Fuel 83 (2004) 781–790

www.fuelfirst.com

Emission characterization of particulate/gaseous phases and size

association for polycyclic aromatic hydrocarbons
from residential coal combustion
Yingjun Chen, Xinhui Bi, Bixian Mai, Guoying Sheng*, Jiamo Fu
State Key Laboratory of Organic Geochemistry, Guangzhou Key Laboratory of Environment and Resource, Guangzhou Institute of Geochemistry,
Chinese Academy of Sciences, Guangzhou 510640, People’s Republic of China
Received 24 June 2003; revised 6 November 2003; accepted 6 November 2003; available online 26 November 2003

Abstract
The emission characterization of polycyclic aromatic hydrocarbons (PAHs) emitted from the commonly used residential coal-stove in
China was studied, including the partition between the particulate and gaseous phases and the distribution as a function of particle size.
Smoke samples were taken by a PUF sampler and a size-segregated sampler through a dilution equipment and analyzed for PAHs using
GC/MS. The contribution of vapor phase to the total PAHs emitted was very important. The emission factors of 17 PAHs and 10 genotoxic
PAHs on a coal-weight basis were 116.65 and 18.41 mg/kg, respectively, greatly lower than the extraction rates of the raw anthracite coal
(2514.50 and 1343.56 mg/kg, respectively). The residential coal-stove burning honeycomb coal briquettes was identified as a clean
combustion system. Submicron particles dominated the size distribution of PAHs mass, and higher molecular weight PAHs tend to distribute
in finer particles.
q 2003 Elsevier Ltd. All rights reserved.
Keywords: Polycyclic aromatic hydrocarbons; Emissions; Residential coal combustion

1. Introduction mortality in Xuanwei, Yunnan Province, and the high

The air pollution in China cities is characterized by coal-
smoke [1,2], which derives from the situation that coal is the
most important energy source in China. Coal accounts for
approximately 75% of the total primary energy consump-
tion in China, which is greatly higher than the global
average level (27.1%) [2]. Among various coal combustors,
residential coal device is one of the important pollution
sources. The main reason of severe air pollution in northern
China cities in winter comes from the great number of
residential coal-stoves used for heating and cooking in
urban homes [1]. There are more than one million domestic
coal-stoves in the urban and suburb areas of Beijing City,
China [3]. Furthermore, residential coal combustion can
result in serious indoor air pollution, and the emitted soot
and toxic organics (such as PAHs) are greatly harmful to
human health, especially together with poor kitchen
ventilation [4 – 8]. For example, the high lung cancer
* Corresponding author. Tel.: þ 86-2085290196; fax: þ 86-2085290192.
E-mail address: shenggy@gig.ac.cn (G. Sheng).
0016-2361/$ - see front matter q 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2003.11.003
esophageal cancer rate in Linxian, Henan Province were
attributed to inhalation of PAH-coated soot particles that
remain air-borne [4 – 7] and ingestion of soot particles that
deposit on food and food-preparation surfaces within the
homes [8], respectively.
Accurate characterization of particulate matter and
organic emissions from residential coal combustion is
needed imperatively, in order to understand its contribution
to air pollution and the human exposure indoors. However,
few studies were reported about this aspect [1,9 – 12]. One
of the important reasons is the very complicated factors
that affect the emission rates of coal combustion, including
coal types, coal combustor types and burning conditions,
etc. Advocated greatly by China government as a clean
combustor, the residential coal-stove burning honeycomb
coal briquette is the commonest one among all kinds of
coal combustion devices, and its heat efficiency is up to
45% [13]. The raw coal is produced into so-called mould
coal by intermixing bond before being burned, and the
common used mould coal is honeycomb coal briquette, of
782 Y. Chen et al. / Fuel 83 (2004) 781–790

which the yearly yield was about 80 Mt till 2000 in China simulate practical domestic coal combustion in common
[13]. Based on the raw coal type and ignition mode, the Chinese homes, and the emissions were collected both by
honeycomb coal briquette can be mainly classified into two a filter/PUF sampler and a size-segregated sampler
types; one is made of anthracite coal and burnt from the through a self-designed dilution sampling equipment.
bottom, and the other is made of bituminous coal and/or PAHs, including the 16 EPA priority PAHs [24] plus
brown coal and burnt from the top. The former is benzo[e]pyrene, coronene, and methylphenanthrene, were
ubiquitously used while the latter is getting popularized selected as the target compounds due to their carcino-
in China [14]. genicity and mutagenicity. The objective of this study
Another reason for few studies on residential coal was to investigate accurately the PAHs emissions
combustion comes from the difficulty of sampling the characters from the commonest residential coal-stove,
emissions. First of all, organic compounds such as including both the partitioning between the particle and
polycyclic aromatic hydrocarbons (PAHs) in the emissions gas phases, and the distribution among various size-
are difficult to measure accurately because these com- ranged particulate matters.
pounds are present in both the gas and particle phases [15].
The partition of organics between the gas and particulate
phases is determined by several factors [16 – 19], such as 2. Experimental section
organics’ vapor pressures, the amount of fine particles, and
ambient temperature. Thus, the phase partition of organic 2.1. Fuel and stove
compounds changes as the source emissions are cooled and
diluted in the atmosphere. Oanh et al. [10] used US EPA The honeycomb coal briquettes were bought from
Modified Method 5 [20] to collect emissions from domestic Guangzhou City and the raw coal came from a nation-
combustion of selected fuels, and found that almost all owned coal mine in Yongxin County, Hunan Province,
PAHs (include high molecular weight compounds such as China. The honeycomb coal briquette is a 12-hole column
benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyr- with a height of 6 cm and a diameter of 9.5 cm, and
ene) presented in vapor phase when coal briquettes and composed of 50 wt% fine particles of anthracite coal and
charcoal were burnt. First, the reason for underestimating 50 wt% clay by weight. The characteristics of the raw coal
the amount of organic particulate matter present came from and the honeycomb coal briquette are shown in Table 1.
the high temperature (around 125 8C) of the filter box The stove for burning honeycomb coal briquette was
during the sampling [15]. Second, the dilution ratio of purchased from Guangzhou city. It is 27 cm in height and
emissions to air and the residence time of flue gas before 21 cm in outer diameter and 12.5 cm in inner diameter,
being sampled can significantly affect the total particle and can contain three briquettes at one time. This coal-
number concentration and size distribution [21,22], which stove has a metallic outer cover and thermal-insulated
also affect the partition of organics between gas and ceramic liner and an iron grate inside separating the
particle phases [10]. A dilution stack sampler was briquette-burning zone and the ash-insulating layer. There
suggested by Hildmann et al. [15], and developed by is a 6 cm-diameter hole for ventilation in the outer cover
Desert Research Institute (DRI, Nevada)[21] and Carnegie near bottom and a corresponding lid for controlling the air
Mellon University (CMU, Pittsburgh)[22] to collect the supply.
organic aerosol emissions from combustion systems, which
cannot only cool the hot emissions to ambient temperature
Table 1
but also allow independent control of the dilution ratio and Analysis of raw coal and honeycomb coal briquette
residence time to examine the effects of the sampling
conditions on the particulate emissions. However, few Raw coal Honeycomb coal briquette
studies were made using dilution sampler to report the
Proximate analysis (wt (%), on air dry (ad) basis)
emission characterization of organic compounds from
Moisture ðMad Þ 1.22 1.44
residential coal combustion, either about the partition Ash ðAad Þ 8.82 52.91
between gas and particle phases or about the distribution as Volatile ðVad Þ 6.68 6.96
a function of particle size. The distribution of the particle Fixed carbon (FCad) 83.28 38.69
size is an important parameter when measuring emission Total S ðSt;ad Þ 0.67 0.42
characteristics from coal combustion, since fine particles Elemental analysis (wt (%), on dry ash-free (daf) basis)
are considered to pose adverse effects on human health Cdaf 90.584
because they have a high specific surface area, and then Hdaf 3.539
Ndaf 0.582
often enriched with toxic species, and because they have
Odaf 1.918
long residence time in the atmosphere and can penetrate H/C (daf) 0.039
deep into the alveolar regions of the lung [23]. O/C (daf) 0.021
In this study, a residential coal-stove and honeycomb
Virtual reflectance ðR0 (%)) 2.5
coal briquette made of anthracite coal were selected to
 Y. Chen et al. / Fuel 83 (2004) 781–790
2.2. Sampling system
A dilution sampling equipment was designed for
collecting the emissions (Fig. 1). The equipment was
composed of a hood, three same-sized pipes (100 cm of
length and 30 cm of diameter) and a long curved pipe (5 cm
in diameter). All of the fittings can be disassembled at the
flanges. These pipes were long enough not only for
the mixture of the emissions with air, but also for cooling
the flue gas. The total volume of three large pipes was about
250 l. There were two sets of curved pipes designed for two
samplers with different sampling flow rates, and their
lengths were 5 and 10 m, respectively, with the correspond-
ing volumes of about 10 and 20 l. Two connectors were
made to connect the samplers with the ends of curved pipes.
All the parts were made of stainless steel, and Teflon was
used for all gaskets to avoid organic contamination.
The samplers used in this study included a PUF sampler
and size-segregated sampler. The PUF sampler was manu-
factured by Andersen Instrument Inc., and can simul-
taneously collect the particulate and gaseous organics using
glass fiber filter (GFF, Whatman, 10.2 cm in diameter) and
polyurethane foam (PUF, 6.5 cm diameter £ 8 cm height).
The size-segregated sampler is a high volume cascade
impactor manufactured by Thermo-Andersen Instrument
Inc., which can collect particles into five stages and a backup
filter (GFF, Whatman). The cut-off size is . 7.2, 3.0 –7.2,
1.5 – 3.0, 0.95 – 1.5, 0.49 – 0.95 and , 0.49 mm at the
designed flow rate of 1.13 m3/min. The actual flow rates
were read from the Manometers integrated in the samplers.
2.3. Sampling procedure
The honeycomb coal briquettes were ignited from the
bottom using a 1.5 kw electric wire instead of the wood
chips and paper commonly used [10] to avoid pollution. The
time for igniting the coal briquette was 20 min, then the
ignited coal briquette was transferred into the stove quickly
and another briquette put atop with all holes aligned. In
order to collect enough mass for organic analysis, two coal
Fig. 1. The dilution sampling system.
783
briquettes were burned with the air-control lid fully opened
in each run. Sampling period lasted for 4 h, which started
when the briquette was ignited and ended when the
combustion was over (two briquette ashes cooled to ambient
temperature). The weight of the two briquettes was recorded
before and after combustion to obtain the weight of actually
coal burned. The related information was given in Table 2.
Before sampling, all parts of the sampling equipment to
be in contact with the flue gas were cleaned properly. When
reassembled, the equipment was checked carefully for leak.
During sampling, the hood was hanged above the stove
without touch to collect the emissions but did not disturb the
burning. The curved pipe was immersed into cool water and
further dropped the emission flue to ambient temperature.
Little deposit was observed in pipes.
The actual temperature of emission flue was recorded
every 10 min and the average temperatures of sampling gas
were 23 and 25 8C, respectively, for the PUF sampler and
the cascade impactor. Since the rate of emissions produced
over the stove was less than 30 l/min, and the flow rates
were about 180 l/min and 1.13 m3/min, respectively, large
volume of additional clean air were sucked into the
sampling system and diluted the emission flue. The dilution
ratios were at least 5 and 37, respectively, for the PUF
sampler and the cascade impactor, while the residence times
of emissions before being sampled were about 88 and 14 s,
respectively, (Table 2).
The laboratory room used for sampling was designed to
contain particle-free air. The whole laboratory was airtight.
At one wall of the room, a exhaust fan was installed to draw
the air out off the room; while at the opposite end, an filter
equipment was fixed in a 30 cm £ 60 cm hole and 3-stage
filter was used to filter the particles and let the clean air in.
The exhaust fan started 30 min before each sampling run
and kept working until the sampling processes ended.
2.4. Analytic method
The analytic procedure for particulate and gaseous PAHs
in filters and PUFs was described elsewhere [25] and only
784 Y. Chen et al. / Fuel 83 (2004) 781–790
Table 2
Summary of burned honeycomb coal briquettes and sampling conditions
Samplesa Fuel
Honeycomb coal Raw coal
briquette (g) (g)
Weight before Weight after Net weight Weight
burning burning burnt burntb
TSP/PUF 908.1 561.1 347.0 380.6
Six-stage 931.6 569.2 362.4 397.4
a
TSP/PUF sample was average of three sets of samples and six-stage sample was average of two sets of samples.
b
The weight of burnt raw coal was the net weight burnt added 8.82% ash.
c
Actual flow rate at 23 8C and 760 mmHg.
d
Volume at 23 8C and 760 mmHg.
was briefly summarized here. The GFFs were baked at
450 8C for 12 h. The PUFs were pre-extracted in dichlor-
omethane (DCM) for 72 h, dried under vacuum condition.
After sampling, filters were wrapped in baked aluminum foil
and foam plugs were stored in glass jars with aluminum foil-
lids in a freezer. The weights of particulate matter collected
on the filters were determined by weighing the filters before
and after sampling under the same conditions (25 8C,
50%RH, 12 h).
Surrogate deuterated PAHs (naphthalene-d 8, ace-
naphthene-d10 , phenanthrene-d 10 , chrysene-d 12, and
perylene-d12) were added prior to extraction. All PUF
samples were extracted for 72 h with DCM in a Soxhlet
apparatus. Filters were extracted ultrasonically three times
with 150 ml DCM. Each extraction lasted 30 mins. The
organic extract was concentrated on a rotary evaporator
(Büchl Rotavapor R-114) and fractionated using 2:1
silica– alumina column chromatography. The PAHs frac-
tion was concentrated to 0.1– 0.5 ml using rotary evapor-
ation followed by a gentle stream of nitrogen. Internal
standard hexamethylbenzene was added for quantification
of individual PAHs.
All samples were analyzed using gas chromatography
with mass selective detection (GC-MS) using a
Hewlett – Packard (HP)-5890 equipped with a 25 m £
0.32 mm i.d. HP-5 capillary column (0.25 mm film
thickness) coupled to a HP-5972 mass spectrometer
operated in the electron impact mode (70 eV). The
chromatographic conditions were as follows: injector
temperature, 280 8C; ion source temperature, 180 8C;
temperature program: 65 8C (5 min), 65 – 290 8C at
3 8C/min, 290 8C (20 min). The carrier gas was Helium
at a constant flow rate of 1.5 ml/min. Sample of 1 ml
was injected with splitless mode. Mass range m/z 50
and 500 was used for quantitative determinations. Data
acquisition and processing were controlled by a HP
Chemstation data system.
Sampling
Sampler Sampling Average Volume Average Residence
time (h) flow rate (m3)d temperature time (s)
(l/min)c of flue (8C)
PUF 4.0 178.7 42.9 23.0 87.7
Sampler
Cascade 4.0 1130.0 271.2 25.0 14.3
impactor
2.5. Quality control
Field blanks, including GFF and PUF blanks for two
samplers, were collected for 4 h to determine the organic
concentrations of clean air and other background contami-
nation. Compared with emissions samples, PAHs were very
low in both GFF and PUF blanks. So, these contaminants in
blanks were not subtracted from emissions samples.
Surrogate standards were added to all the samples (includ-
ing blank samples) to monitor procedural performance and
matrix effects. The recoveries for deuteratd PAHs ranged
from 74 to 98%, except the mean recovery for naphthalene-
d8 was less than 30%. PAHs concentrations were corrected
by the recovery efficiency of deuteratd PAHs, while the
result of naphthalene was not included in the study because
of its low recovery.
The repeatability of the collecting procedure was
checked in three separate experiments for PUF sampler
and two for cascade impactor. The two sets of six-stage
samples were combined for analysis while the three sets of
GFF/PUF samples were analyzed separately. All the
analytical results of PAHs in GFFs and PUFs were given
by the arithmetical mean values, since the relative standard
deviations (RSD) were less than 20%.
Compound sampling breakthrough for GFF and PUF was
checked at this study by adding an additional GFF and 1/3
PUF during the repeated sampling processes. Generally, the
backup GFF contained , 7% of the total particle com-
ponent, while the backup PUF contained only , 4% of the
vapor phase component. Individually, lighter PAH had
greater penetration to the second GFF and PUF. For
example, the backup PUF contained about 23% (Fluorene)
to 33% (Acenaphthylene) for lighter PAHs but less than 2%
for higher PAHs of total concentration in vapor phase; in
particle phase, there are more than 20% for PAHs lighter
than Phenanthrene found in the backup filter, but no PAHs
higher than Benzo[a]pyrene were detected in the backup
 Y. Chen et al. / Fuel 83 (2004) 781–790 785

GFF. So, the PAH compounds in the backup materials were
not added in the corresponding total concentrations.
3. Results and discussion
3.1. PAHs in raw coal extracts
The raw anthracite coal for the honeycomb coal briquette
burned in this study was extracted for 72 h with DCM in a
Soxhlet apparatus after being crushed to 2 100 mesh
(150 mm) for PAHs analysis. The results are presented in
Table 3, with corresponding average mass percent distri-
butions summarized in Fig. 2A. 17 PAHs were identified in
the extract of the anthracite coal, including six carcinogens
(BaA, Chry, BbkF, BaP, DBahA and IncdP) and 4 co-
carcinogens (Flu, Pyr, BeP and BghiP). The PAHs mass in
the extract were dominated by Phe, BbkF, Mphe, BeP,
Fl, Chry, Pyr and BghiP, while other PAHs individually
accounted for less than 5% of the total (Fig. 2A).
The extraction rate of the total 17 PAHs on a coal-weight
basis was 2514.50 mg/kg, in which 10 genotoxic PAHs (i.e.
the carcinogenic and co-carcinogenic PAHs) accounted for
more than half of the total amount, 1343.56 mg/kg. Zhao ZB
et al. [26] analyzed the PAH components in DCM extracts
of eight bituminous coals, but did not identify PAHs with
boiling points higher than 490 8C (Benzo[b]fluoranthene).
The sum of identified three PAHs (Naphthalene, Methyl-
phenanthrene, Phenanthrene) extracted from a low volatile
bituminous coal, which had the characteristics (Cdaf,
90.42%, Hdaf, 4.61%, Ndaf, 1.39%, Sdaf, 0.46%, Ashd,
9.42%) close to the anthracite coal in this study, was
0.59 mg/kg [26]. Both the amount and type of PAHs
identified from the low volatile bituminous coal were
greatly less than that from this anthracite. In addition to
different coal types, this difference may be due to the shorter
extraction time (6 h) [26].
3.2. PAHs emission factors
The emission factors of the identified 17 PAHs in particle
and gas phases were calculated both on a coal-weight basis

Table 3
Extraction rates from raw coal and emission factors from coal combustion of PAHs

PAHsa Extraction rates from raw coal Emission factors from coal combustion
(mg/kg coal)
Particle phase Vapor phase Total emissions Vapor percent (%)b
(mg/kg) (mg/kg) (mg/kg)

Coalc Briquetted Coal Briquette Coal Briquette

Acy 0.449 0.003 0.001 0.748 0.316 0.750 0.317 99.7

Ace 3.253 nde Nd 0.534 0.225 0.534 0.225 100
Fl 223.109 0.004 0.002 8.215 3.459 8.219 3.461 100
Mphe 319.470 0.015 0.006 3.422 1.435 3.437 1.442 99.6
Phe 545.906 0.064 0.027 82.086 34.532 82.150 34.559 99.9
Ant 2.741 0.002 0.001 2.031 0.854 2.034 0.855 99.9
Flu 38.644 0.069 0.029 4.622 1.940 4.691 1.969 98.5
Pyr 151.840 0.075 0.031 4.340 1.825 4.415 1.857 98.3
BaA 7.977 0.073 0.031 0.144 0.060 0.217 0.091 66.3
Chry 186.898 0.696 0.293 1.441 0.605 2.138 0.898 67.4
BbkF 361.413 2.045 0.861 0.356 0.150 2.401 1.011 14.8
BeP 284.292 1.713 0.721 0.145 0.062 1.857 0.783 7.8
BaP 28.671 0.171 0.072 nd nd 0.171 0.072 0
IncdP 63.305 0.829 0.349 nd nd 0.829 0.349 0
DbahA 89.109 0.591 0.250 nd nd 0.591 0.250 0
BghiP 131.408 1.097 0.461 nd nd 1.097 0.461 0
Cor 76.012 1.119 0.472 nd nd 1.119 0.472 0
SPAH 2514.498 8.566 3.608 108.083 45.466 116.649 49.074 93
Sgen-PAH 1343.557 7.359 3.099 11.047 4.644 18.406 7.742 60
BaPEf 112.979 0.740 0.312 0.034 0.014 0.773 0.326 4.4
a
Abbreviations of PAHs: Acy, acenaphthylene; Ace, acenaphthene; Fl, fluorene; Mphe, methylphenanthrene (the sum of four isomers, i.e., 1-, 2-, 3-, and
9-methylphenanthrene); Phe, phenanthrene; Ant, anthracene; Flu, fluoranthene; Pyr, pyrene; BaA, benzo[a]anthracene; Chry, chrysene; BbkF,
benzo[b þ k]fluoranthene; BeP, benzo[e]pyrene; BaP, benzo[a]pyrene; IncdP, indeno[1,2,3-c,d]pyrene; DBahA, dibenzo[ah]anthracene; BghiP, benzo[ghi]-
perylene; Cor, coronene; SPAH, the sum of 17 PAHs listed above; Sgen-PAH, the sum of six carcinogenic PAHs (BaA, Chry, BbkF, BaP, DBahA and IncdP)
and four co-carcinogenic PAHs (Flu, Pyr, BeP and BghiP).
b
PAH in vapor phase in percentage of total PAH detected both in particle and in vapor phases.
c
Emission factors of individual PAHs on the basis of coal-weight.
d
Emission factors of individual PAHs on the basis honeycomb coal briquette-weight.
e
nd, not detected.
f
Benzo[a]pyrene-equivalent carcinogenic power (BaPE ¼ BaA £ 0.06 þ BbkF £ 0.07 þ BaP þ DBahA £ 0.6 þ IncdP £ 0.08).
786 Y. Chen et al. / Fuel 83 (2004) 781–790

Fig. 2. Mass percent distributions of PAHs. (A) Extractions from raw coal. (B) Total emissions from coal combustion. (C) Emissions in particle and gas phases
from coal combustion.

and on a honeycomb coal briquette-weight basis (mg/kg)
(Table 3). The emission factors of total 17 PAHs on the two
bases were 116.65 and 49.07 mg/kg, respectively; while the
emission factors of 10 genotoxic PAHs were totally 18.41
and 7.74 mg/kg, respectively. Among 17 PAHs in the total
emission factors, Phe was the most abundant compound,
and made up more than 70% of the total amount. Other
PAHs with more than 2% of the total mass were Fl, Flu, Pyr,
Mphe and BbkF (Fig. 2B).
Compared with the extraction rate from raw anthracite
coal, the emission factor of total 17 PAHs from coal
combustion was lower by 20 times; while the emission
factor of 10 genotoxic PAHs was lower by about two
orders of magnitude (Table 3). In the extracts of raw coal,
Phe and Mphe were among the most abundant compounds,
as mentioned above; their sum accounted for 34.42% of the
total 17 PAHs mass, and the ratio of Mphe to Phe was 0.59.
In the emissions of coal burning, Phe dominated the total
mass, and the value of Mphe/Phe was only 0.04. This
indicated that most PAHs in raw coal were consumed
during combustion, while a little part of PAHs were
volatilized into emission flue and/or generated during coal
burning. Lighter compounds were easier to volatilize and
escape into emission gas, while higher molecular-weight
species such as genotoxic PAHs were burnt off during
combustion.
 Y. Chen et al. / Fuel 83 (2004) 781–790 787

Table 4 from coal combustion in an atmospheric fluidized bed pilot

PAH emissions calculated as BaP equivalents and percent contribution of plant at different conditions [27].
10 PAHs to BaP equivalents
For better parameterizing the carcinogenicity of the
PAHs TEFa Emission factor BaPeq whole PAH fraction, Benzo[a]pyrene- equivalent carcino-
(EF)(mg/kg coal) (%)b genic power (BaPE) was introduced by Cecinato [28] as an
index instead of the sole Benzo[a]pyrene. The BaPE values
Phenanthrene (Phe) 0.0005 82.15 24.02 of extracts from raw coal and emission samples were
Anthracene (Ant) 0.0005 2.03 0.59
calculated using the following formula [28] and listed in
Fluoranthene (Flu) 0.05 4.69 137.16
Pyrene (Pyr) 0.001 4.42 2.58 Table 3.
Benzo[a]anthracene (BaA) 0.005 0.22 0.63
Chrysene (Chry) 0.03 2.14 37.51 BaPE ¼ BaA £ 0:06 þ BbkF £ 0:07 þ BaP þ DBahA
Benzo[b þ k]fluoranthene (BbkF) 0.075 2.40 105.31
Benzo[a]pyrene (BaP) 1 0.17 100.00 £ 0:6 þ IncdP £ 0:08 ð1Þ
Indeno[1,2,3-c,d]pyrene (IncdP) 0.1 0.83 48.48
Benzo[g,h,i]perylene (BghiP) 0.02 1.10 12.83 Based on BaPE, the emissions from honeycomb coal
a
Toxic equivalence factors (TEF) obtained from Larsen and Larsen (Ref.
briquette combustion had greatly less toxicity than raw coal
[27]), the value of BbkF is the average TEF of Benzo[b]fluoranthene (0.05) extracts, the same trend as the total and genotoxic PAHs.
and Benzo[k]fluoranthene (0.1). However, gas phase only contributed less than 5% of the
b
BðaÞPeq ð%Þ ¼ ðXTEF XEF Þ=ðBaPTEF BaPEF Þ £ 100; where X is the indi- toxicity of total emissions although it contained most PAHs
vidual PAH and EF is emission factor. mass.
Table 4 lists individual PAHs emissions calculated as
The mass percent distributions of individual PAHs were BaP equivalents and percentage of 10 PAHs to BaP
greatly different between the particulate and gas phases equivalents using toxic equivalence factors (TEF) as
(Table 3 and Fig. 2C). The most abundant PAH species in the introduced by Larsen and Larsen [29]. By using TEFs,
particle phase were those with molecular weight higher than the carcinogenic properties of the individual PAHs can be
Chry, while the sum of other lighter PAHs accounted for less discussed. From a carcinogenic point of view, Flu is an
than 4% of the total mass. The mass distribution in the vapor important compound other than BaP in emissions from coal
phase was dominated by Fl, Mphe, Phe, Ant, Flu and Pyr, combustion, and followed by BbkF (Table 4). Hedberg
with Phe as the maximum (about 82%). BaP and higher et al. also considered that Flu was as important a
molecular weight PAH species were not detected in gas contributor to cancer risk as BaP in emissions from wood
phase. The ratio of vapor phase to the sum of both phases was burning [30].
93 and 60% for 17 PAHs and 10 genotoxic PAHs, Some previous reports are listed in Table 5, including
respectively. So it could be concluded that the amount of research results on the emission factors of PAHs from
PAHs existing in the gas phase dominated the total emission coal burning by both residential stoves and industrial
mass of coal combustion although the emission flue had been plants burning coals. Although the coal types varied
dropped to ambient temperature. The similar finding also was greatly from brown coal to bituminous coal, the tendency
made by Mastral et al. when they studied the PAH emissions can be clearly seen that the emission factors from

Table 5
Previous studies on the emission factors of PAHs from various coal combustors

PAHsa Emission factors from residential combustion (mg/kg) Emission factors from power plant (mg/kg)

Anthracite Coal Brown Coal (p)e Bitu- Bitu- Coalh

coal in briquetteb coal (p)c,d minousf minousg
this study
Lignite Brown Sub-bitu- Bitu- Polish French S. African Australian
minous minous

SPAH 0.117 101.44 31.87 436 204 2137 3848 556 569 2.37 8.5 35 165
Sgen-PAHs 0.018 6.46 31.65 61 64 1010 2737 119 57.55 2.37 8.5 9.54 90.65
a
Abbreviations of PAHs refer to Table 3.
b
Refers to Oanh et al. [10].
c
p means particle phase in which PAHs were calculated, while others were the sum of particle and gas phases.
d
Refers to Grimmer et al. [11].
e
Refers to Oros and Simoneit [12].
f
Refers to Levenids and Atal [31].
g
Refers to Yang et al. [32].
h
Refers to Masclet et al. [33].
788 Y. Chen et al. / Fuel 83 (2004) 781–790
residential stoves [11,12] are 3-4 orders of magnitude
greater than from industrial plant stacks [31,32,33]. The
emission factors of total 17 PAHs from residential coal-
stoves ranged from 31.87 to 3848 mg/kg, while the rates
from industrial plants varied from 2.37 to 569 mg/kg; the
emission factors of total 10 genotoxic PAH species from
these two sources ranged from 6.46 to 2737 mg/kg and
from 2.37 to 119 mg/kg, respectively. The PAHs emis-
sion factors from honeycomb coal briquette stove in this
study are greatly lower than that from other residential
coal-stoves and close to the emission factors from
industrial plants (Table 5). One reason for this is due
to the anthracite coal burnt in this study, since this kind
of coal is relatively cleaner than brown coal and
bituminous coal. The other reason may come from the
high efficiency of this clean combustion style, which is
being widely spread in China [2,13,14], especially when
the air-control cover is fully opened. A greater emission
factors can be anticipated when the cover is closed
somewhat. Obviously higher emissions of PAHs from
coal combustion were observed under smoldering con-
ditions in the study of Oros and Simoneit because of the
lack of air [12].
3.3. Gas-particle partitioning
Eight PAHs (Fl, Phe, Ant, Flu, Pyr, BaA, Chry, and BeP)
have been taken as model compounds for the study of the
gas-particle equilibrium partitioning of organics. The
concentrations of these compounds in the two phases and
total particulate matter were used for calculating the
partition coefficient Kp (m3/mg), defined as Kp ¼ Cp =ðCg £
TSPÞ; where Cp and Cg are the concentrations of compounds
in the particle and gas phases, respectively, and TSP is
the concentration of total particulate matter (mg/m3). The
correlation between the partition coefficient Kp and the
temperature-corrected subcooled liquid vapor pressure PoL
(pa) is often expressed by the equation
logKp ¼ m log PoL þ b
Fig. 3. Plot of log Kp (m3/mg) vs log PO
L (Pa) for eight PAHs in the emission sample from coal combustion.
Under equilibrium conditions and for a given sample and
given temperature, the expected slope ðmÞ of Eq. (2) is 2 1
[34,35].
In this study, a good linear relationship between Kp and
PoL is observed ðR2 ¼ 0:9628Þ while the m value is 2 0.85
(Fig. 3). This may indicate that the partitioning of PAHs
between particle and gas phases did not reach equilibrium
yet, although in this study the temperature of the sampled
flue gas (23 8C) was lower and the average residence time of
the flue gas before being sampled (88 s) was longer than in
the study by Oanh et al. during which the sampling
temperature was 57 – 64 8C and the residence time was
2 – 3 s when burning coal briquettes, and PAHs emission
associated with particulate matter was only 0.1% of the total
amount [10].
3.4. PM and PAHs size distributions
The weights of particulate matter collected on the six
stage filters were recorded for calculating the mass
percentage of each stage to total weight and the mass
median aerodynamic diameter (MMAD, particle diameter
where one half of the particle mass is smaller and the other
half is larger [36]) (Table 6). The particulate matter on the
sixth stage (backup filter, aerodynamic diameter is under
0.49 mm) accounted for more than 88% of total particle
mass. The calculated MMAD of emitted particle was
0.28 mm. This indicates that the particulate matter emitted
from honeycomb coal briquette combustion was dominated
by submicron particles at a residence time of 14 s and a
dilution ratio of 37, as mentioned earlier. Longer residence
time in actual emission into atmosphere will shift the
particle mass to larger sizes, while greater dilution ratio will
increase the concentration of ultrafine particles [21,22].
Therefore, the particulate matter from this type of coal-
stoves will pose greatly adverse effect on the human health.
The results of field- and laboratory-scale studies on
emissions from pulverized coal combustors of industrial
ð2Þ plants indicated that the particle size distributions were
 Y. Chen et al. / Fuel 83 (2004) 781–790 789

Table 6
Mass percentage for PAHs and PM of six stages to total emission mass

Compounda .7.2b 3.0–7.2 1.5– 3.0 0.95–1.5 0.49–0.95 ,0.49 MMADc

Acy ndd 7.41 3.30 10.63 16.00 62.66 0.39

Ace nd Nd nd nd nd nd
Fl nd 10.39 8.89 9.64 11.71 59.38 0.41
Mphe 8.96 6.65 4.95 7.89 15.06 56.49 0.43
Phe 7.44 6.96 6.34 8.29 14.57 56.39 0.44
Ant 0.00 1.64 nd nd 22.03 76.33 0.32
Flu 1.96 3.19 3.57 7.02 20.22 64.04 0.38
Pyr 1.34 2.00 2.33 5.85 21.63 66.84 0.37
BaA 0.41 0.77 1.23 5.13 24.14 68.32 0.36
Chry 1.35 2.10 2.54 5.97 20.34 67.69 0.36
BbkF 0.67 0.99 1.32 4.42 19.35 73.25 0.34
BeP 0.55 0.81 1.09 3.91 17.27 76.36 0.32
BaP 0.21 0.39 0.67 4.90 29.51 64.31 0.38
IncdP 0.27 0.27 0.49 4.50 23.39 71.07 0.35
DbahA nd Nd nd 2.06 26.08 71.86 0.34
BghiP 0.29 0.30 0.55 3.68 21.54 73.63 0.34
Cor nd Nd nd 0.49 25.24 74.27 0.33
PMe 0.80 1.05 1.05 2.24 6.54 88.31 0.28
a
The abbreviations of PAHs refer to Table 3.
b
The cut-off size (mm).
c
Mass median aerodynamic diameter (mm).
d
Not detected.
e
Particulate matter.

typically bimodal, and the fine particle mode is around
0.1 mm which appears to result from a vaporization –
condensation process [37 – 39]. The different particle sizes
from these two emission sources may be due to different
coal combustion styles and the measurement techniques,
since the lowest cut-off size of cascade impactor used in this
study was only 0.49 mm.
The emission mass distribution of PAHs as a function of
particle size based on the percentage of total mass was
calculated and listed in Table 6. The mass distributions of all
PAH compounds were found to vary significantly with the
size of the particles. The backup filter (, 0.49 mm) contained
the most mass percent of all PAHs, which varied from
56.39% (Phe) to 76.36% (BeP); and the fifth stage
(0.49 – 0.95 mm) contributed the second important part of
PAHs mass, ranging from 11.71% (Fl) to 29.51% (BaP),
while other stages contained less than 10% of total PAHs
mass (Table 6, Fig. 4). Therefore, PAHs emitted from this
residential coal-stove distributed mainly in the submicron
particles, and this may be attributed to the greater adsorb-
ability of the finer particles (such as soots) because of their
greater surface area with respect to their mass [40]. PAHs
will pose stronger toxicity and then do greater threat to
human health when associated with submicron particles [41].
It is anticipated that the MMAD of organic compound is
smaller than that of the total particulate matter if a
condensation mechanism prevails [36]. However, the
MMAD values of PAHs calculated in this study varied
from 0.32 mm (BeP) to 0.44 mm (Phe), somewhat larger
than the particulate MMAD (0.28 mm). The reason may be
attributed to the great deal of fine mineral ashes existing in
submicron particles, since the color of filter samples
was gray, not the expected black; and these fine mineral
particles formed by a vaporization – condensation process
during combustion [37 – 39] and had less adsorbability
for PAHs than soots. However, this needs further
confirmation.
Another variety tendency on the distributions of PAHs
among various size particles was found that the compounds
with higher molecular weight existed much more in finer
particles (Table 6, Fig. 4). For example, only about 71% of
total Phe was contained in submicron particles, while other
mass part was distributed evenly in the other four stages.
BghiP had more than 95% of total mass in submicron
particles, and even three quarters existed in the finest size
particles (, 0.49 mm). Chry showed the transitional distri-
butions between the above two compounds. This distri-
bution trend was due to the different vapor pressures of PAH
compounds with different molecular weight. Higher weight
Fig. 4. Mass percent distribution of PAHs as a function of particle size.
790 Y. Chen et al. / Fuel 83 (2004) 781–790
species, generated along with soot and adsorbed onto the
fine particles, were more difficult to escape into vapor phase;
while lighter PAHs were easier to equilibrate between the
gas and particle phases and then were easier to redistribute
among various size particles.
4. Conclusions
Emission characterization of PAHs such as particulate
and gaseous partition and particulate size association from
the commonly used residential coal stove burning honey-
comb coal briquettes was studied through a dilution
sampling system. At ambient temperature, the contribution
of vapor phase was very important to the total PAH emitted
from this combustion system, and submicron sited particle
was dominant in the emitted PAHs. These results are helpful
to abate the adverse effect of this coal combustor on human
health. Furthermore, this residential coal stove was
identified as a comparative clean combustion system,
especially when the air-control cover was fully opened.
Although emission of PAHs from honeycomb briquettes
was studied in the present study, it is necessary to compare
the emission of PAHs from the honeycomb briquettes using
anthracite with that using bituminous coal. PAHs can be
released as primary products as well as being formed during
combustion. Further study will investigate the PAHs
formation process.
Acknowledgements
This work was supported by the Chinese National
Natural Science Foundation (No. 4013010). We would
like to thank Mr Li Zhengyue and Mr Chen Deyi for their
help in designing and manufacturing the sampling
equipment and laboratory room, and Mr. Xiang Tongshou
for technical assistance and GC-MS data acquisition. We
also greatly appreciated the helpful comments from the
anonymous reviewers.
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