8.8 Ethylbenzene <5 6.8 Xylenes <15 <15, traces

Alkylated benzenes larger than xylene

<20 <20

Nonylphenol <5 <5

Di-n-butyl phthalate 16 10

Benzyl butyl phthalate 1.9 <1

Diethyl hexyl phthalate 16 110

Alkylated naphtalenes NA 160

Unpolar aliphatic hydrocarbons

<100 <500 Total conc. of extractable

organic material (μg organic carbon per L)

17000 25000

Other compounds searched for were 2-chlorotoluene, 4-chlorotoluen, bromobenzene, trichloroethylene, 1,3-dichloropropane, 1,1,1-trichloroethane, bromodichloromethane, hexachlorobutadiene, 1,2-dibromo-3-chloropropane, 1,1,2,2-tetrachloroethane, dimethyl phthalate, diethyl phthalate, bis(2-ethylhexyl) adipate, di-n-octyl phthalate. All of these had concentrations below 1 μg/L.

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Table 5.17 PAH in the run-off water [mg/L] Analysis T2 T4 Benz(a)anthracene 0.0022 0.0078 Benzo(a)pyrene 0.0008 0.0038 Benzo(b)fluoranthene 0.0015 0.0071 Benzo(k)fluoranthene 0.0003 0.0015 Chrysene/Triphenylene 0.0030 0.011 Dibenz(a,h)anthracene 0.0002 0.0009 Indeno(1,2,3-cd)pyrene 0.0004 0.0022

PAH, total carcinogenic 0.0084 0.034

Acenaphtene <0.0001 <0.0001 Acenaphthylene 0.024 0.062 Anthracene 0.015 0.026 Benzo(ghi)perylene 0.0004 0.0018 Phenanthrene 0.10 0.17 Fluoranthene 0.017 0.036 Fluorene 0.017 0.027 Naphtalene 0.018 0.056 Pyrene 0.0092 0.020

PAH, total others 0.20 0.40

Table 5.18 PCDD and PCDF in the run-off water [ng/L]

Congener T2 T4 2378 TCDD 0.087 0.044 12378 PeCDD 0.078 0.037 123478 HxCDD 0.041 0.014 123678 HxCDD 0.082 0.022 123789 HxCDD 0.032 0.0078 1234678 HpCDD 0.30 0.14 OCDD 0.34 0.97 2378 TCDF 0.60 0.91 12378 PeCDF 0.74 0.54 23478 PeCDF 0.75 0.64 123478 HxCDF 0.74 0.61 123678 HxCDF 0.84 0.72 234678 HxCDF 0.38 0.34 123789 HxCDF 0.97 0.79 1234678 HpCDF 2.2 7.3 1234789 HpCDF 0.97 1.1 OCDF 5.6 20

TCDD-ekv I-TEQ Lower Bound 0.95 0.86 TCDD-ekv I-TEQ Upper Bound 0.95 0.86

TCDD-ekv Nordic 0.92 0.84

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Table 5.19 Brominated flame retardants in the run-off water [ng/L] Congener T2 T4 2,2’,4,4’-TeBDE, #47 1100 0.53 2,2’,4,4’,6-PnBDE, #100 0.18 0.058 2,2’,4,4’,5-PnBDE, #99 0.65 0.45 2,2’,3,4,4’-PnBDE, #85 0.032 0.027 2,2’,4,4’,5,6’-HxBDE, #154 0.065 0.053 2,2’,4,4’,5,5’-HxBDE, #153 0.061 0.071 2,2’,3,4,4’,5’-HxBDE, #138 0.011 0.017 DekaBDE, #209 470 35 Tetrabromobisphenol A (TBBP A) <1 7.8 2,4,6-Tribromophenol 6.5 NA

Table 5.20 Metals in the run-off water [μg/L]. The concentration for all other elements was less than 1 μg/L. The five metals with the highest concentration in each test are presented in bold. Element T2 T4 Element T2 T4 Aluminium, Al 5600 2300 Lithium, Li 41 110 Antimony, Sb 890 4300 Magnesium, Mg 6100 7400 Arsenic, As 8 20 Manganese, Mn 1800 2200 Barium, Ba 3600 8400 Molybdenum, Mo 6 <1 Lead, Pb 11000 7300 Sodium, Na 22000 88000 Boron, B 780 <1 Neodymium, Nd <1 <1 Bromine, Br 1700000 2500000 Nickel, Ni 300 100 Cerium, Ce 2 2 Rubidium, Rb 23 42 Europium, Eu 1 <1 Selenium, Se 2 <1 Phosphorus, P 11 13 Silver, Ag 1 17 Gadolinium, Gd <1 300 Scandium, Sc 4 <1 Iodine, I 28 480 Strontium, Sr 680 850 Iron, Fe 68000 62000 Sulfur, S <1 <1 Cadmium, Cd 110 300 Tellurium, Te <1 3 Calcium, Ca 260000 390000 Tin, Sn 1300 700 Potassium, K 10000 17000 Titanium, Ti 650 1200 Silicon, Si 110 190 Vanadium, V 2 <1 Cobalt, Co 27 34 Bismuth, Bi 5 4 Carbon, C 47000 9900 Tungsten, W <1 <1 Copper, Cu 2400 2700 Yttrium, Y 35 60 Chromium, Cr 120 <1 Zinc, Zn 76000 120000 Lanthanum, La 2 3 Zirconium, Zr 1 <1

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5.5 Analyses of fire debris

Samples of debris were taken from all tests. Most of the analyses were performed within another project [13]. In Table 5.21 the results of the analyses of PCDD and PCDF in the debris from the tests T1 and T4, respectively, are presented.

Table 5.21 Dioxins and furans in the fire debris.

Congener Concentration (ng/kg DS) T1 T4 2378 TCDD <3 4.3 12378 PeCDD <2 7.7 123478 HxCDD <1 3.0 123678 HxCDD <1 4.5 123789 HxCDD <1 4.1 1234678 HpCDD 2.4 9.3 OCDD 2.5 6.0 2378 TCDF 140 140 12378 PeCDF 150 88 23478 PeCDF 100 76 123478 HxCDF 62 69 123678 HxCDF 69 94 123789 HxCDF 36 33 234678 HxCDF 51 89 1234678 HpCDF 45 130 1234789 HpCDF 23 36 OCDF 11 71

TCDD-ekv I-TEQ Lower Bound 94 96

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6 Discussion and conclusions

Four tests with EE-waste were performed. EE-waste representative of what is collected by recycling companies (242 kg in each test). Even if it was assured that each test contained the same composition of EE-waste, no analysis was performed of the material itself. Therefore, the material composition and total element distribution could vary between the tests. Test T4 was a repetition test of test T2. The results for most of the analysed species were similar in these two tests. It is only for the brominated flame retardants in the extinguishing water that the yields of a few of the species were much higher in test T2. However, the overall results show that there is a good repeatability. The report includes many different results, both time resolved and integrated. It is not possible here to discuss all the individual results, but some general trends are discussed. The application of water increases the yields of organic species. This is the case for VOC, PAH, PCDD/PCDF, PBDD/PBDF, and brominated flame retardants. For particles the case is the opposite, i.e. a lower yield of particles are measured when water is applied compared to the case without water. The reason for this is probably that the smoke is “washed” by the water. When it comes to the different methods for determining the amount of particles, the manual gravimetric method usually is the most accurate one, but the results show best correspondence between the ELPI and the laser method. Only in test T1 the manual gravimetric method correlate well with the other methods. However, the three methods differ in what they measure and this could be one of the explanations for the differences. On the particles zinc, lead, and antimony dominate among the metals. Other metals with high yields are cupper, chromium, and nickel. Note that this ordering is made only from the yields with no regards to their effect on the environment or health. In the run-off water the metals calcium, zinc, sodium, and iron were found in highest concentration. The element found in highest concentration was bromine. The bromine probably emanate from flame retardants in the plastics within the electronic waste. The yield of PBDD/PBDF was higher than that for PCDD/PCDF. For both the PCDD/PCDF and the PBDD/PBDF the total fraction of furans was higher than the fraction of dioxins.

The restriction of the ventilation did not significantly affect the results. However, the restriction (in test T3) was not a major change from the well-ventilated case (in test T1) and the ventilation must still be considered as an important factor. The temperature in the centre of the set-up was lower in test T3 than in test T1. It could be observed during the test T3 that the flames followed the sides (probably due to the heated steel plates) rather than going straight up as a fire plume usually does.

It is always interesting to compare experimental results to other test series where the conditions or scales may vary. The results presented in this report are comparable to those obtain in tests with TV-sets (both the case material and the full TV-set) [16, 17]. Both European and US TVs were tested and as mentioned are the TV results comparable to the results from test T1 to T4 even if the US TV in some cases produced higher yields, e.g. for some of the VOCs and some of the PAHs. However, also test T4 produced higher yields in some case, especially for the PCDD/PCDF and the PBDD/PBDF.

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7 References

1. SFS 2000:208, "Förordning om producentansvar för glödlampor och vissa belysningsarmaturer", 2000 (in Swedish).

2. SFS 2005:209, "Förordning om producentansvar för elektriska och elektroniska produkter", 2005 (in Swedish).

3. SFS 2005:210, "Förordning om ändring i förordningen (2000:208) om

producentansvar för elektriska och elektroniska produkter", 2005 (in Swedish). 4. Nyberg, L., "Personal communication", El-Kretsen i Sverige AB, 2004. 5. Lönnermark, A. and Blomqvist, P., "Emissions from Tyre Fires", SP Swedish

National Testing and Research Institute, SP REPORT 2005:43, Borås, Sweden, 2005.

6. Dahlberg, M., "The SP Industry Calorimeter: For rate of heat release measurements up to 10 MW", SP Swedish National Testing and Research Institute, SP REPORT 1992:43, Borås, Sweden, 1993.

7. Dahlberg, M., "Error Analysis for Heat Release Rate Measurement with the SP Industri Calorimeter", SP Swedish National Testing and Research Institute, SP REPORT 1994:29, Borås, 1994.

8. McCaffrey, B. J. and Heskestad, G., "Brief Communications: A Robust

Bidirectional Low-Velocity Probe for Flame and Fire Application", Combustion

and Flame, 26, 125-127, 1976.

9. Huggett, C., "Estimation of Rate of Heat Release by Means of Oxygen Consumption Measurements", Fire and Materials, 4, 2, 61-65, 1980.

10. Parker, W. J., "Calculations of the Heat Release Rate by Oxygen Consumption for Varios Applications", National Bureau of Standards, NBSIR 81-2427, Gaithersburg, USA, 1982.

11. Blomqvist, P., Lindberg, P., and Månsson, M., "TOXFIRE - Fire Characteristics and Smoke Gas Analyses in Under-ventilated Large-scale Combustion

Experiments: FTIR Measurements", SP Swedish National Testing and Research Institute, SP REPORT 1996:47, Borås, Sweden, 1998.

12. Hakkarainen, T., Mikkola, E., Laperre, J., Gensous, F., Fardell, P., Le Tallec, Y., Baiocchi, C., Paul, K., Simonson, M., Deleu, C., and Metcalfe, E., "Smoke Gas Analysis by Fourier Transform Infrared Spectroscopy - Summary of the SAFIR Project Results", Fire and Materials, 24, 101-112, 2000.

13. Lönnermark, A., "Analyses of Fire Debris after Tyre Fires and Fires in Electrical and Electronics Waste", SP Swedish National Testing and Research Institute, SP REPORT 2005:44, Borås, Sweden, 2005.

14. WHO, "Assessment of the health risk of dioxins: re-evaluation of the Tolerable Daily Intake (TDI)", WHO, Geneva, Switzerland, 1998.

15. Choi, M. Y., Mulholland, G. W., Hamins, A., and Kashiwagi, T., "Comparisons of the soot Volume Fraction Using Gravimetric and Light Extinction

Techniques", Combustion and Flame, 102, 161-169, 1995.

16. Simonson, M., Blomqvist, P., Boldizar, A., Möller, K., Rosell, L., Tullin, C., Stripple, H., and Sundqvist, J. O., "Fire-LCA Model: TV Case Study", SP Swedish National Testing and Research Institute, SP REPORT 2000:13, Borås, Sweden, 2000.

17. Blomqvist, P., Rosell, L., and Simonson, M., "Emissions from Fires Part I: Fire Retarded and Non-Fire Retarded TV-Sets", Fire Technology, 40, 39-58, 2004.

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Appendix 1 Test protocols

T1

-2:00 Measurement start 0:00 Propane burner on

0:30 Flame height 2/3 of the height of the cage

2:00 Propane burner off. Start of accumulative sampling 2:15 Explosion of a picture tube

2:50 Explosion of a picture tube

5:00 A crackling sound can be heard. The flames are approximately 5 m high 6:00 The fire has spread to the micro wave oven

7:00 Small pool fires is created in the 4 m2 pool 8:15 Much of the TVs are consumed

9:00 Most of the commodities are involved in the fire, except for parts of the micro and the DVD on top. Flame height is approx. 3 m.

11:00 Flame height is 2.5 m to 3 m.

13:00 The pool fires are small, but the flames pass through the bottom and out to the sides.

19:00 The pool fires have become somewhat larger, especially on the left side. 28:00 Accumulative sampling stopped.

40:00 Manual extinguishment 43:00 Measurement stop

T2

0:50 Flames reach the top of the cage 1:00 Flames reach 0.5 m above the cage 2:00 Propane burner off.

2:05 Explosion of a picture tube 2:30 Flames reach 3 m above the cage 3:00 Explosion of a picture tube

6:00 Start of accumulative sampling. Water application on.

25:30 Holes are drilled in the 4 m2 pool to drain the extinguishment water into small pools.

26:00 Accumulative sampling stopped.

33:00 Manual extinguishment (6.68 L water used) 35:00 Water application off

T3

1:50 Explosion of a picture tube

2:00 Propane burner off. Start of accumulative sampling 5:30 Flames reach 3-4 m.

8:30 Plastics melt and drip, but no pool fire is formed

10:00 Still dripping of melted plastics and a small pool fire is formed 14:00 Flame height is 2 m

23:00 Flame height is 1.5 - 2 m

32:00 Accumulative sampling (except soot) stopped 48:00 Soot sampling off

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50:00 Manually extinguished

T4

0:52 Flames reach the top of the cage 1:10 Flames reach 1 m above the cage 1:55 Explosion of a picture tube 2:00 Propane burner off. 3:05 Explosion of a picture tube

Flames reach 3-4 m above the cage

6:00 Start of accumulative sampling. Water application on. 12:00 Flames reach just above the cage

19:00 A VCR is sheltering some of the flames from the water 26:00 Accumulative sampling stopped. Water application off. 28:00 Manually extinguished (8.08 L water used)

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Appendix 2 Time-resolved results

In this appendix results from the time-resolved measurements are presented. For the tests results from measurements of heat release rate, temperature within the experimental set-up, particle concentration as function of time, particle concentration as function of aerodynamic particle diameter (at different times), smoke production rate (SPR), and gas concentrations (CO2, CO, HCN and HCl) are given.

T1 0 500 1000 1500 2000 0 10 20 30 40 50 HRRtot [kW] HRRconv [kW] H e at r el e as e r ate [k W ] Time [min] 0 500 1000 1500 0 10 20 30 40 50 0cm [o C] -25cm [o_C] -50cm [o_C] T e m per at ur e [ o C] Time [min] 1 10 100 1000 104 105 106 107 108 0 10 20 30 40 50 P a rt ic le c on cen tr at io n [1 /c m 3] Time [min] 0.01 1 100 104 106 108 0.01 0.1 1 10 Time = 5 min Time = 10 min Time = 15 min Time = 20 min P a rt ic le c on cen tr at io n [1 /c m 3]

Aerodynamic particle diameter [μm]

0 50 100 150 200 0 10 20 30 40 50 SPR [m2/s] SP R [ m 2 /s ] Time [min]

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0 50 100 150 200 0 10 20 30 40 50 Time (min) CO 2 ( g /s ) 0 2 4 6 8 10 0 10 20 30 40 50 Time (min) CO (g/s) 0.0 0.1 0.2 0.3 0.4 0.5 0 10 20 30 40 50 Time (min) H CN (g /s) 0.0 0.5 1.0 1.5 2.0 0 10 20 30 40 50 Time (min) HCl (g/s)

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T2 0 500 1000 1500 2000 0 10 20 30 40 50 HRRtot [kW] HRRconv [kW] H e at r el e as e r ate [k W ] Time [min] 0 500 1000 1500 0 10 20 30 40 50 0cm [o_C] -25cm [o_C] -50cm [o_C] T e m per at ur e [ o C] Time [min] 1 10 100 1000 104 105 106 107 108 0 10 20 30 40 50 P a rt ic le c on cen tr at io n [1 /c m 3] Time [min] 0.01 1 100 104 106 108 0.01 0.1 1 10 Time = 5 min Time = 10 min Time = 15 min Time = 20 min P a rt ic le c on cen tr at io n [1 /c m 3]

0 50 100 150 200 0 10 20 30 40 50 SPR [m2/s] SP R [ m 2 /s ] Time [min]

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0 50 100 150 200 0 10 20 30 40 50 Time (min) CO 2 (g/s ) 0 2 4 6 8 10 0 10 20 30 40 50 Time (min) CO ( g /s) 0.0 0.1 0.2 0.3 0.4 0.5 0 10 20 30 40 50 Time (min) HCN (g /s) 0.0 1.0 2.0 3.0 4.0 0 10 20 30 40 50 Time (min) HCl (g/ s )

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T3 0 500 1000 1500 2000 0 10 20 30 40 50 HRRtot [kW] HRRconv [kW] H e at r el e as e r ate [k W ] Time [min] 0 500 1000 1500 0 10 20 30 40 50 0cm [o_C] -25cm [o_C] -50cm [o_C] T e m per at ur e [ o C] Time [min] 1 10 100 1000 104 105 106 107 108 0 10 20 30 40 50 P a rt ic le c on cen tr at io n [1 /c m 3] Time [min] 0.01 1 100 104 106 108 0.01 0.1 1 10 Time = 5 min Time = 10 min Time = 15 min Time = 20 min P a rt ic le c on cen tr at io n [1 /c m 3]

0 20 40 60 80 100 0 10 20 30 40 50 60 SPR [m2/s] SP R [ m 2 /s ] Time [min]

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T4 0 500 1000 1500 2000 0 10 20 30 40 50 HRRtot [kW] HRRconv [kW] H e at r el e as e r ate [k W ] Time [min] 0 500 1000 1500 0 10 20 30 40 50 C25 T 0cm [o_C] C24 T -25cm [o_C] C23 T -50cm [o_C] T e m per at ur e [ o C] Time [min] 1 10 100 1000 104 105 106 107 108 0 10 20 30 40 50 P a rt ic le c on cen tr at io n [1 /c m 3] Time [min] 0.01 1 100 104 106 108 0.01 0.1 1 10 Time = 5 min Time = 10 min Time = 15 min Time = 20 min P a rt ic le c on cen tr at io n [1 /c m 3]

0 50 100 150 200 0 5 10 15 20 25 30 35 40 SPR [m2/s] SP R [ m 2 /s ] Time [min]

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Appendix 3 Photos from the tests

a) b)

Figure A3.1 The square propane burner used for ignition, seen a) from the seen under the steel pan and b) from above through the square hole in the steel pan.

Figure A3.2 Example of a cage used in the tests.

Figure A3.3 Test T1 in the early stages.

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Figure A3.6 Test T3 with steel plates around the sides. Figure A3.7 Test T3.

Figure A3.8 Test T3. Figure A3.9 Holes in the bottom after test T3.

Figure A3.10 During the early stages of test T4.

Figure A3.11 Test T4 with water application.

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SP Fire Technology SP REPORT 2005:42 ISBN 91-85303-74-7 ISSN 0284-5172

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Emissions from Fires in Electrical and Electronics Waste

Emissions from Fires in Electrical

and Electronics Waste

SP Swedish National T

Emissions from Fires in Electrical

and Electronics Waste

Abstract

Contents

Preface

Sammanfattning

1

Introduction

2

Commodities and experimental set-up

3

Experimental procedure

4

Measurement, sampling and analysis

methods

4.1

Gas analysis

4.1.1

Collection of smoke gases and HRR measurement

4.1.2

Analysis of the smoke gases

4.2

Analysis of extinguishing water

4.3

Analysis of fire debris

5

Results

5.1

Heat release rate and temperature

5.2

Mass loss

5.3

Gas analyses

m

m

Y

Δ

=

5.3.1

Inorganic gases

5.3.2

VOC

5.3.3

PAH

5.3.4

Dioxins and furans

5.3.5

Brominated flame retardants

5.3.6

Particles

5.3.7

Metals

5.4

Water application

5.4.1

Extinguishment

5.4.2

Water analyses

5.5

Analyses of fire debris

6

Discussion and conclusions

7

References

Appendix 1 Test protocols

Appendix 2

Time-resolved results

Appendix 3

Photos from the tests