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Benker, S. Weinbruch, Y. Thomassen, D. G. Ellingsen and B. Berlinger, Environ. Sci.: Processes Impacts,
2019, DOI: 10.1039/C8EM00518D.
Volume 20 Number 5 May 2018 Pages 737–856 This is an Accepted Manuscript, which has been through the
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Page 1 of 36 Environmental Science: Processes & Impacts
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3 Environmental impact View Article Online
DOI: 10.1039/C8EM00518D
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5 The production of silicon carbide (SiC) is a worldwide industry that is expected to grow in the coming
6
years. Previous investigations on the particulate matter (PM) in the SiC industry concentrate mainly on
Environmental Science: Processes & Impacts Accepted Manuscript

7
8 the mechanical generated dust, and a complete characterization of the airborne PM is still missing. It
9
10 was therefore the aim of this work to investigate the overall workplace atmosphere in the SiC production
11
with focus on the size distribution, phase composition, morphology and mixing state of the PM. The
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13 results show a complex mixture of particles with the relative abundance of different particle groups
14
strongly depending on the size range. In addition new particle groups not considered before were
Published on 21 January 2019. Downloaded by University of Winnipeg on 1/30/2019 10:44:55 AM.
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16 identified. Such detailed particle characterization is key for identifying and minimising emissions of
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18 PM, recognizing risk factors for epidemiological studies and finally to mitigate workers exposure.
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Environmental Science: Processes & Impacts Page 2 of 36
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4 Size Distribution and Single Particle Characterization of Airborne
DOI: 10.1039/C8EM00518D
View Article Online
5 Particulate Matter collected in a Silicon Carbide Plant

6

7 Torunn Kringlen Ervik1*, Nathalie Benker2, Stephan Weinbruch1, 2, Yngvar Thomassen1, Dag G. Ellingsen1,
8 Balázs Berlinger1
9
1Department of Chemical and Biological Work Environment, National Institute of Occupational Health, P.O.Box
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11 5330 Majorstuen, NO-0304 Oslo, Norway
2Institute of Applied Geosciences, Technical University Darmstadt, Schnittspahnstr. 9, D-64287 Darmstadt,
12
13 Germany
14
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16 *Corresponding author: Torunn Kringlen Ervik, Torunn.Ervik@Stami.no, +4723195337
17
18 Abstract
19
20 The global SiC market is projected to grow in the coming years, and research on potential health effects
21 as well as epidemiological studies is therefore of importance. A detailed characterization in terms of Lo que sé
22 ustedes a y
23 phase composition, morphology and mixing state of the airborne PM is still missing, though highly objetivo
24
25
necessary to identify sources and to understand the risk factors in this industry. Particles in the size range
26 10 nm–10 µm were collected by a 13-stage NanoMOUDI impactor in the Acheson Furnace Hall as well
27
28 as in processing departments during two sampling campaigns. Particle mass concentrations, including
29 the fraction of ultrafine particles (UFP), were lower in the processing departments in comparison to the
30
31 Acheson Furnace Hall. Particle-number size distribution measured by a scanning mobility particle sizer
32
confirmed the low amount of UFP in the processing departments compared to the furnace hall.
33
34 Significant differences in particle mass concentration and distribution were observed in the Acheson
35
36 Furnace Hall during the two sampling campaigns. The PM size distribution depend upon sampling
37 location, on the cycle of the nearby furnaces as well as on special incidents occurring during a furnace
38
39 run. Scanning and transmission electron microscopy (SEM, TEM) showed that the size range of 0.32 – Resultad
os Sem
40 10 µm (aerodynamic diameter) is dominated by carbon (C) rich particles, which were identified as
41
42 petroleum coke, graphite, soot and amorphous spherical C-rich particles. Soot was further classified into
43
three types based on primary particle size, morphology and composition. Diesel powered vehicles,
44
45 pyrolysis of petroleum coke and incomplete combustion of volatile components from this pyrolysis are
46
47 suggested as sources for the different soot particle types. Amorphous spherical C-rich particles were
48 also sub-classified based on morphology and composition as tar balls (TB) and C-spherical type 2. The
49
50 amount of SiC-fibers and crystalline SiO2 was found to be low. In the size fraction below 0.32 µm
51
(aerodynamic diameter), sulphur (S) rich particles dominate. This knowledge of particle size distribution
52
53 as well as chemical and physical properties of the PM occurring in the SiC production is fundamental
54 Importancia
55 for an appropriate risk assessment, and these findings should have implications for future
56 epidemiological studies and for the mitigation of workers exposure.
57
58 1. Introduction
59
60
1
1
2
3 Silicon carbide (SiC) is a hard and brittle ceramic material and beside the wide use as an abrasive in Online
View Article
DOI: 10.1039/C8EM00518D
4
5 cutting and grinding industry, SiC is also applied in the refractory and foundry industry, electronic Usos SiC
6 industry and in diesel particulate filters 1, 2. The annual global production was estimated to 1.5 million

7
8 ton in 2016 3. Industrial SiC production applies the Acheson process in which sand, petrol coke are Como se
fabrica
9
mixed together and charged in massive open furnaces to produce SiC. A core of graphite serves as
10
11 heating element and heats the mixture to ~2500 ˚C (core temperature) for 30-60 hours. “Crude” is the
12
13 expression used for the solid SiC cylindrical ingot surrounding the graphite core after a completed
14 heating cycle. Both crystal structure and impurity content vary over the cross section of the crude. The
15
16 inner layer consists of α-SiC (hexagonal structure) followed by a layer of β-SiC (cubic), while the outer
17
layers consist of partly and unreacted raw materials4. Two different purity grades of SiC can be
18
19 produced. A core of green SiC has higher purity and hardness and is made from a virgin mix of sand
20 Verde y
negro and coke, whereas black SiC is made from a mix that also includes recycled material from previous
21
22 process cycles5. The crude is sorted and thereby crushed and grinded into granules with sizes depending
23
24 on the final application 4.
25 Consecuencias del SiC
26 Production of SiC generates a range of different airborne particulate matter (PM), consisting of
27
28 Que crystalline silica (α-quartz and cristobalite), amorphous silica, SiC fibres, non-fibrous SiC, polyaromatic
29 compuesto hydrocarbons (PAH), graphite and other carbonaceous material, as well as gases, such as carbon
30 genera el SiC
31 monoxide (CO) and sulphur dioxide (SO2) 6-8. Several studies characterized the PM in the Acheson
32 Furnace Hall 9-12, often with a special focus on airborne SiC fibres, which are one of the suspected agents
33
34 responsible for the historical increased risk of cancer reported in this industry, in addition to crystalline
35
silica (quartz and cristobalite) 13-15. Bugge et al. 16 used a comprehensive job-exposure matrix to examine
36
37 the relative importance of specific exposure factors. Results from their study indicated that cristobalite
38
39 is the most important occupational risk factor with an additional effect from SiC fibres. Other health
40 Problemaseffects related to SiC production include impaired lung function and increased mortality from non-
41 a la salud
42 que malignant respiratory diseases 17, 18. Føreland et al. 19 assessed the personal exposure to fibres, crystalline
43 ocasiona
silica, SiC and SO2 for different job groups and departments in the Norwegian SiC industry. Air
44
Normas del
45 concentrations generally below the Norwegian administrative norms (AN) were reported for the various aire y
46 componentes
47
agents. However, high air concentrations of fibres and respirable dust, above the AN (>0.1 fibre cm-3
48 for fibres and >0.5 mg m-3 for respirable dust in the SiC industry), occurred in the Acheson Furnace
49
50 Hall. A more recent study aimed to investigate the ultrafine particles (UFP, particles with aerodynamic
51 diameter less than 100 nm) fraction during SiC production 20. An electrical low pressure impactor (ELPI)
52
53 was used to collect particles for SEM and TEM investigations; however, particles below 379 nm could
54
not be studied accurately because they were embedded by the grease used on each stage to avoid Lo que se
55 encontró
56 bouncing. Nevertheless, for the investigated stages with sizes ranging from 0.379 – 9.85 µm it was sobre
57 carbon
58 concluded that carbonaceous particles dominate in the Acheson Furnace hall. Carbonaceous particles
59 can originate from many different sources inside the Acheson Furnace Hall: graphite from the heating
60
Origen de las
partículas de
carbón
2
Origen de las
1
partículas de
2
carbón
3 element, petroleum coke from raw materials and soot from both, diesel vehicles and from the furnace
View Article Online
DOI: 10.1039/C8EM00518D
4
5 process itself.
6 Entonces la importancia será..

7 Despite the existence of the above-mentioned PM investigations, a detailed characterization of the phase
8
9 composition, morphology and mixing state of the airborne PM is missing in this industry. Most of the
10 previous work on characterization and exposure assessments focus primarily on the mechanically
11
12 generated dust, which in an exposure situation depend strongly on the job function. Our aim was to
13 investigate individual particles from the overall workroom air, taking into account the thermally
14 Objetivo
15 generated particles, which also includes UFPs. Thus, an in-depth characterization of individual particles
16
in the Acheson Furnace Hall is necessary to elucidate the various particle groups as a function of size,
17
18 as well as to identify their sources. Electron microscopy, both SEM and TEM, is the preferred technique
19
20 for such study 21-23. The present study focusses particularly on C-rich particles that appear to dominate
21 Tamaños
the PM in the Acheson furnace hall, at least for particles in the size range of 0.32 – 10 µm. que miden
22
23
2. Materials and Methods
24
25 2.1. Sampling
26
Air sampling was performed in a SiC plant in Norway during two sampling campaigns, hereafter called
27
28 Campaign 1 and Campaign 2. In Campaign 1, samples were only collected in the Acheson Furnace Hall Lugar
29 muestreo
30 whereas Campaign 2 also included sampling in the processing departments, the Sorting Department and
31 the Diesel Particulate Filter (DPF) Department. Air samples for gravimetric measurements were
32 Filtro y
33 collected with a 13 stage Model 125R NanoMOUDI-IITM (Microorifice Uniform Deposit Impactor) método
34 (MSP corporation, TSI, Shoreview, MN, USA) on 47 mm polyvinyl chloride (PVC) filters (Merck
35
36 Millipore, Burlington, MA, USA) with pore size of 5 µm. Sampling times were in the range of 140 to
37
300 minutes and the impactor was operated at a flow rate of 10 L min-1. The 50 % cut-size for particle
38
39 aerodynamic diameter for each stage were: 10, 5.6, 3.2, 1.8, 1.0, 0.56, 0.32, 0.18, 0.10, 0.056, 0.032,
40
41 0.018 and 0.01 µm, respectively. The cut-size is given in parentheses for the corresponding stages
42 throughout the manuscript. A TSI Scanning Mobility Particle Sizer (SMPS) instrument (model 3034,
43
44 TSI Inc., Shoreview, MN, USA) with flow rate 1 l min-1 was operated in parallel with the NanoMOUDI
45
impactor during sampling Campaign 2. In SMPS model 3034, the components are integrated into a
46
47 single box. The differential mobility analyzer (DMA) sheath flow is maintained at 4.0 L min-1 and the
48
49 condensation particle counter (CPC) operates as an optical particle counter where butanol is used as
50 condensation fluid. The instruments were placed next to each other on a table close (~1 m) to one of the
51
52 active furnaces (see Figure S1 in the Electronic Supplementary Information, ESI). The Acheson hall
53 contains many furnaces and these are operated in cycles and in sets of four. The four furnaces are at
54
55 different operating phases, one in the process of being built, one is active, one is cooling down and one
56
is in the dismantling phase 20. The height above the ground was approximately 1.50 m for the
57
58 NanoMOUDI inlet. The SMPS counts particles within the size range of 10-487 nm electrical mobility Rango de
59
60 diameter. During sampling Campaign 1, the NanoMOUDI impactor was additionally used to collect partículas
medidas
particles in the Acheson furnace hall for electron microscopy. Copper (Cu) TEM grids with holey carbon
3
1
2
3 films (EMresolution, Sheffield, UK) were affixed to the surface of the PVC filters thatDOI:
were used as Online
View Article
10.1039/C8EM00518D
4
5 impactor substrates in all stages of the impactor, except for the after filter. When collecting particles on
6 TEM grids in the impactor, the sampling time was 3 minutes. This sampling time was chosen based on

7
8 previous experiences from various smelting plants.
9
10 Muestre ador de particulas
11 The electrostatic sampler ESPnano model 100 (ESPnano Inc., Spokane, WA, USA) is designed to
12
13 collect particles in the sub-micron range directly onto Cu TEM grids with holey carbon films 24. The
14 sampling times varied between 20 and 200 sec depending on air concentration, where approximate
15
16 sampling time recommendations were given by the producer. The number concentrations monitored by
17
the SMPS also gives information about which sampling time to use. Several samples with various time
18
19 durations were collected at each sampling location. Air samples were collected close to one of the
20
21 running Acheson furnaces, in the Sorting Department and in the DPF Department.
22
23
24 2.2 Gravimetric measurements
25
26 The collected aerosol particulate masses were determined gravimetrically by a Sartorius Micro model
27
28 MC5 balance (max capacity 5.1 g, stability < 1 µm, Sartorius AG, Göttingen, Germany) in a weighing
29 room dedicated to low filter mass measurements, under controlled relative humidity (40  2%) and
30
31 temperature (20  1 °C) conditions. The balance was calibrated daily. The mass detection limits
32
calculated as 3 times standard deviation of all field blanks were 0.005 mg for the PVC substrates used
33
34 in the study. The PVC substrates were chosen based on their weight stability and non-hygroscopicity25.
35
36 Both before and after exposure the substrates were stored in the weighing room for at least two days to
37 be conditioned prior to the weighing procedure. All filters were discharged by a 210-Po source prior to
38
39 weighing.
40
41 2.3 SEM and TEM Characterization
42
43 PM collected on Cu TEM grids by ESPnano and NanoMOUDI was investigated directly in SEM and
44
45 TEM without further sample preparation. Samples were imaged and analysed with a Hitachi SU6600
46
field emission SEM (Hitachi, Tokyo, Japan) equipped with a Bruker energy-dispersive X-ray
47
48 spectrometry (EDX) detector (Bruker Nano GmbH, Berlin, Germany) and a NORDIF electron
49
50 backscatter diffraction (EBSD) detector (NORDIF, Trondheim, Norway). Samples were also
51 investigated by TEM using a Jeol 2100 F (Jeol, Tokyo, Japan) instrument (field emission gun) coupled
52
53 with a X-Max EDX silicon drift detector (Oxford Instruments, Abingdon, UK). The microscope was
Modo
54
operated in scanning transmission electron microscopy (STEM) and TEM mode. The acceleration microscopio
55
56 voltage was 200 kV leading to a point resolution of approximately 0.22 nm. Images were recorded with
57
58 a charge-coupled device (CCD) camera and treated with Digital Micrograph software (Gatan Inc.,
59 Pleasanton, USA) and FIJI image processing software 26. All substrates of the NanoMOUDI were
60
investigated by SEM. Stages 3, 5, 7 and 9 (3.2, 1.0, 0.32 and 0.10 µm respectively) were further
4
1
2
3 investigated by TEM for detailed characterization of certain particle groups. BecauseDOI:
of 10.1039/C8EM00518D
the View
short
Article Online
4
5 sampling time, stages 10, 11, 12 and 13 (0.056, 0.032, 0.018 and 0.010 µm respectively) contained very
6 few particles, but a longer sampling time would lead to overloading of the grids on the top stages. These

7
8 stages were therefore not included in the analysis of particle group abundance. Automated EDX particle
9
analysis is challenging on such samples as some particles cannot be differentiated in terms of
10
11 composition and size/shape. In addition, quantitative EDX analyses are not always straightforward,
12
13 especially on small particles 27. Therefore, in addition to EDX analysis, a visual evaluation was
14 performed for every particle. On stage 1-9 (10 µm – 0.1 µm) of the NanoMOUDI, a minimum of 200
15
16 particles were analysed.
17
18
19
20 3. Results and discussion
21
22
23
24 3.1 Particle size distribution
25
26 The particle mass size distributions determined by NanoMOUDI are presented as lognormal
27 distributions in Figure 1 for the Acheson Furnace Hall (two measurements), the Sorting Department and
28
29 the DPF Department. The overall PM air mass concentrations are lower in the processing departments
30 Donde hay
than in the Acheson Furnace Hall. However, the mass concentrations measured in the Acheson Furnace más uPF
31
32 Hall during the two sampling campaigns differ significantly with higher values for sampling Campaign
33
34 2 (Figure 1 a). In addition, the relative amount of UFPs is 1.2% for Campaign 1 versus 17.8% for
35 Campaign 2. The amount of UFPs in terms of mass relative to the size fraction below 1 µm aerodynamic
36
37 diameter is 5.9% and 43% for Campaign 1 and 2, respectively. The variations in PM air mass
38 concentration and size distribution can relate to a number of parameters of which sampling location and
39
40 operating status of the nearby furnaces are most important. After a finalized process run, the top layers
41
42
of unreacted raw materials are removed, and the newly made SiC cylinder is uncovered. Large chunks
43 of material are broken off and transported to further cleaning. The graphite core which acted as the
44
45 heating element is also removed and recycled. This mechanical process generates high amounts of Lo que se
46 genera en
relatively coarse particulates, whereas a furnace in the heating up or burning phase emits finer particles. el proceso
47
48 A particular incident called a blow can also occur during a process run. This is an eruption of hot gases,
49
which is related to local overpressure in the furnace. The hot gases include SiO vapour, which condenses
50
51 and oxidizes to ultrafine particles of amorphous SiO2. In addition, the blow whirls up dry furnace charge
52
53 from the surface. Altogether, the combination of these mechanical and thermal processes creates a
54 complex mixture of PM, which varies inside the Acheson Furnace Hall throughout the day. In the
55
56 Sorting and DPF Departments, PM can be expected to contain less UFP since no thermal processes are
57 taking place. This is in agreement with the NanoMOUDI measurements shown in Figure 1 b and c. A
58
59 low concentration of UFPs was particularly observed for samples from the DPF Department. It is
60
important to keep in mind that sampling artefacts might arise when using cascade impactors. The
5
1
2
3 reported main weakness of cascade impactors is the fine particle loss and bouncing, and bouncing occurs
View Article Online
DOI: 10.1039/C8EM00518D
4 Proceso
5 Bounce especially for the stages with small cut-sizes because of high impaction velocity 28-30. For outdoor air
6 samples, the NanoMOUDI impactor has previously been found to show a good agreement for particles

7
8 above 320 nm, however, below 320 nm larger mass concentrations were reported than that in the internal
9
reference 31. The exact reason for this behaviour was not known, but could be related to particle bounce,
10
11 to the dissociation of semi volatiles in the coarser stages and/or to particle shrinkage 31. Nevertheless,
12
13 such sampling artefacts will depend on the sampled aerosol, on the type of filters used and on the
14 sampling conditions. Grease has often been used to avoid particle bouncing. A previous investigation
15
16 by Cena et al. 32 on the collection of welding fume samples indicated that PVC filters without grease
Filtros de
17
pvc evitan presented minimal particle bouncing in the MOUDI stages. Based on this knowledge, PVC filters were
18 bounce
19 chosen as substrates. On the other hand, it is difficult to completely avoid such effects and particle
20
21 bouncing will inevitably present an uncertainty in these measurements.
22
23 The average number size distributions from SMPS measurements are shown in Figure 2 and illustrate
Fig 2
24
the low amount of UFPs in the processing departments compared to the Acheson Furnace Hall. The
25
26 variability in number concentration inside the Acheson Furnace Hall are shown in Figure S2 in ESI
27
28 where the number concentration for four different mobility diameters as a function of time is shown.
29 The peak seen at 11:43 was significant for mobility diameters ranging from 55 nm to 130 nm and may
30
31 have been caused by a blow of a nearby furnace. After approximately 10 minutes, the number
32 concentrations returned to the former levels.
33
34
35
36 3.2 Electron microscopy results
37
38 Few particles were found on the samples from the sorting and DPF Departments. Despite using the
39
40 recommended sampling times from the producer for specific air concentrations, the sampling times in
41 the two processing departments were too short. The variation of the PM was expected to be lower in the
42
43 processing departments compared to the Acheson Furnace Hall. The few particles found in the DPF
Lo que se
44
encontró Department consisted of only Si and C, which indicates pure SiC. No carbonaceous particles were found
45
en DPF
46
Departmenton the grids from the processing departments.
47
48 Lo que la The dominant particle groups found on Cu-grids collected in the ESPnano in the Acheson Furnace Hall
49 regilla
50 captó were agglomerates of spherical amorphous SiO2, spherical carbon (C) rich particles, sulphur (S) rich
51
particles and soot particles. The effluent CO gas contains a small amount of SiO vapour 1. This vapour
52
53 condenses to SiO with further oxidation to ultrafine amorphous SiO2 particles which settle in the furnace
54
55 mix and on the furnace surface. If a blow occurs, SiO2 particles forms from the hot gas. Almost all the
56 SiO2 particles were found as agglomerates (Figure 3 a). The amorphous nature of the particle is shown
57
58 in Figure 3 b. The other particle types are discussed below.
59
60 The relative abundance of selected particle groups are shown in Figure 4. In general, the first seven
stages of the NanoMOUDI were dominated by C-rich particles, as was also reported by Jorgensen et al.
6
1
2
3 20. On stage 1-7 (10 µm -0.32 µm) approximately 50-80 % of the particles analysed were found to View
be C-Article Online
DOI: 10.1039/C8EM00518D
4
5 rich particles. Stages 8 (0.18 µm) and 9 (0.10 µm) had a high amount of spherical S-rich particles
6 (described below) and therefore a lower share of C-rich particles. This was due to the high number of

7
8 S-rich particles in the size range 50-200 nm. Consequently, a higher number than 200 particles had to
9
be analysed to obtain a representative number of C-rich particles. The relative abundance of C-rich
10
11 particles on stages 1-9 (10 µm – 0.1 µm) of NanoMOUDI is summarized in Figure 5. Industrial high
12
13 temperature processes can generate high amounts of UFP, however, the primary particles are often
14 agglomerated or aggregated 21, 23, 33. In the industry investigated, a high number of primary particles
15
16 identified as either C-spherical or S-rich were observed. This might explain the relative high mass
17
concentration of UFP, especially observed for sampling Campaign 2 (Figure 1 b). The few particles
18
19 found and investigated on stage 10, 11, 12 and 13 (0.056, 0.032, 0.018 and 0.010 µm) were assigned to
20
21 either the C-spherical or the S-rich particle groups, with the majority being S-rich particles. Again,
22 sampling artefacts from the NanoMOUDI might affect the results. Noël et al.28 assessed the contribution
23
24 of electron microscopy to nanoparticle characterization sampled with cascade impactors. In their
25 investigation, the MOUDI impactor gave more stable results and smaller geometric standard deviations
26
27 per stage when compared to a ELPI 28. This was thought to be related to the rotation of the collection
28
stages, which can minimize the resuspension of particles. However, as mentioned by Fonseca et al.31
29
30 rotational plates can generate heat inside the MOUDI and subsequently lead to particle volatilisation.
31
32 The error introduced by such effects will again depend on the aerosol type and the sampling conditions.
33 An additional finding in the work of Noël et al.28 was that sampling on Cu-TEM grids gave better results
34
35 than sampling on Al substrates, and this was related to particle bouncing.
36
37 The particle groups were identified based on morphology and chemistry in SEM with support from TEM
38
39 analysis where the nanostructure was investigated in detail. The C-rich particles are termed based on
40 their characterization by electron microscopy, where soot and tar balls are well established terms 34.
41
42 Below follows a description and proposed source for each particle group. The characteristics of the main
43 particle groups is summarized in Table 2.
44
45
46 Petroleum coke
47
48 A substantial amount of the carbon rich particles, especially on stages 1-6 (10 µm-0.56 µm) (Figure 5)
49
has a shape and a chemical composition that indicate petroleum coke, a raw material in the process. On
50
51 stage 1 in NanoMOUDI, only this type of C-rich particles was found. A typical example of a coke
52
53 particle, a HRTEM image and its corresponding EDX spectrum are shown in Figure S3 in ESI. In TEM,
54 these particles were identified to be amorphous. A S signal always exists in the EDX spectrum for
55
56 petroleum coke, which typically contains 1-7% sulphur 4. Since petroleum coke is brittle and low in
57 strength the airborne particles are expected to be fragments from larger coke grains mechanically
58
59 generated during transportation, charging and cleaning of the furnaces. Debris from an unintended blow
60
may also be a source of coke particles.
7
1
2
3 Graphite View Article Online
DOI: 10.1039/C8EM00518D
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5
In addition to the amorphous C-rich particles, crystalline carbonaceous particles were found, often with
6

7 a flaky shape that indicates graphite. A typical example of a graphite particle, its corresponding EBSD
8
9 pattern and EDX spectrum are shown in Figure S4 in ESI. In contrast to the coke particles, graphite does
10 not show a S signal in the X-ray spectrum. A small Si signal is also observed in the spectrum, but the
11
12 exact origin is not known. Other graphite particles did not show a Si signal and it is therefore likely that
13 the origin is another particle attached to the graphite grain. EBSD in SEM can be used to characterize
14
15 the phase composition of particles 35, and all potential graphite particles were investigated by EBSD to
16
confirm their crystallinity. The inner core of the furnace is a layer of graphite used as heating element.
17
18 The graphite electrodes are removed and recycled after each run. In addition, graphite is formed in the
19
20 furnace as part of the petroleum coke transforms to graphite during the high temperature process. A
21 detachable layer of this secondary graphite particles may adhere to the inner surfaces 4, and after cleaning
22
23 and separating the final material, the particles may be emitted into the environment.
24
25 Soot
26
27 Other C-rich particles found include fractal-like soot agglomerates with primary particles showing the
28
29 typical onion-shell structure with a concentric arrangement of graphene layers. In the present work, the
30
term soot is used in accordance with Buseck et al. for all carbonaceous particles consisting of
31
32 nanospheres of concentrically arranged graphene-like layers of carbon 34. Soot was found on most stages
33
34 of the NanoMOUDI, with the highest relative abundances below stage 5 (1.0 µm) (Figure 5). SEM and
35 HRTEM images of soot particles are shown in Figure 6. The size variation of the primary particles (~20
36
37 nm up to 500 nm) is significant and may indicate different sources.
38
39 Freshly emitted diesel soot is known to form chain-like agglomerates. The average diameter of the
40
41 primary particles of diesel soot collected in aluminium smelters was previously found to vary between
42 23.3 ± 5.3 nm and 27.7 ± 7.9 nm 36. Even with varying operating conditions of the engine, the diameter
43
44 of primary particles in diesel soot agglomerates has been shown to remain within a narrow range around
45
25 nm 37. A quantitative measurement of primary particle size was not performed in the present study.
46
47 However, the few particle sizes measured are within this size range. This may indicate that many of the
48
49 soot particles with the smallest primary particle size (Figure 6 a, d) originate from diesel-fuelled vehicles
50 or machinery, which do exist in the Acheson Furnace Hall. The chemical composition of soot particles
51
52 may further help to determine their sources. A typical EDX spectrum of soot is shown in Figure S5 a in
53 ESI. In addition to the dominating C signal, signals of O and Si are always observed for the soot
54
55 agglomerates with the smallest primary particle sizes. Diesel soot is in general expected to only show
56
57
signals of C and O by EDX analysis. There are many sources of Si in the Acheson Furnace Hall. SiO
58 vapor that condenses to SiO2 can coat soot agglomerates and this is observed for the larger soot particles
59
60 described below. However, Si has also been found as a trace material in soot from diesel engines not in
relation to a SiC production plant 38, 39.
8
1
2
3 There exist other sources of soot than diesel engines in the investigated industry. When the pet coke is Online
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DOI: 10.1039/C8EM00518D
4
5 pyrolysed, volatile components, such as tars and gases are driven off at relatively low temperatures and
6 are transported along with CO to the furnace surface where they are burned with insufficient oxygen

7
8 (O2) 4. Soot can in general be formed directly from the pyrolysis products and during the combustion of
9
these. The soot particles displayed in Fig. 6 b and c might originate from both sources. The soot in Figure
10
11 6 b shows the typical fractal-like geometry, though apparently with significant larger primary particle
12
13 sizes (50 – 100 nm) than the presumed diesel soot. The corresponding EDX-spectrum is shown in Figure
14 S5 b in ESI. For this soot type, an additional S signal was always observed. Sulphur, a volatile impurity
15
16 in coke, is emitted as SO2 during the process and S containing species may be incorporated into the soot
17
particles during their formation. In addition, the diameter and the number concentration of soot particles
18
19 may be affected by SO2 and sulphur trioxide SO3 since the presence of these gases in lean flames are
20
21 reported to enhance the acetylene formation - the presumed main participant in the growth of soot
22 particles 40. Nevertheless, since SO2 gas exists in the hall, diesel soot may also be internally mixed with
23
24 sulphur containing species, and S is therefore not a suitable element for unequivocal source
25 identification in this industry. Again, a Si signal was observed, though with higher intensities than for
26
27 diesel soot. HRTEM (Figure 6 e) showed an amorphous surface layer (approximately 5 nm thickness)
28
on this kind of soot particles, which consists according to EDX and element distribution images (Figure
29
30 7) of SiO2. The presence of an amorphous SiO2 layer might indicate that these soot particles are formed
31
32 inside the furnace or at the surface of the furnace where the SiO vapour condenses. Other soot
33 agglomerates appear to be embedded in the SiO2 coating. Embedded and compact soot particles were
34
35 frequently found in the ambient atmosphere after long-range transport and in samples from wildfires 41,
36 42. They were often coated by hygroscopic secondary organic material, which led to further compaction
37
38 of the open-structure agglomerate 43. We cannot exclude the possibility that some soot agglomerates are
39
40
coated by other inorganic or organic species. A wide range of hydrocarbons is released by the pyrolysis
41 of coke and can condense on the surface of soot agglomerates.
42
43 An additional type of soot with much larger primary particle size (diameter up to 500 nm) is shown in
44
45 Figure 6 c. A HRTEM image is shown in Figure 6 f. Similar soot particles were reported in the pyrolysis
46
47
of coal, pet coke and asphaltenes 44-46. Temperature and residence time are factors that influence the
48 primary particle size of soot. In pyrolysis of coal and asphaltenes, the size of the generated particles
49
50 decreased with increasing temperature 46. This was further related to secondary reactions of tar, where
51 cracking at lower temperatures leads to a high concentration of light gases such as acetylene. The time
52
53 spent at high temperatures is also important since the primary soot particles have more time for surface
54
growth and mass addition 45. The large primary particle size observed for this soot type might therefore
55
56 indicate that they were formed inside the furnace where they have sufficient time and high concentration
57
58 of light gases to grow. SEM and TEM characterization also indicate that a small layer of amorphous
59 SiO2 also exist on these soot particles. Nevertheless, the relative amount of these particles is low and
60
9
1
2
3 may be explained by the low temperatures at which the volatiles are driven off. In the EDX spectrum,
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4
5 Figure S5 c in ESI, a very weak O signal might further suggest that the O2 supply was minimal.
6

7 Amorphous spherical C-rich particles
8
9 The fourth type of C-rich particles are spherical or nearly spherical particles, termed C-spherical in
10 Figure 5. Many of the C-spherical particles correspond well with so-called tar balls (TB) found in
11
12 ambient air samples 47-49. A typical example is shown Figure S6 a in ESI. Tar balls were described as
13
14
amorphous, carbonaceous spherules, with diameters typically between 30 and 500 nm which are formed
15 by gas-to-particle conversion within smoke plumes associated with burning of biomass and biofuel 47.
16
17 They are stable under electron bombardment in the high vacuum of SEM and TEM. A high percentage
18 of the particles interpreted as TBs in this study was found on stage 7 and 8 (0.32 µm and 0.18 µm). In
19
20 the Acheson process, TBs could form from volatile tars residing in the pet coke. Furthermore, EDX
21
analysis in both SEM and TEM indicate that the TBs were coated with a Si-rich layer, which again could
22
23 be SiO2 (see Figure S7 in ESI). Not all the C-spherical particles are similar to TBs. Spherical C-rich
24
25 particles, hereafter called C-spherical type 2, with a slightly different composition and morphology were
26 also found, especially on stage 8 and 9. These particles can sometimes resemble TBs and the distinction
27
28 between the two particle types in SEM is not always straightforward (see Figure S6 in ESI). Similar
29 particles were reported in ambient air samples and were termed organic particles due to the high C-
30
31 content 47, 48, 50. The particles in the current study are presumably also organic particles, however, this
32
33
assumption is based only analysis in SEM and TEM. In contrast to TBs, C-spherical type 2 particles are
34 not perfectly spherical, and the particle morphology suggests that these particles were hydrated when
35
36 collected. In addition, they are more sensitive to the electron beam and are often mixed with S-
37 compounds in which the S-rich part evaporate when exposed to the electron beam. In TEM, TBs are
38
39 stable and compact whereas C-spherical type 2 particles are unstable and contain voids and inclusions
40
(Figure S6 c and d in ESI). Both TBs and C-spherical type 2 were consistently found with varying
41
42 amounts of C, O, S and Si in the EDX spectra. Ternary diagrams of 117 particles identified as TBs and
43
44 137 particles identified as C-spherical type 2 particles are displayed in Figure 8 a and b, respectively. In
45 addition to higher amounts of O, Si and S, the C-spherical type 2 particles also contained elements such
46
47 as phosphorus (P), potassium (K) and sodium (Na).
48
49
50 S-rich particles
51
52 Spherical S-rich particles with diameters between 50 and 200 nm are found regularly distributed on the
53
54 grids from stage 7 (<0.32 µm) and below (Figure 9). It is generally difficult to image these S-rich
55 compounds at high magnifications in the microscope since they evaporate within a few seconds when
56
57 exposed to the electron beam leaving behind a small residue (Figure 9) which cannot be measured
58
accurately by EDX in SEM. Approximately 80-95% of the particles on stage 8 and 9 (0.18 µm and 0.10
59
60 µm) are S-rich compounds (Figure 5). Soot and C-spherical type 2 particles are often internally mixed
10
1
2
3 with S-rich species. TEM investigations revealed that some S-rich particles had a residueDOI:
at the border
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4
5 (Figure S8 a and b in ESI). Such border residues were observed in ambient air samples and were
6 interpreted as organic films on the S-rich particles 47, 51. It can not be deduced from the element

7
8 distribution maps whether the border residue is an amourphous SiO2 layer or an film of organic material.
9
10 Other particle groups
11
12 Besides the C-rich and S-rich particles, spherical Si-O rich particles, presumably amorphous SiO2, were
13
14
found on most of the NanoMOUDI stages. Their relative amount ranged from 9 to 22% on stage 2-7
15 (5.6 µm-0.32 µm), with the highest amount found on stage 6 (0.56 µm) (Figure 4). In contrast to the
16
17 ESPnano results, primary SiO2 particles in the size range 10-500 nm were also found in addition to the
18 agglomerated SiO2 particles. The high number of single SiO2 particles may result from the relatively
19
20 rough process of impaction, which might break the weak interactions in an agglomerate.
21
22 Some particles were identified as α-quartz with the majority found on stage 1 (10 µm). The phase
23
24 composition of these particles was confirmed by EBSD 35. Quartz is, in addition to pet coke, a raw
25 material in the process. In contrast to petroleum coke, the relative amount of quartz was found to be low.
26
27 The reason might be that airborne particles of petroleum coke are easier generated than quartz due to
28
brittleness and lower strength.
29
30
31 On the top four stages of the NanoMoudi, a few SiC-fibres were identified. Even though earlier studies
32 focussed on SiC fibres, their relative amount was found to be low on the investigated substrates. To
33
34 estimate the total number of fibres collected by the NanoMOUDI during the 3 min sampling time, the
35
exposed area of the substrate was calculated using ImageJ 52. Knowing the area of the Cu-grid and the
36
37 number of fibres collected on the grids, the total number of fibres was estimated to 0.02 fibres/cm3. This
38
39 is a highly uncertain number and does not exclude the possibility that some workers are exposed to
40 higher amounts of fibres as shown in the work of Foreland et al.19 . It is also important to remember that
41
42 the NanoMOUDI impactor is not the approved sampling instrument for fibres and that fibres normally
43 are collected by total dust cassettes. However, the NanoMOUDI impactor should collect many of the
44
45 fibres in the respirable size range. According to the work of Skogstad et al.9 all investigated fibres were
46
in this size range.
47
48
49 Table 1 lists previous investigations on PM in the SiC industry and the recent findings from this study.
50 In addition to the PM listed below, measures of PAH and SO2 has also been conducted 6, 7, 19.
51
52
53 Table 1: Particle types identified in the SiC industry.
54
55 Particle types Reference
56
crystalline silica (quartz, cristobalite, tridymite ) Smith et al. 6, Dufresne et al. 7, Scanscetti et al. 53, Dion
57
58 et al. 8, Føreland et al. 19, this study
59 SiC fibers Bye et al. 10, Dufresne et al. 7, Scansetti et al.53, Dion
60
et al.8, Skogstad et al.9, Føreland et al.19, this study
11
1
2
3 SiC-non fibrous Dufresne et al.7, Føreland et al.19, this study View Article Online
DOI: 10.1039/C8EM00518D
4
5 carbonaceous particles (petroleum coke and graphite ) Dufresne et al.7, Jørgensen et al. 20, this study
6 amorphous silica Jørgensen et al. 20, this study

7
8 soot (three different types) This study
9 C-rich spherical particles (including tar balls) This study
10
S-rich UFP particles This study
11
12
13
14 Conclusion
15
16
17 The PM collected in the SiC plant consist of a complex mixture of particles with the relative abundance
18 of different particle groups strongly depending on the size range. The mechanically generated particles
19 ParticLas Partículas as de
20 mecánicas are found in high amounts in the size range from 0.5 µm-10 µm, whereas thermally generated PMcombustión.
21 including combustion particles are found in higher amounts below 0.5 µm. Carbon rich particles
22
23 dominate in the size range 0.32 µm – 10 µm (aerodynamic diameter). The C-rich particles were
24
classified into coke, graphite, soot and spherical C-rich particles. One important result is the
25
26 identification of various types of soot, presumably generated by diesel powered vehicles or machinery
27
28 and the Acheson process, respectively. Soot agglomerates emitted from the Acheson furnace appear to
29 be coated with amorphous SiO2, an unwanted side product from the process, which is regularly observed
30
31 as agglomerates of ultrafine amorphous SiO2 particles. Amorphous spherical C-rich particles were also
32
sub-classified based on morphology and composition as tar balls (TB) and C-spherical type 2. In the
33
34 size fraction below 0.32 µm (aerodynamic diameter), sulphur (S) rich particles dominate. The results
35
36 acquired in this study might be used for identifying and minimising emissions, recognizing airborne risk
37 factors for epidemiological studies as well as for toxicological assays where particle size and physical
38
39 characteristics are essential.
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3 Table 2: Characteristics of the different particle groups.
4

5
Particle group Chemical composition Structure Morphology Particle/agglomerate size
6
7 coke major element: C amorphous layered and fractured surface 0.5-13 µm
8
minor element: S, O
9
10 graphite major element: C graphite flakes 5-10 µm
11
12
13 diesel soot major element: C onion shell structure of fractal-like agglomerates of primary particle size 20 – 30 nm
14 minor element: O, Si graphen layers primary particles
15
16 soot from incomplete combustion major element: C onion shell structure of fractal-like agglomerates of primary particle size 50 – 100 nm
17 of hydrocarbons on the furnace minor element: O, Si, S graphen layers primary particles with
18
19 surface amorphous SiO2 coating
20 pyrolysis soot major element: C onion shell structure of large individual spheres primary particle size 100 – 500 nm
21
minor element: O, Si graphen layers
22
23 tar balls major element: C amorphous spherical 50-500 nm
24
minor element: O, S, Si
25
26 spherical C-rich particles type 2 major element: C amorphous nearly spherical 100-500 nm
27 minor element: O, S, Si
28
29 S-rich particles A large S signal is observed evaporate within a few nearly spherical or elliptical 50- 200 nm
30 for a few sec before seconds when exposed to before electron bombardment
31
32 decreasing rapidly the electron beam
33 Si-O-rich particles major element: Si, O amorphous spherical 10-500 nm
34
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43 13
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3 Acknowledgments View Article Online
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5
6
This study got financial support from the Sickness Absence, Work and Health program of the Norwegian

7
8 Research Council under Grant 218350 as well as well as from the Confederation of Norwegian
9
10 Enterprise Working Environment Fund.
11
12
13 The authors declare no conflict of interest relating to the material presented in this article. Its contents,
14 including any opinions and/or conclusions expressed, are solely those of the authors.
15
16
17
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Figure 1: Gravimetric mass distribution for particles collected with the NanoMOUDI impactor in: Acheson
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Furnace Hall, Campaign 1 and Campaign 2, Sorting Department, Campaign 2 and DPF Department,
33 Campaign 2. (Detection limit: 0.002 mg/m3)
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35 157x122mm (150 x 150 DPI)
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37 Figure 2: Particle number size distribution for the three departments measured by SMPS.
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39 165x156mm (150 x 150 DPI)
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43 The average number size distributions from SMPS measurements are shown
44 in Figure 2 and illustrate the low amount of UFPs in the processing
45 departments compared to the Acheson Furnace Hall.
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DOI: 10.1039/C8EM00518D
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35 Figure 3: TEM image of a SiO2 agglomerate (a),
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41 The effluent CO gas contains a small amount of SiO vapour
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44 If a blow occurs, SiO 2particles forms from the hot gas. Almost all the SiO 2particles
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DOI: 10.1039/C8EM00518D
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35 HRTEM image showing the amorphous nature of the SiO2 particles (b).
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DOI: 10.1039/C8EM00518D
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Figure 4: Relative number abundance of particle groups found on stages 1-9 (cut size for each stage is
28 shown) in NanoMOUDI. Stages 10-13 are not included in the figure due to the low number of particles
29 collected on these stages. n= number of particles analysed. *numbers from stage 8 and 9 are estimated by
30 analysing and counting particle groups in two frames on the Cu-grid.
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32 149x95mm (150 x 150 DPI)
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36 The relative abundance of selected particle groups are shown in Figure 4. In general, the first seven stages of
37 the NanoMOUDI were dominated by C-rich particles
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DOI: 10.1039/C8EM00518D
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Figure 5: Relative number abundance of C-rich particle groups found on stages 1-9 (cut size for each stage
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is shown) in NanoMOUDI, Stages 10-13 are not included in the figure due to the low number of particles on
29 these stages. n= number of particles analysed.
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31 147x95mm (150 x 150 DPI)
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34 A substantial amount of the carbon rich particles, especially on stages 1-6 (10
35 µm-0.56 µm) (Figure 5) has a shape and a chemical composition that indicate
petroleum coke, a raw material in the process.
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39 Since petroleum coke is brittle and low in strength the airborne particles are expected to
be fragments from larger coke grains mechanically generated during transportation,
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charging and cleaning of the furnaces
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DOI: 10.1039/C8EM00518D
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31 Figure 6: SEM image of a soot agglomerate showing the typical fractal-like geometry (a),
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33 116x88mm (150 x 150 DPI)
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37 Freshly emitted diesel soot is known to form chain-like agglomerates. T
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DOI: 10.1039/C8EM00518D
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29 soot agglomerate with larger primary particle size (b),
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DOI: 10.1039/C8EM00518D
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29 and soot spherule with primary particle size of 100 – 500 nm (c).
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31 127x89mm (150 x 150 DPI)
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DOI: 10.1039/C8EM00518D
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36 HRTEM images of soot type shown in a (d),
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DOI: 10.1039/C8EM00518D
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38 soot agglomerate type shown in b (e),
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173x168mm (150 x 150 DPI)
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DOI: 10.1039/C8EM00518D
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37 and large soot spherule of approximately 100 nm size of the soot type shown in c (f).
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39 176x168mm (150 x 150 DPI)
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DOI: 10.1039/C8EM00518D
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29 Figure 7: Secondary electron (SE) image and distribution images for C, O, S and Si of the soot agglomerate
type shown in Figure 6 b and e
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31 234x159mm (150 x 150 DPI)
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DOI: 10.1039/C8EM00518D
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34 Figure 8: Composition of tar balls (a)
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DOI: 10.1039/C8EM00518D
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34 and C-spherical type 2 particles (b).
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DOI: 10.1039/C8EM00518D
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29 Figure 9: SEM images of stage 9 before (a)
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DOI: 10.1039/C8EM00518D
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29 and after evaporation of S-rich particles (b).
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1
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3 A detailed characterization of particles as function of particle size in the size range 10 nmDOI:
– 10 µmView Article Online
10.1039/C8EM00518D
4 (aerodynamic diameter) collected from a silicon carbide plant in Norway.
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DOI: 10.1039/C8EM00518D
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5 Particulate Matter collected in a Silicon Carbide Plant

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