Science of the Total Environment 612 (2018) 636–648

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Chemical composition and speciation of particulate organic matter from

modern residential small-scale wood combustion appliances
Hendryk Czech a, Toni Miersch a, Jürgen Orasche a,b,c, Gülcin Abbaszade b,c, Olli Sippula c,d, Jarkko Tissari d,
Bernhard Michalke e, Jürgen Schnelle-Kreis b,c, Thorsten Streibel a,b,c,⁎,
Jorma Jokiniemi c,d, Ralf Zimmermann a,b,c
a
Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, Institute of Chemistry, University of Rostock, 18059 Rostock, Germany
b
Joint Mass Spectrometry Centre, Cooperation Group “Comprehensive Molecular Analytics” (CMA), Helmholtz Zentrum München – German Research Centre for Environmental Health, 85764
Neuherberg, Germany
c
Helmholtz Virtual Institute of Complex Molecular Systems in Environmental Health (HICE), Germany
d
Fine Particle and Aerosol Technology Laboratory, Department of Environmental and Biological Sciences, University of Eastern Finland, FIN-70211 Kuopio, Finland
e
Research Unit Analytical BioGeochemistry, Helmholtz Zentrum München – German Research Centre for Environmental Health, 85764 Neuherberg, Germany

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• PM2.5 composition from two modern

wood combustion appliances
• Advanced targeted and non-targeted
mass spectrometric techniques
• Emission factors for N 100 organic parti-
cle constituents
• Low abundance of established wood
combustion markers
• Slow ignition can shift emission pattern
compared to regular combustion.

a r t i c l e i n f o a b s t r a c t

Article history: Combustion technologies of small-scale wood combustion appliances are continuously developed decrease emis-
Received 27 June 2017 sions of various pollutants and increase energy conversion. One strategy to reduce emissions is the implementa-
Received in revised form 23 August 2017 tion of air staging technology in secondary air supply, which became an established technique for modern wood
Accepted 26 August 2017
combustion appliances. On that account, emissions from a modern masonry heater fuelled with three types of
Available online 1 September 2017
common logwood (beech, birch and spruce) and a modern pellet boiler fuelled with commercial softwood pellets
Editor: D. Barcelo were investigated, which refer to representative combustion appliances in northern Europe In particular, empha-
sis was put on the organic constituents of PM2.5, including polycyclic aromatic hydrocarbons (PAHs), oxygenated
Keywords: PAHs (OPAHs) and phenolic species, by targeted and non-targeted mass spectrometric analysis techniques. Com-
Diagnostic ratios pared to conventional wood stoves and pellet boilers, organic emissions from the modern appliances were re-
Wood smoke duced by at least one order of magnitude, but to a different extent for single species. Hence, characteristic
PAH ratios of emission constituents and emission profiles for wood combustion identification and speciation do not
OPAH hold for this type of advanced combustion technology. Additionally, an overall substantial reduction of typical
Phenolics
wood combustion markers, such as phenolic species and anhydrous sugars, were observed. Finally, it was
Photoionisation mass spectrometry
found that slow ignition of log woods changes the distribution of characteristic resin acids and phytosterols as

⁎ Corresponding author at: Joint Mass Spectrometry Centre, Chair of Analytical Chemistry, University of Rostock, 18059 Rostock, Germany.

http://dx.doi.org/10.1016/j.scitotenv.2017.08.263
0048-9697/© 2017 Elsevier B.V. All rights reserved.
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648
well as their thermal alteration products, which are used as markers for specific wood types. Our results should
be considered for wood combustion identification in positive matrix factorisation or chemical mass balance in
northern Europe.
1. Introduction
In many countries of Europe as well as in North America, the resi-
dential combustion of biomass, in particular wood, as a renewable ener-
gy source is encouraged by legislation to decrease the dependence on
fossil fuels and contribution to global warming. Conventional logwood
stoves, pellet stoves and pellet boilers have been recognised to be sub-
stantial emitters of greenhouse gases, black or elemental carbon and
brown carbon (Evtyugina et al., 2014; Martinsson et al., 2015; Orasche
et al., 2012), which counteract the widely considered CO2-neutrality
and thus affect the climate (Andreae and Ramanathan, 2013). Further-
more, residential wood burning causes elevated ambient concentra-
tions of inhalable particulate matter (PM) with an aerodynamic
diameter below 2.5 μm (PM2.5) (Fuller et al., 2013), which has been as-
sociated with toxicological responses, such as genotoxicity, cytotoxicity,
oxidative stress, systemic inflammation and cardiovascular diseases
(Croft et al., 2017; Miljevic et al., 2010; Naeher et al., 2007; Sehlstedt
et al., 2010). Also, the emissions of volatile organic compounds (VOCs)
from wood combustion cover a substantial potential for secondary or-
ganic aerosol (SOA) formation (Bruns et al., 2016), which may have dif-
ferent health effects than the primary emissions (Künzi et al., 2013;
Nordin et al., 2015) and additionally contributes to ambient PM2.5
levels.
In order to tackle these emissions, new and more complete combus-
tion technologies were developed which may significantly reduce the
toxicity potential of primary wood combustion aerosols (Jalava et al.,
2012). Secondary air supply through air staging became an established
emission abatement strategy, which substantial reduce the emissions of
several organic and inorganic pollutants (Nuutinen et al., 2014). Air
staging is characterised by splitting the total combustion air into
under-stoichiometric air-to-fuel ratios for primary air (λ b 1) and
consecutive addition of low excess secondary air (λ N 1.5), which is
well-mixed with the pyrolysis gases through different feedings. Thus,
high temperatures and more complete combustion are achieved
(Nussbaumer, 2003). However, some pollutants correlate inversely
with increasing secondary air flow rates, such as the trade-off between
CO and NOx (Khodaei et al., 2017).
Emissions from a masonry heater and a pellet boiler, equipped with
air staging technology, were previously investigated regarding PM, CO,
NOx (NO + NO2), total VOC (Lamberg et al., 2011a; Lamberg et al.,
2011b; Nuutinen et al., 2014) and VOC composition (Czech et al.,
2017; Czech et al., 2016; Reda et al., 2015), as well as their SOA forma-
tion potential (Kari et al., 2017; Tiitta et al., 2016). In this study, an addi-
tional detailed characterisation of the PM2.5 composition is presented
with emphasis on the organic constituents, whose emission factors
(EFs) are compared to conventional and other modern wood stoves.
The implications for source apportionment studies of the results on
chemical patterns of emissions are also discussed, especially the impli-
cations for selecting common diagnostic ratios to trace sources and
quantify source contributions from biomass burning to ambient PM
concentrations. Moreover, differences of EFs and emission profiles be-
tween wood types are related to effects observed in toxicological stud-
ies (Kasurinen et al., 2017).
Although the masonry heater and the pellet boiler of this study are
only representative domestic combustion appliances in northern
Europe, it was pointed out that especially features of regional emission
activity are important for emission inventories and source apportion-
ment (Hellén et al., 2008; Pastorello et al., 2011). In the end, the EFs
from the two combustion appliances can be also involved in simulations
637
© 2017 Elsevier B.V. All rights reserved.
of future emission scenarios to estimate benefits of emission abatement
technologies on air quality (Fountoukis et al., 2014).
2. Material and methods
2.1. Experimental setup
2.1.1. Combustion appliances
The emissions of two small-scale wood combustion appliances with
advanced secondary air supply for residential heating were investigat-
ed. The modern masonry heater (Hiisi 4, Tulikivi Ltd., Finland) com-
prises of a massive soap stone of app. 1.3 tons for slow heat release, an
upright enclosed firebox and a double glass window door. In the firebox,
the secondary air is supplied through panels with small rifts in the
upper combustion chamber (air staging) to generate a secondary com-
bustion zone, which was shown to substantially reduce emissions of CO,
VOCs and organic matter (Nuutinen et al., 2014). The modern masonry
heater was operated at approximate nominal load.
The second appliance is an automatically-fired top-feed pellet boiler
(PZ25RL, Biotech Energietechnik GmbH, Austria), which was continu-
ously operated at its nominal power of 25 kW. A more detailed descrip-
tion of the pellet boiler and the effect of air staging can be found in
Lamberg et al. (2011b).
In the following, the term “modern” refers to wood combustion ap-
pliances with air staging and “conventional” without.
This study was part of experiments by Helmholtz Virtual Institute of
Complex Molecular System in Environmental Health (HICE), which
aims to explore biological effects of emissions on human lung epithelial
cells (Kanashova et al., 2017). In particular, emissions from state-of-the-
art combustion appliances and emerging fuels are of interest as they
may represent future scenarios. The two combustion appliances were
chosen due to their known low emissions of bulk components from pre-
vious studies (Nuutinen et al., 2014; Lamberg et al., 2011b) and their
representativeness for single houses in terms of energy output and mar-
ket availability.
2.1.2. Fuels and combustion procedure
The modern masonry heater was fuelled by beech (Fagus sylvatica)
and spruce (Picea abies), which are common firewood in central
Europe, as well as birch (Betula pubescens), which is a typical firewood
in northern Europe. In Table 1, physico-chemical properties of the
three types of firewood are summarised. In total 15 kg of logwood
was burned in a single experiment, split up in six consecutive batches
of 2.5 kg each. The ignition of the first batch in the cold stove was carried
out from top down with 150 g of small wood sticks/chips. After 35 min,
the next batch was put in the wood combustion residues for self-
ignition and burned for further 35 min. Subsequent to the sixth batch,
remaining ember was stoked and the secondary air supply was blocked
according to manufacture instructions for 30 min to cover a total exper-
imental time of 4 h.
In two (spruce* and birch*) of the total log wood combustion exper-
iments, a slow ignition of the first batch was observed. Due to qualita-
tive and quantitative differences in emissions of these experiments
compared to the other ones, the effect of slow ignition on the total EFs
is discussed more in detail in Section 3.5.
The pellet boiler was operated with commercial softwood pellets
(produced from pine and spruce stem wood, physico-chemical properties
in Table 1) under stable conditions over 4 h and connected to a heat ex-
changer. Those boilers are usually connected to a reservoir of water for
638 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648

Table 1
Physico-chemical properties of the wood fuels.

Parameter Unit Limit of quantification Method Beech logs Birch logs Spruce logs Softwood pellets

Moisture % (w/w) 0.1 DIN EN 14774-2 9.0 7.2 7.4 7.3

Ash content % (w/w, dry) 0.1 DIN EN 14775 1.3 0.69 0.58 0.36
C % (w/w, dry) 0.2 DIN EN 15104 50.3 51.0 52.0 51.7
H % (w/w, dry) 0.1 DIN EN 15104 5.8 6.0 5.9 6.0
N % (w/w, dry) 0.05 DIN EN 15104 0.36 0.40 0.36 0.29
O % (w/w, dry) Calculated 42.3 41.9 41.1 41.6
S % (w/w, dry) 0.005 DIN EN 15289 0.037 0.006 0.009 0.006
Cl % (w/w, dry) 0.005 DIN EN 15289 b0.005 b0.005 0.005 0.006
Zn mg/kg (dry) 1 DIN EN ISO 17294-2 5 33 25 14
Si mg/kg (dry) 1 DIN EN ISO 11885 6.3 17.5 5.8 14.5
K mg/kg (dry) 1 DIN EN ISO 11885 14.5 9.3 14.5 12.1
Net heating value kJ/kg 200 DIN EN 14918 17,790 18,140 18,640 18,380

warm water supply and therefore have to constantly produce heat in con-
trast to pellet stoves, which refers to room heating appliances. A more de-
tailed description of the combustion experiments can be found in Reda
et al. (2015).
2.2. Instrumentation
2.2.1. Gas measurements
Flue gases were led from the firebox to the upper combustion cham-
ber and then downwards through side ducts into the stack. The stack
was placed below a hood, and draught was regulated with two
dampers. The target value for the pressure in the stack was (12.0 ±
0.5) Pa below ambient pressure. CO, CO2, NOx and O2 were continuously
measured by a gas analyser system (ABB, Limas 11 UV, Switzerland).
Organic gaseous carbon (OGC), a quantity for total organic vapours,
were quantified by a flame ionisation detector (ABB, Multi-FID 14,
Switzerland), which was calibrated against propane. All gaseous emis-
sions were measured directly from undiluted stack gas through an insu-
lated and externally heated sampling line at 180 °C.
From the analysis of O2 in the flue gas, emission factors (EFs) were
calculated based on the instruction of the Finnish Standard Association
method SFS 5624 as described in Reda et al. (2015).
2.2.2. Filter sampling of PM2.5
The emitted aerosol of the wood combustion appliances was
isokinetically sampled from the stack, diluted at a dilution ratio of 40
by using a porous-tube/ejector dilutor (Venacontra, Finland) and cooled
to room temperature to enable condensation of semi-volatile species.
Subsequently, particles were segregated to an aerodynamic diameter
smaller than 2.5 μm and isokinetically sampled on quartz fibre filters
(T293, Munktell, Sweden) over the total experiment duration of 4 h. Fi-
nally, the filter samples were stored at −20 °C until analysis. An over-
view about the total experimental setup can be found in Weggler et al.
(2016). Please note that gas-particle partitioning, which affects the
emission factors, are dependent on the applied dilution technique and
dilution ratio (Nuutinen et al., 2014). The applied dilution ratio around
40 has been widely used for sampling PM emissions, but it was demon-
strated that towards higher dilutions the sampled PM mass decreases
substantially (Lipsky and Robinson, 2006). Thus, the presented EFs can
be regarded as an upper limit.
2.2.3. Organic PM2.5 constituents
The analysis of the organic fraction of the PM2.5 emissions was
carried out by targeted and untargeted mass spectrometric techniques.
Thermal/optical carbon analysis (TOCA) coupled to resonance-
enhanced multi-photon ionisation time-of-flight mass spectrometry
(REMPI-TOFMS) refers to an untargeted technique and enables to quan-
tify organic (OC) and elemental carbon (EC), but also to investigate the
molecular composition of the thermal sub-fractions related to OC (Diab
et al., 2015). A filter punch of 0.5 cm2 was placed into thermal-optical
carbon analyser (DRI model 2001a) and analysed following the
ImproveA protocol (Chow et al., 2007). During the four thermal sub-
fractions of OC (OC1 to OC4) with upper temperature limits of 140 °C,
280 °C, 480 °C and 580 °C, approximately 8% of the total flow enters
the TOFMS through a deactivated transfer capillary (inner diameter of
320 μm), which is connected to the carbon analyser oven by a modified
quartz cross stepwise heated from 230 °C to 245 °C to prevent conden-
sation (Grabowsky et al., 2011). In the ion source, UV radiation of
266 nm which is provided by the fourth harmonic generation of an
Nd:YAG laser (Spitlight400, Innolas, Germany; 20 Hz repetition rate,
1064 nm fundamental radiation, energy of 1 mJ at 266 nm) ionises se-
lectively desorbed aromatic constituents of the particles in the REMPI
process. In addition to the optical selectivity, REMPI denotes a soft
ionisation technique leading to predominantly molecular ions and low
yields of fragments (Boesl, 2000). The generated ions were subsequent-
ly analysed by a TOFMS (compact reflectron time-of-flight spectrometer II,
Stefan Kaesdorf Geräte für Forschung und Industrie, Germany) with a
mass resolution of 1000 at m/z 78 and 1 s time resolution. Finally, the
obtained mass spectra were summed according to their occurrence in
the four fractions of OC.
For targeted analysis, in-situ derivatisation direct thermal desorp-
tion gas chromatography time-of-flight mass spectrometry (IDTD-GC-
TOFMS) with electron ionisation (Orasche et al., 2011) was applied to
quantify in total 105 particle-bound organic compounds covering the
substance classes of polycyclic aromatic hydrocarbons (PAHs), oxygen-
ated PAHs (OPAHs), hydroxy-PAH (OH-PAHs), polycyclic aromatic
sulphur-containing hydrocarbons (PASH), anhydrous sugars, phenolic
species, resin acids and phytosterols. The derivatisation is based on
silylation with N-Methyl-N-trimethylsilyltrifluoroacetamide (MSTFA)
during the step of thermal desorption from quartz fibre filter. Detected
compounds were identified by library match of electron ionisation spec-
tra as well as retention index and quantified by isotope-labelled internal
standards of the same substance or chemically similar substances.
2.2.4. Inorganic PM2.5 constituents
Samples of particulate matter were reconditioned prior to elemental
analysis by inductively-coupled plasma optical emission spectrometry
(ICP-OES, Spectro Ciros Vision, SPECTRO Analytical Instruments GmbH
& Co., Germany) as described in Sections 1.1 to 1.3 of the Supplementary
data. In total 19 elements, including Al, B, Ba, Bi, Ca, Cd, Cr, Cu, Fe, K, Li,
Mn, Mo, Na, Pb, S, Ti, W and Zn were quantified and presented if at
least 50% of the samples of one wood type contained concentrations
higher than the limit of quantification.
2.2.5. Data analysis and statistics
For all statistical analysis, including cluster analysis and analysis of
variance (ANOVA), Matlab® basic functions and Statistic Toolbox
(R2014b, The MathWorks Inc., Massachusetts, USA) was used. In case
of significance at a level of 0.05, ANOVA was followed by Bonferroni cor-
rection method to avoid accumulation of type I error at multiple testing.
If not otherwise indicated, reported p-values in the following refer to re-
sults of multiple comparison tests. A result is called significant if p-
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648 639

values appear below the significance level α of 0.05. A summary of fold

changes and p-values for all comparisons between the four wood types
is depicted in volcano diagrams (Figs. S1–S6). Compounds with concen-
trations below the limit of quantification in each single experiment for
one wood fuel were not considered in the visualisation.

3. Results & discussion

3.1. Gaseous emissions

Regarding the main gaseous constituents in the flue gas of the ma-
sonry heater, only marginal differences between the mean EFs of the
different wood types could be observed, which is also reflected by the
similar modified combustion efficiencies (MCE = ΔCO2 / (ΔCO2 +
ΔCO; Δ denotes background correction) in the range of 0.983 (spruce)
to 0.988 (birch). In contrast to that, the more controlled and continuous
combustion in the pellet boiler resulted in about one order of magnitude
lower emissions of CO and OGC, despite lower excess flue gas O2 con-
centration. Generally, emissions of NOx predominantly result from
fuel nitrogen and appear in the range of 83 to 109 mg MJ−1, which is
comparable to other wood stoves and pellet boilers of older types
(Orasche et al., 2012). A comparison of the gaseous and VOC emissions
from these two wood combustion appliances with literature data from
logwood stoves, pellet stoves and boiler of older types was already de-
scribed by Czech et al. (2016) and Czech et al. (2017).

3.2. Inorganic PM2.5 constituents

Inorganic emissions from the wood combustion appliances are af-
fected by the content of the respective element in the fuel, the fuel
bed temperature, the volatility of the element and concentrations of
possible binding partners. K, S, Na and Zn denote the most abundant in-
organic particle constituents. In particular, the highest emissions of al-
kali, alkaline earth and transient metals were detected in emissions
from birch wood and pellet combustion. In all multiple comparisons
after significant ANOVA results, significant elevated EFs for Zn, Cd and
W were found for birch wood with a fold change above 1.5. The pellet
boiler operated on softwood pellets revealed significantly increased
EFs for Na, K and S (Figs. S3, S5 and S6). Interestingly, Bi, Li and Mo
were even only detected in particles from pellet combustion. On the
contrary, Cd was only detected in the particles from logwood combus-
tion although the Cd content of the woods was below the limit of quan-
tification of 0.2 mg/kg for all investigated wood fuels.
Of all analysed metals, only Zn showed a steady increase and signif-
icant linear correlation (r = 0.907, p = 1.2 · 10−6) between particle-
bound Zn emissions and increasing content in the fuel, independently
from the combustion appliance (Fig. 1). Fractions of 19%, 37%, 22% and
18% of the fuel-Zn are released in particle emissions for beech, birch,
spruce and pellets, respectively, which agrees well with earlier observa-
tions on Zn release from various wood-fired combustion appliances
(Lamberg et al., 2011b; Sippula et al., 2017). Particulate Zn, solely pres-
ent as ZnO in wood smoke particles, is of great interest because it has
been found to be an important driver of cytotoxicity (Uski et al.,
2015). For all possible comparisons, birch wood led always to signifi-
cantly enhanced Zn emissions with a minimum fold change of 4. On
that account, Zn emission can be lowered by preferring Zn-poor fire-
wood or detaching the bark in which Zn is enriched (Wiinikka et al.,
2013).
K in PM2.5 emissions, which used as one indicator for biomass com-
bustion in source apportionment studies (Watson et al., 2001), did not
correlate with fuel-K. The release of K is generally affected by the avail-
ability and ratio of Si to K and S to Cl. These factors have been found to
influence the partitioning of K between coarse-sized ashes (bottom
ash and coarse fly ash) and fine fly ashes, which forms part of the fine
particulate emission (Sippula et al., 2017; Sommersacher et al., 2012).
A higher content of Cl in the wood fuel leads to the formation of more
Fig. 1. Scatter plot of the Zn (upper panel) and K (lower panel) content of the wood fuels
beech (circles), birch (diamonds), spruce (triangles) and pellets (pentagrams) versus EF of
Zn and K. Numbers in the lower panel refers to sulphur-to-chlorine ratio of the wood fuels.
volatile KCl, whereas higher fuel-sulphur favours the formation of less
volatile K2(SO4) (Sippula et al., 2007; Sippula et al., 2008). In agreement
with that, a significant moderate correlation (r = 0.55, p = 0.02) was
found for the ratio of Cl to S and K. However, for some fuels only
upper limits for the ratio of Cl to S could be used because of Cl concen-
trations below the limit of quantification (Table 1). Furthermore, the
Si content of the fuel can decrease the release of K through formation
of low-volatile potassium silicates, which remain in the bottom ash
(Sommersacher et al., 2012). However, a correlation between the ratio
of Si to K of the fuel and K in the emissions could not be found.
3.3. Targeted analysis of carbonaceous PM2.5 constituents
3.3.1. Organic and elemental carbon
The combustion of all types of logwood in the masonry heater led to
more than one order of magnitude higher emissions of both OC and EC
compared to the pellet boiler (OC: 0.15 mg MJ−1; EC: 0.27 mg MJ−1).
However, some significant differences were recognised between the
logwood types. The combustion of the hardwoods beech and birch
emitted more total carbon (TC) than spruce, but birch produced
47 mg MJ−1 EC compared to 28 mg MJ−1 EC for beech and only
13 mg MJ−1 EC for spruce. Regarding OC, a three-fold higher EF was
found for beech (20 mg MJ−1) compare to the equal EFs for birch and
spruce (6.1 mg MJ−1). Generally, carbonaceous particulate emissions
were substantially lower compared to wood combustion appliances
without air-staging (Calvo et al., 2015; Orasche et al., 2012) and compa-
rable to other advanced stoves with primary, secondary and post-
combustion air supply (Tschamber et al., 2016).
The ratio of OC to EC (OC/EC) has been widely applied in atmospher-
ic sciences for the apportionment of emission sources, such as to bio-
mass burning, combustion of fossil fuel or SOA. In particular, the
minimum OC/EC plays an important role to estimate the amount of
SOA on ambient particles while OC/EC b 1 was associated with fossil
fuel combustion (Pio et al., 2011). Although it has been demonstrated
that the air-staging of the investigated modern masonry heater has a
640 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648
only small effect on the emission of total carbon in PM2.5 (Lamberg
et al., 2011a; Nuutinen et al., 2014), the data reveals consistently OC/
EC b 1 for each single combustion experiment, which might lead to mis-
interpretation of ambient air studies in areas where this type of wood
stoves are used. Moreover, the combustion of birch logs generated par-
ticles with the lowest OC/EC of 0.13 ± 0.02, which is significantly differ-
ent compared to beech logs (0.71 ± 0.14) and pellets (0.65 ± 0.23).
Compared to spruce (0.48 ± 0.13), the difference of OC/EC from birch
logs was not significant, but substantial (p = 0.058).
In this context it must be mentioned that the amount of carbonates
(inorganic carbon, IC), which were not analysed in this study, may bias
the OC/EC results. In particular for the pellet boiler IC can cover the same
range as OC or EC (Lamberg et al., 2011a; Lamberg et al., 2011b). How-
ever, in TOCA the contribution of IC either to OC or EC depends on the
decomposition temperature and therefore on the cation of the
carbonate.
3.3.2. Anhydrous sugars
Among all anhydrous sugars, levoglucosan denotes the most rele-
vant one because of its established application as marker compound
for biomass combustion (Simoneit, 2002). It originates from the thermal
decomposition of cellulose (Shafizadeh, 1968) and generally refers to
one of the most abundant organic compounds in wood combustion par-
ticles. Despite the large differences in mean EFs of levoglucosan be-
tween the combustion experiments, ranging from 113 μg MJ− 1
(beech) to 10 μg MJ− 1 (pellet), no significance was identified by
ANOVA. The highest concentrations of the levoglucosan are emitted
during the ignition of the wood (Elsasser et al., 2013), which is concur-
rently the part of the combustion with the highest variation and might
give an explanation of this finding. It was observed that logs of birch ig-
nited faster than the other two logwoods and showed the lowest
amount of residues in the chamber before the introduction of the con-
secutive batch, which supports the explanation. However, the percent-
age of levoglucosan to the total particle mass in the presented
experiments was generally very low. Although total PM2.5 mass was
not determined, it can be estimated by assuming that TC represents ap-
proximately 50% of PM2.5. Hence, levoglucosan accounts for b 0.3% of
PM2.5 for all particle emissions from the masonry heater, which is
very low compared to the literature data (Orasche et al., 2012;
Schmidl et al., 2008; Vicente et al., 2015a) and might be a feature of
the applied combustion technology and associated higher temperatures
in the firebox. In this context, only the pellet boiler led to comparable re-
sults to previous studies with 2.7% levoglucosan in PM (Orasche et al.,
2012; Vicente et al., 2015b). However, please note that Vicente et al.
(2015a), Vicente et al. (2015b) and Schmidl et al. (2008) sampled
PM10 instead of PM2.5 as in this study which might affect the results
as single analytes can vary over size fractions of combustion particles
(Kleeman et al., 2008). Although wood combustion PM2.5 from the
two appliances of this study even appear solely in the fraction of PM1,
it is not known for stoves of previous studies, so a direct comparison
was omitted. Nevertheless, the obtained ratios of levoglucosan to OC,
quantified from PM2.5, of 9% for beech logwood (Calvo et al., 2015)
and 19% and 10% for beech and spruce logwood (Orasche et al., 2012)
from conventional stoves were substantially higher than for the modern
masonry heater (beech: 0.58%; birch: 0.88%; spruce: 1.18%), which sup-
ports our findings.
The EFs of the further quantified anhydrous sugars, mannosan and
galactosan, were one order of magnitude lower than levoglucosan in
all experiments. Mannosan is released from the decomposition of hemi-
cellulose, thus the ratio of levoglucosan to mannosan (LGS/MNS) has
been proposed to differentiate between hardwood and softwood com-
bustion. Hard- and softwoods contain different amounts of cellulose
and hemicellulose, which is also reflected in the emission. LGS/MNS of
15.0 ± 7.1 for beech, 19.3 ± 13.5 for birch and 8.5 ± 2.4 for spruce re-
veal the same trend as previously reported, but with higher standard
deviations (Schmidl et al., 2008). In addition to that, this concept does
not work for automatically-fired combustion appliances even though
levoglucosan and mannosan could be detected (Schmidl et al., 2011).
For the pellet boiler, LGS/MNS of 24.8 ± 8.1 exceeded the higher LGS/
MNS for hardwood although the pellets were solely comprised of
softwood.
Galactosan was the lowest abundant anhydrous sugar without sig-
nificant differences between the three logwoods. Regarding the pellet
boiler particles, galactosan concentrations in each single combustion ex-
periment were found below the limit of quantification.
3.3.3. Phenolic species
The EFs of 23 quantified phenolic species cover a range from below
limit of quantification to 36 μg MJ−1 with molecular patterns according
to the current knowledge of lignin monomers in different wood species.
Syringyl and sinapyl alcohols and their derivatives on particulate emis-
sions are associated with hardwoods, whereas softwood burning emis-
sions contain higher relative amounts of coniferyl-derived compounds.
Guaiacol as another abundant building block of the wood is emitted by
both wood families in equal amounts (Simoneit, 2002). These three
basic rules also hold for the performed experiments. Concerning total
particle-bound phenolic species, beech wood showed the highest EF
(72 μg MJ− 1), followed by birch (20 μg MJ− 1), spruce (8.4 μg MJ−1)
and pellets (0.59 μg MJ−1). In the pellet emissions only 5 of the 23 pre-
sented phenolic species appeared above the limit of quantification,
which complicates the identification of pellet boiler emissions in atmo-
spheric studies. Furthermore, the question of possibly enhanced toxicity
of the released particles is raised because phenolic species are known as
antioxidants and scavengers of reactive oxygen species. Thus phenolic
species could hypothetically mitigate the overall toxicity of harmful
substances (Kjällstrand and Petersson, 2001).
For atmospheric studies and a comparison between the investigated
stoves with stoves of older design, the relative amount of phenolic spe-
cies to other particle constituents is more important than the absolute
quantity. Therefore, the total phenolic content of the particles was nor-
malised to OC. Beech, birch and pellet combustion featured similar, but
significantly higher contents of phenolic species per OC (3.7 mg/gOC,
3.4 mg/gOC and 3.9 mg/gOC) than spruce (1.7 mg/gOC). In comparison
with combustion appliances without air-staging (Table 3), absolute
emissions of particle-bound phenolic species and phenolic species per
OC from both masonry heater and pellet boiler were one order of mag-
nitude lower. Although different combustion scenarios are considered,
the comparison can be regarded as conservative because only the hot ig-
nition of three consecutive batches, known for lower emissions of phe-
nolic species than cold starts (Orasche et al., 2012), was taken into
account, whereas the combustion in this study included six consecutive
batches and a char-burning phase, but a cold start as well. Moreover, the
analysed 23 phenolic species were the most abundant ones in this
study. Therefore, the emissions of these two stoves with air-staging sec-
ondary air supply represent a different type of emission pattern, which
becomes even more relevant since combustion technologies in small-
scale appliances are currently developing and old stoves are constantly
replaced by more efficient modern stoves.
3.3.4. Resin acids and phytosterols
The detected resin acids comprise derivatives and thermal degrada-
tion products of abietic acid and its isomers pimaric and isopimaric acid.
These resin compounds are known to be mainly released during the
start phase of the combustion of coniferous wood (Orasche et al.,
2012). Of all resin compounds, dehydroabietic acid was the most abun-
dant compound with a mean EF of 42.12 μg MJ−1 for spruce wood, but
partially oxidised derivatives and products from elimination reactions
of abietic acid were present as well. Small amounts of dehydroabietic
acid were also found on particles from birch wood combustion (8.56
μg MJ−1), which raise suspicion that these EFs were caused by carry-
over effects. However, this EF results from two of four birch wood com-
bustion experiments which were not carried out directly after spruce
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648
wood. Furthermore, a porous-tube dilutor, which was cleaned every
day, was used in the sampling instead of a dilution tunnel which was
proposed to minimise carry-over effects (Orasche et al., 2012). There-
fore, we regard the detected quantities as truly abundant in the birch
particulate emissions.
In addition to spruce, one characteristic substance was found for
each of the investigated wood fuels. β-Sitosterol was only abundant in
the particulate emissions of the pellet boiler (10.4 μg MJ−1) in two of
three experiments. According to the manufacturer, the main material
of the pellets was spruce and pine wood, but concentrations of β-
sitosterol occurred below the limit of quantification in every single com-
bustion experiment of spruce logwood. Substantial quantities of this
triterpenoid were measured on particles from the combustion of differ-
ent pine species (Oros and Simoneit, 2001a), thus the emission of β-
sitosterol is likely associated with content of pine wood of the pellets.
Lupa-2,22(29)-dien-28-ol refers to an thermal alteration product of
betulin, which is one of the major components in essential oil of birch
wood, especially in its bark (Laszczyk et al., 2006). Its EF accounts for
29.0 μg MJ− 1 for birch wood, but some smaller quantities could be
also detected for spruce wood.
For beech, substantial amounts of stigmasta-3,5-dien-7-one, an al-
teration product of stigmastan, was found with an EF of 173.90
μg MJ−1. Minor amounts (5.41 μg MJ−1) were also detected for birch,
which belongs to deciduous trees as well as beech, that this stigmastan
and derivatives were previously proposed as marker for this type of
woods (Gonçalves et al., 2011).
It must be added that the analysed resin acids and triterpenoids only
represent a minor part of the total alteration products of abietic acid,
betulin and stigmastan (Oros and Simoneit, 2001a; Oros and Simoneit,
2001b). On that account, marker substances for specific wood species
or classes cannot be derived.
3.3.5. Parent and alkylated PAH
3.3.5.1. Emission profiles and factors. In all combustion experiments,
phenanthrene, pyrene and fluoranthene were the most abundant
PAHs and accounted from 48.1% (spruce) up to 73.0% (pellets) of the
total analysed PAHs. However, the gas-particle partitioning of especially
these PAHs is sensitive to even small changes in sampling temperature,
which could have affected the presented EFs for particle-bound PAHs.
Although significant differences could be found between the logwoods,
the combustion of spruce logs slightly shifted the emission pattern to-
wards PAHs of higher molecular weight, which might be caused by py-
rolysis of resin components. Additionally, a higher degree of alkylation
can be observed for spruce wood which is relevant for the development
of diagnostic ratios for source apportionment (Tobiszewski and
Namieśnik, 2012). A more detailed discussion on aromatic profiles can
be found in Section 3.4.
The EF of total PAHs from the pellet boiler (0.89 μg MJ−1) was more
than one order of magnitude lower than from the masonry heater
fuelled with any logwood (beech: 35.31 μg MJ− 1; birch: 32.31
μg MJ−1; spruce: 22.16 μg MJ−1), which emphasises the efficiency of
this combustion appliance. Generally, the EFs of particle-bound PAH
were one to two orders of magnitude lower compared to conventional
wood stoves and pellet boilers (Orasche et al., 2012), but similar to
other modern masonry heaters (Tschamber et al., 2016), which also
agrees with the trend of volatile aromatic emissions investigated in pre-
vious studies (Czech et al., 2017; Czech et al., 2016).
3.3.5.2. PAH toxicity equivalents (PAH-TEQ). PAHs adsorbed on particu-
late matter are well-known for their carcinogenic and mutagenic activ-
ity (Lewtas, 2007). On that account, the approach of PAH toxicity
equivalent (PAH-TEQ) was developed to assess the health risk potential
at workplace exposures by multiplication of single PAH concentrations
or EFs with its corresponding toxicity equivalent factor (TEF). TEFs are
related to benzo[a]pyrene which accounts for 1 and taken from the
641
German Research Foundation as described in Orasche et al. (2012). Fi-
nally, the TEQs of single PAHs were summed up to the total PAH-TEQ
for a single combustion experiment.
PAH-TEQ EFs of logwood combustion range from 0.57 μg MJ−1 to 1.4
μg MJ−1 without significant differences between the investigated wood
types. Similar to the PAH-EFs, PAH-TEQ EFs of the pellet boiler were al-
most two orders of magnitude lower than the logwoods of this study
with values from 0.019 μg MJ−1 to 0.034 μg MJ−1. These findings are
in line with other small-scale wood stoves with advanced combustion
technology and more than one order of magnitude lower than conven-
tional stoves (Fig. 2) and agree with the general trend of decreasing
TEQ-EFs for automatically-fired wood combustion appliances. However,
the concept of PAH-TEQ only considers the abundance of PAHs and does
not include other harmful compounds or even easing synergetic effects,
such as the influence of antioxidants.
3.3.6. PAH-derivatives
In this section, aromatic hydrocarbons with heteroatoms within or
at the periphery of the core structure are discussed. The most abundant
hydroxyl- and oxy-PAHs (OH-PAHs and OPAHs) were denoted by 1,8-
naphthalic anhydride, 9H-fluoren-9-one, 1-hydroxynaphthalene and
9,10-anthracenedione. All OH\\ and OPAHs were significantly lower
in the pellet boiler particle emissions (1.90 μg MJ−1 in total) or appeared
below the limit of quantification, whereas differences between the log-
wood were less pronounced. Only for spruce significantly elevated EFs
were observed for 7H-benzo[c]fluoren-7-one, 11H-benzo[b]fluoren-
11-one and 7H-benzo[de]anthracen-7-one compared to birch. Never-
theless, the highest EFs for total OH\\ and OPAH were obtained for
beech (63.4 μg MJ−1) with almost equal EFs for birch (40.9 μg MJ−1)
and spruce (40.4 μg MJ−1). Dibenzothiophene was the only sulphur-
containing polycyclic aromatic compound (PASH) found on the parti-
cles with substantial increased EFs for birch wood.
Compared to conventional stoves and pellet boilers, the total emis-
sion of OH\\ and OPAH was decreased by more than one order of
Fig. 2. EFs of PAH-TEQ values for different wood combustion appliances. The dashed line
separates results of this study (left) from literature data (aTschamber et al., 2016;
b
Orasche et al., 2012) (right). WABI and XP54-IN denote wood stoves with modern
combustion technology, while pellet and LS (logwood stove) are conventional wood
combustion appliances at cold start (CS) or nominal load (NL). Error bars represent
minimum and maximum PAH-TEQ of repeated experiments. The results demonstrate
that modern technology for batchwise wood combustion not only reduces EFs by one
order of magnitude, but also the toxicological potential of the emissions related to the
same heating values of the wood fuels. PAH-TEQ EFs for the pellet boiler are even
reduced by an additional order of magnitude.
642 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648
magnitude. Additionally, their distribution was shifted towards com-
pounds of lower molecular weight for the same type of fuel wood
(Orasche et al., 2012). Therefore, the differences in OH\\and OPAH pat-
terns might be explained by the level of combustion technology.
3.4. Untargeted analysis of particle-bound aromatic compounds by TOCA-
REMPI-TOFMS
An approach for the rapid characterisation of aromatic compounds
in thermal fractions of particulate matter offers the hyphenation of
resonance-enhanced multi-photon ionisation time-of-flight mass spec-
trometry (REMPI-TOFMS) to thermal/optical carbon analysis (TOCA).
The first two OC-fractions defined by the ImproveA protocol for carbon
analysis were combined because it is assumed that organic particle con-
stituents predominantly evaporate without decomposition. In OC3 and
OC4, pyrolysis occurs which shifts the mass spectrum towards lower m/
z (Diab et al., 2015).
In Fig. 4, mean REMPI mass spectra for each wood fuel are illus-
trated with labels of the most important homologue alkylation series
of phenanthrene (m/z 178), pyrene (m/z 202), benzo[a]anthraces/
chrysene (m/z 228) and dibenzofuran (m/z 168) with m/z incre-
ments of + 14. Although response factor (photoionisation cross sec-
tions) can vary substantially (Boesl, 2000), peak intensities reflected
the relations between the wood fuels described by the quantitative
results from IDTD-GCMS.
Highest peak intensities were observed for phenanthrenes and
pyrenes with its respective maximum at the parent PAH and a steady
decay towards higher degrees of alkylation, which was also found for
particles from other wood stoves (Bente et al., 2008; Diab et al., 2015)
and volatile PAH emissions as well (Elsasser et al., 2013). However, a
slight increase from methyl- to C2-phenanthrene (sum of all isomers
of dimethyl- and ethyl-phenanthrene) can be observed in beech-,
birch- and pellet-derived particles, which is possibly an issue of mass
interference with another isobaric compound of m/z 206, e.g.
phenanthrene-9-carboxaldehyd. Furthermore, the thermal degradation
of abietic acid from spruce wood leads to the formation of retene (m/z
234), but to lower alkylated phenanthrenes as well (e.g. pimanthrene
(Simoneit, 2002)), so the findings from other PAH homologue series
cannot be transferred to phenanthrenes. In contrast to distinct
abundancies of phenolic species in PM2.5 of conventional wood stoves
(Diab et al., 2015), the absence of such m/z supports the results from
IDTD-GC/MS measurements and the general low emissions of the mod-
ern masonry heater.
In the m/z range of the spectra, which can be regarded as fingerprint
region for the wood types, peaks up to m/z 400 were still detected. Al-
though reliable assignments to molecular structures were not possible,
the number of potential formula can be reduced by the constraints that
the detected compound must be an aromatic constituent of wood
smoke due to the ionisation selectivity. Hence, it is hypothesised that
the peaks in the m/z range from 300 to 400 (small panels on Fig. 3) be-
long to lignans, i.e. dimers of monomers derived from lignin, or alter-
ation products of steroids and triterpenoids, which may become
aromatised under thermal stress and thus become accessible for
REMPI. The latter proposed compound class seems to be more likely be-
cause substantially more peaks were detected for birch wood combus-
tion. In contrast to the other wood fuels, birch contains high amounts
of triterpenoids, such as betulin or betulinic acid, in its bark (Laszczyk
et al., 2006), which leads to a variety of possible thermal alteration prod-
ucts (Oros and Simoneit, 2001b) and may justify the higher number of
peaks in the upper m/z range.
In the pyrolysis fraction OC3 (Fig. S7), a shift towards lower m/z, in-
cluding the appearance of volatile aromatic compounds such as naph-
thalene or phenol, could be observed as expected because of the
decomposition of larger molecular structures. Apart from retene as an
indicator for the combustion of coniferous wood, no specific peaks or ar-
omatic patterns were found. The obtained mass spectra of OC4 were
poor in peak number and intensity and therefore were not considered
further.
In the preceding sections, the discussion of the two experiments
with slow ignition, spruce* and birch*, were omitted because of differ-
ences in aromatic patterns. With all combustion experiments, a hierar-
chical cluster analysis was performed based on unweighted pair group
method with arithmetic means (Sokal and Rohlf, 1962) with coefficient
of congruence as distance metric (Abdi, 2010). Three clusters were ob-
tained and assigned to spruce, pellets and the hardwoods birch and
beech (Fig. 4). Despite the correct assignment of spruce*, its distance
was remarkably larger than between the other spruce combustion ex-
periments. Moreover, birch* appeared isolated from the other birch
combustion experiments closer related to the pellets. Both spruce*
and birch* emitted higher amounts of OGC during the first of the six
batches, which prompts an inappropriate or slow ignition. In a previous
study, the molecular composition of the VOCs during the first batch of
spruce* revealed higher quantities of typical primary decomposition
products from lignin or carbohydrates, e.g. coniferyl alcohol and
levoglucosenone, as it can be observed when combustion efficiency de-
creases (Czech et al., 2016). Due to the fact that these combustion
events of a relatively short period remarkably affect the emissions of
the entire 4 h experiment, spruce* and birch are separately discussed
in the following section.
3.5. Effect of slow ignition
3.5.1. Spruce wood
The REMPI spectrum of spruce* with slow ignition showed a higher
number of peaks, a broader m/z range and a different pattern than the
spruce wood experiments with proper ignition (Fig. 5, top). Parent
PAHs were less dominating the homologue series so that the general de-
gree of alkylation is higher than in the regular combustion experiments.
Moreover, larger PAHs, such as the homologue series of benzopyrenes
and benzoperylenes, appeared with higher abundances. Many peaks
were located between the signals of PAH homologue series and likely
belong to monomers of the lignin decomposition, which are increasing-
ly released at lower combustion temperature, i.e. during smouldering
(Kjällstrand and Petersson, 2001). Additionally, abietic acid (m/z 302)
undergoes aromatisation of its saturated rings through thermal alter-
ation and become accessible for REMPI, for example as dihydroretene
or simonellite (Oros and Simoneit, 2001a). Peaks of m/z N 302 may be
assigned to lignans or larger PAHs as discussed in a previous section.
Generally, the observed higher intensities for spruce* compared to the
regular experiments were confirmed by the higher EFs for several or-
ganic compounds from IDTD-GCMS analysis.
With the EFs of Table 2, a Dean-Dixon outlier test (at α = 0.05)
was performed to identify significantly increased or decreased sub-
stances for slow ignition. Dean-Dixon test was chosen because it
does not assume normal distribution of the data and is generally rec-
ommended for small sample sizes (Dean and Dixon, 1951). In
addition to previously mentioned enhancement of OGC, a variety
of PAHs, OH\\ and OPAHs, among others benzo[a]anthracene,
benzo[a]pyrene and 7H-benzo[de]anthracen-7-one, were identified
as outliers with increased EFs. Therefore, it was not surprising that
the PAH-TEQ EF were changed by a factor of six (8.82 μg MJ− 1) com-
pared to the regular spruce combustion (1.44 μg MJ− 1 ). Further-
more, primary decomposition products from lignin, such as vanillic
acid, coniferyl aldehyde and guaiacylacetone, were more prominent
in spruce*, in agreement with the REMPI mass spectra, as well as the
anhydrous sugars levoglucosan and mannosan. Regarding inorganic
emissions, spruce* was the only spruce combustion experiment in
which chromium was found above the limit of quantification. How-
ever, on the basis of the presented data this phenomenon could not
be explained, but since chromium does not belongs to volatile metals
in wood combustion, contamination is assumed. Further inorganic
particle constituents were not affected by the slow ignition.
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648 643

Fig. 3. Mean REMPI mass spectra of summed intensities of OC1 + OC2 for the four investigated wood types. Symbols denote the most abundant series of parent PAHs and alkylated
homologues, namely dibenzofuran (green triangles), phenanthrene (red squares), pyrene (cyan stars) and chrysene/benzo[a]anthracene (blue circles). Panels in the upper right corner
belong to fingerprint regions of the wood types, which contain alteration products of phytosterols and lignans and enable wood type identification despite similar alkylation patterns.
Figures with logarithmic y-scale can be found in the Supplementary data (Fig. S8).

Out of nine quantified components or alteration products of the

spruce wood resin, four (isopimaric acid, abietic acid, dehydroabietic
acid and dehydroabietic acid methyl ester) were found as outliers
with higher abundance than in the regular spruce wood combustion
and one (7-oxo-abietic acid) with lower abundance. Isopimaric acid
and abietic acid were even not detected in each of the regular spruce
combustion experiments, but with EFs of 73.27 μg MJ−1 and 435.58
μg MJ−1 in spruce*, suggesting an enhanced distillation-like release dur-
ing the start phase of the first batch (Orasche et al., 2012). In contrast,
the absence of 7-oxo-abietic acid in spruce* implies its formation during
higher temperatures sufficient to partially oxidise abietic acid. Due to
the fact that pimaric acid, a primary resin constituent as well, were
only found in the regular spruce combustion experiments, a possible
heat-induced isomerisation between pimaric, isopimaric and abietic
acid might occur. All together, these results emphasise the necessary de-
tection of many possible resin acids and their alteration products if
quantitative conclusion are drawn in source apportionment studies
since the abundance of a single markers strongly depends on the com-
bustion condition.

3.5.2. Birch wood

Fig. 4. Dendrogram from cluster analysis of REMPI mass spectra from OC1 + OC2 using the
unweighted pair group method with arithmetic means and coefficient of congruence as
distance metric. Experiments spruce* and birch* were regarded as outliers and separately
discussed in the Section 3.5.
Although birch* was classified as slow ignition experiment as well, it
exhibited a different emission pattern than spruce* (Fig. 5, bottom). In
this case, the slow ignition caused a distinct shift towards higher m/z
644 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648

Fig. 5. Mean REMPI mass spectra of summed intensities of OC1 + OC2 for combustion experiment with slow ignition. Symbols denote the homologue series of dibenzofuran (green up-
pointing triangles), phenanthrene (red squares), pyrene (cyan stars), chrysene/benzo[a]anthracene (blue circles), benzpyrene (magenta diamonds) and benzo[ghi]perylene (black down-
pointing triangles). Panels in the upper right corner belong to fingerprint regions of the wood fuels, which contain lignans and alteration products of phytosterols. Although both
combustion experiments reveal a shift towards larger PAH emissions, the spectrum of spruce* contains numerous peaks, possibly from thermal resin alteration, while for birch*
emissions parent PAHs are more pronounced in the alkylation series. Figures with logarithmic y-scale can be found in the Supplementary data (Fig. S9).

and an elevated contribution of parent PAHs to their homologue series.
Moreover, pyrene (m/z 202) replaced phenanthrene (m/z 178) as the
most abundant PAH. However, apart from PAH homologue series the
number of peaks and peak intensities were low, indicating that primary
decomposition products from lignin were not or less elevated in this
combustion scenario. Therefore, birch* was located closer to the pellet
boiler particles in the cluster analysis (Fig. 4).
Also in this case the findings from the REMPI mass spectra agree
with the results obtained from IDTD-GCMS analysis and Dean-Dixon
test. 25 PAHs, among others the carcinogenic benzo[a]pyrene,
dibenz[ah]anthracene and anthanthrene, and seven alkylated PAHs
were found to be statistical outliers compared to the regular birch com-
bustion experiments, which accompany the 14-fold increased PAH-TEQ
(birch*: 11.3 μg MJ−1; mean regular birch: 0.82 μg MJ−1). Additionally,
12 OPAHs with two to five rings were classified as outliers as well with
fold changes between 5 and 34, which is more pronounced than for
spruce*. The majority of the 12 OPAHs and 25 PAHs were found to cor-
relate well and significantly with the formation of reactive oxygen spe-
cies (Sklorz et al., 2007) and therefore OPAHs are of toxicological
interest although they are not considered in the TEQ concept.
With the Dean-Dixon test primary decomposition products were not
identified as outliers except syringol, so birch* deals with a different in-
fluence of the slow ignition than spruce*. However, it could not be con-
cluded whether the different emission patterns belong to features of the
wood species or combustion conditions because of the number of
experiments.
4. Conclusion
In this comprehensive study of wood combustion PM2.5 from two
modern small-scale combustion appliances (masonry heater and pellet
boiler) equipped with air staging, several emission factors for organic
and inorganic particle constituents were presented and compared to
other state-of-the-art and conventional wood stoves. Generally, mason-
ry heater emissions appeared in the same order of magnitude as for a
woods stoves equipped with primary, secondary and post-combustion
air (Tschamber et al., 2016), but more than one order of magnitude
lower than the conventional wood stove (Orasche et al., 2012). Howev-
er, the pellet boiler even reduces carbonaceous emissions by an addi-
tional order of magnitude. Pellet boiler PM2.5 is mainly comprised of
inorganic constituents, which differ qualitatively and quantitatively
from the investigated masonry heater emissions. For both modern ma-
sonry heater and pellet boiler, wood-specific combustion products from
the decomposition of lignin and carbohydrates were detected, but sub-
stantially lower compared to conventional wood stoves and pellet
boilers. Although the major single component of organics in the PM2.5
was levoglucosan, its contribution to OC was found at the lower limit
described in the literature, which also holds for phenolic species. Con-
versely, the higher relative amount of general products of incomplete
combustion, such as parent PAHs and OPAHs, complicates the assign-
ment of this type of emissions to wood combustion in atmospheric
source apportionment studies. This holds especially for CMB modelling
and simpler approaches, such as the estimation of wood smoke mass
from ambient levoglucosan concentrations (Schmidl et al., 2008), but
also for PMF factor identification as tracers for wood combustion are
substantially reduced (Bari et al., 2009). This might become a more im-
portant issue in the future because of the rather long period of use for
wood stoves and boiler. Especially the pellet boiler lacks wood combus-
tion markers, but β-sitosterol was found to be only component which
was more abundant in the pellet boiler emissions than in the modern
masonry heater emissions. However, β-sitosterol cannot be regarded
as marker for pellet emissions because of its high dependency on the
wood type. Nevertheless, our results provide comprehensive emission
profiles of modern wood combustion appliances which can be already
used in chemical mass balances for areas of northern Europe.
With the hyphenation of thermal/optical carbon analysis to
resonance-enhanced multi-photon ionisation time-of-flight mass spec-
trometry (TOCA-REMPI-TOFMS), differences in aromatic fingerprints
and PAH alkylation series of the different PM2.5 samples were
discussed. Moreover, it was shown that slow ignition of the first batch
in batchwise logwood combustion increased EFs of single species in dif-
ferent manners and also shifted the aromatic pattern to larger struc-
tures. Slow ignition could be linked to elevated PAH-TEQ values as
well as different quantities of phytosterols and the distribution of their
thermal alteration products, which are used as wood-specific markers.
Finally, emission source apportionment should be connected to
more sophisticated toxicological approaches instead of simple concepts
of PAH-TEQ. Due to the presence of substantial amounts of antioxidants
in the wood smoke which may counteract harmful effects on human
health by single particle constituents, further studies under realistic
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648 645

Table 2
Mean emission factors (EFs) and concentrations of gaseous analytes, particulate carbons, inorganic elements, PAHs, PAH-derivatives, phenolic species, resin constituents and sterols as well
as toxicity equivalents (TEQ) and modified combustion efficiency (MCE) from regular combustion experiments (modern masonry heater: beech, birch and spruce; pellet boiler: softwood
pellets) and combustion experiments with slow ignition (modern masonry heater: spruce* and birch*; see Section 3.5). Minimum and maximum EFs are listed in Table S2. EFs can be
related to the amount of burned fuel by using respective net heating values from Table 1. Entries of b.l.q. refer to EFs below the limit of quantification.

Unit Beech Birch Spruce Pellet Spruce* Birch*

Number of experiments n 4 4 3 3 1 1

Gaseous analytes
O2 % 16.8 16.0 15.9 12.0 16.1 15.5
CO2 % 3.91 4.55 4.38 8.55 4.48 4.56
CO mg MJ−1 1320 1430 1640 42.4 1290a 1230
OGC mg MJ−1 24.0 15.4 20.1 1.25 45.0a 18.6
NOx mg MJ−1 110 104 83.0 89.0 83.1 99.9
MCE [] 0.987 0.988 0.983 0.999 0.986a 0.984a

Particulate carbon
OC mg MJ−1 20 6.1 6.1 0.15 11 5.7
EC mg MJ−1 27 47 13 0.27 17 34
TC mg MJ−1 47.0 53.1 19.1 0.42 28.0 39.7

Inorganic particle constituents

Al μg MJ−1 45.1 82.5 39.1 22.3 38.5 30.4
B μg MJ−1 3.64 5.45 4.35 5.31 b.l.q. 3.92
Ba μg MJ−1 1.63 1.67 1.94 1.16 1.40 1.17
Bi μg MJ−1 b.l.q. b.l.q. b.l.q. 15.74 b.l.q. b.l.q.
Ca μg MJ−1 83.7 89.1 101.7 24.2 51.3 109
Cd μg MJ−1 0.97 2.49 0.22 b.l.q. b.l.q. 1.59
Cr μg MJ−1 2.42 3.78 b.l.q. 1.68 8.38a 2.17
Cu μg MJ−1 15.5 6.36 4.18 7.65 6.52 11.7
Fe μg MJ−1 20.5 38.2 29.0 12.1 21.8 18.3
K μg MJ−1 1630 2050 1600 3010 1120 1440
Li μg MJ−1 b.l.q. b.l.q. b.l.q. 4.95 b.l.q. b.l.q.
Mn μg MJ−1 4.75 7.51 7.41 9.31 4.80 5.99
Mo μg MJ−1 b.l.q. b.l.q. b.l.q. 0.84 b.l.q. 1.40a
Na μg MJ−1 51.2 52.6 53.7 924 b.l.q. 49.1
Pb μg MJ−1 9.80 8.89 b.l.q. 1.21 b.l.q. 6.44
S μg MJ−1 393 370 337 754 301 266
Ti μg MJ−1 0.90 1.62 1.16 0.47 1.03 1.87
W μg MJ−1 b.l.q. 13.0 3.76 2.80 7.44 9.49
Zn μg MJ−1 53.5 683 302 139 269 513

Particle-bound PAH
Phenanthrene μg MJ−1 9.34 11.4 2.62 0.25 1.30 16.6
Anthracene μg MJ−1 1.27 1.28 0.42 0.02 b.l.q. b.l.q.
Fluoranthene μg MJ−1 7.65 6.38 4.47 0.22 3.40 20.6a
Acephenanthrylene μg MJ−1 0.63 0.71 0.33 0.01 1.16 4.08a
Pyrene μg MJ−1 6.74 5.28 3.56 0.18 4.62 20.1a
Benzo[a]fluorene μg MJ−1 0.43 0.14 0.46 0.01 1.52 3.15a
Benzo[b]fluorene μg MJ−1 0.43 0.20 0.55 0.01 1.33 1.69a
Benzo[c]phenanthrene μg MJ−1 0.37 0.41 0.34 0.01 1.23a 2.33a
Benzo[ghi]fluoranthene μg MJ−1 1.78 1.69 1.38 0.03 4.31 10.1a
Benz[a]anthracene μg MJ−1 0.75 0.55 0.83 0.01 4.73a 5.99a
Cyclopenta[cd]pyrene μg MJ−1 b.l.q. 0.10 b.l.q. b.l.q. 6.75a 2.71a
Chrysene μg MJ−1 1.38 1.14 1.46 0.03 5.00a 10.2a
2,2′-Binaphthalene μg MJ−1 b.l.q. b.l.q. 0.09 b.l.q. b.l.q. 0.48a
sum Benzo[b,j,k]fluoranthene μg MJ−1 2.02 1.31 2.24 0.04 11.6a 14.2a
Benz[e]pyrene μg MJ−1 0.78 0.48 0.88 0.02 3.86a 5.68a
Benz[a]pyrene μg MJ−1 0.88 0.55 0.97 0.02 5.81a 7.77a
Perylene μg MJ−1 0.03 0.02 0.10 b.l.q. 1.01a 1.07a
Indeno[1,2,3-cd]fluoranthene μg MJ−1 b.l.q. 0.24 b.l.q. b.l.q. 0.12a 0.06
Benzo[b]triphenylene μg MJ−1 b.l.q. b.l.q. 0.01 b.l.q. 0.10a 0.07a
Indeno[7,1,2,3-cdef]chrysene μg MJ−1 b.l.q. b.l.q. 0.04 b.l.q. 0.57a 0.33a
1-Phenylpyrene μg MJ−1 b.l.q. b.l.q. 0.01 b.l.q. b.l.q. 0.10a
Dibenz[ah]anthracene μg MJ−1 b.l.q. b.l.q. 0.04 b.l.q. 0.23 0.46a
Indeno[1,2,3-cd]pyrene μg MJ−1 0.33 0.18 0.48 b.l.q. 1.75 3.6a
Benzo[b]chrysene μg MJ−1 b.l.q. b.l.q. 0.01 b.l.q. b.l.q. 0.08a
Pentaphene μg MJ−1 b.l.q. 0.04 0.01 b.l.q. b.l.q. 0.06
Picene μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. 0.31a 0.04a
Benzo[ghi]perylene μg MJ−1 0.50 0.18 0.69 0.02 3.23 5.51a
Anthanthrene μg MJ−1 b.l.q. b.l.q. 0.02 b.l.q. 0.50a 0.40a
Coronene μg MJ−1 b.l.q. b.l.q. 0.15 0.01 1.3a 1.9a
Sum PAH μg MJ−1 35.3 32.4 22.2 0.9 65.8 139.3a
PAH-TEQ μg MJ−1 1.26 0.818 1.44 0.028 8.82a 11.3a

Particle-bound OH-PAH, OPAH & PASH

1-Hydroxynaphthalene μg MJ−1 7.5 1.5 1.7 1.0 b.l.q. 2.5
2-Hydroxynaphthalene μg MJ−1 0.38 0.61 0.44 b.l.q. b.l.q. 2.8
1,8-Dihydroxynaphthalene μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. 1.4a b.l.q.

(continued on next page)

646 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648

Table 2 (continued)

Unit Beech Birch Spruce Pellet Spruce* Birch*

Number of experiments n 4 4 3 3 1 1

1-Naphthalenecarboxaldehyde μg MJ−1 b.l.q. 0.10 b.l.q. b.l.q. b.l.q. 0.26

2-Naphthalenecarboxaldehyde μg MJ−1 0.08 0.35 b.l.q. b.l.q. b.l.q. 0.55
1(2H)-Acenaphthylenone μg MJ−1 0.07 0.07 0.05 b.l.q. 0.02 0.28
9H-Fluoren-9-one μg MJ−1 6.9 10 5.1 0.30 0.88 17
1H-Phenalen-1-one μg MJ−1 3.3 2.2 3.6 0.07 20a 20a
Xanthone μg MJ−1 3.5 2.0 2.8 0.08 3.9 6.0
9,10-Anthracenedione μg MJ−1 3.9 3.1 5.2 0.10 6.6 17a
Benzo[b]naphtho[1,2-d]furan μg MJ−1 1.8 0.22 0.44 0.19 b.l.q.a 0.43a
Cyclopenta(def)phenanthrenone μg MJ−1 3.5 2.5 3.6 0.08 3.4 17
1,8-Naphthalic anhydride μg MJ−1 27 15 8.0 b.l.q. 50a 49.7
Benzo[b]naphtho[2,1-d]furan μg MJ−1 1.2 0.46 0.92 0.02 b.l.q. 4.6a
2,3-5,6-Dibenzoxalene μg MJ−1 0.35 0.19 0.37 0.01 b.l.q. 1.1
Benzo[b]naphtho[2,3-d]furan μg MJ−1 0.37 0.11 0.37 0.01 b.l.q. 1.7
Benzo[kl]xanthene μg MJ−1 0.33 0.16 0.38 b.l.q. b.l.q. 1.6a
11H-Benzo[a]fluoren-11-one μg MJ−1 0.20 0.07 0.43 0.01 1.4 1.4a
7H-Benzo[c]fluorene-7-one μg MJ−1 0.09 0.03 0.14 b.l.q. b.l.q. 0.54a
11H-Benzo[b]fluoren-11-one μg MJ−1 0.45 0.11 1.0 0.01 2.8 3.8a
7H-Benzo[de]anthracen-7-one μg MJ−1 0.83 0.24 1.4 0.01 5.0a 7.2a
Naphtho[2,1,8,7-klmn]xanthene μg MJ−1 0.46 0.54 0.55 0.01 b.l.q. 1.8
Benz[a]anthracene-7,12-dione μg MJ−1 b.l.q. 0.15 0.6 b.l.q. 0.31 1.1
5,12-Naphthacenedione μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q. 0.21a
Phenanthro[3,4-c]furan-1,3-dione μg MJ−1 0.09 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
6H-Benzo[cd]pyren-6-on μg MJ−1 1.8 0.73 3.3 0.02 3.0 15a
Dibenzothiophene μg MJ−1 0.01 0.06 0.01 b.l.q. b.l.q. 0.13

Particle-bound alkylated PAH

9-Methylphenanthrene μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q. 0.19a
3,6-Dimethylphenanthrene μg MJ−1 0.02 0.22 0.51 b.l.q. b.l.q. 0.37
Retene μg MJ−1 b.l.q. 0.20 6.5 0.04 11a b.l.q.
Sum 2-/8-methylfluoranthene μg MJ−1 0.45 0.19 0.48 0.01 0.64 2.0a
Sum 1-/3-/7-methylfluoranthene μg MJ−1 0.62 0.28 0.64 0.02 1.0 2.9a
4-Methylpyrene μg MJ−1 0.22 0.07 0.28 b.l.q. 0.62 2.0a
2-Methylpyrene μg MJ−1 0.59 0.31 0.69 0.02 1.2 2.5a
1-Methylpyrene μg MJ−1 0.46 0.23 0.52 0.02 1.9a 2.4a
4,5-Dimethylpyrene μg MJ−1 0.06 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
2,3,6,7-Tetramethylanthracene μg MJ−1 b.l.q. b.l.q. 0.35 b.l.q. b.l.q. b.l.q.
1-Methyl-benz[a]anthracene μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q. 0.53a

Particle-bound anhydrous sugars

Galactosan μg MJ−1 2.3 2.2 2.9 b.l.q. 15 5.9
Mannosan μg MJ−1 7.9 3.8 9.2 0.47 150a 6.7
Levoglucosan μg MJ−1 110 53 72 10 1100a 56

Particle-bound phenolic species

4-Hydroxyphenylethanol μg MJ−1 1.3 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
4-Hydroxybenzoic acid μg MJ−1 4.0 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Vanillin μg MJ−1 10.1 14.0 5.94 0.37 13.7 11.6
Isoeugenol μg MJ−1 2.45 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Acetovanillone μg MJ−1 2.1 0.5 0.8 b.l.q. b.l.q. 0.61
Methylvanillate μg MJ−1 1.1 b.l.q. 0.27 0.01 b.l.q.a b.l.q.
Vanillic acid μg MJ−1 0.37 1.5 b.l.q. b.l.q. 16a 0.8
3-Guaiacylpropanol μg MJ−1 0.60 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Coniferaldehyde μg MJ−1 1.30 b.l.q. 0.80 b.l.q. 470a b.l.q.
Guaiacylacetone μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. 0.63a b.l.q.
4-Guaiacylbutanoic acid μg MJ−1 0.57 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Syringol μg MJ−1 1.74 0.04 b.l.q. b.l.q. b.l.q. 0.46a
4-Methylsyringol μg MJ−1 1.11 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
4-Ethylsyringol μg MJ−1 1.19 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Allylsyringol μg MJ−1 0.08 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Syringaldehyde μg MJ−1 36 3.7 0.44 0.09 b.l.q. 1.9
Syringylpropene μg MJ−1 0.71 0.13 0.02 0.01 b.l.q. 0.06
Acetosyringone μg MJ−1 4.4 0.29 0.03 b.l.q. b.l.q. 0.21
Syringic acid, methyl ester μg MJ−1 0.91 0.04 b.l.q. b.l.q. b.l.q. 0.03
Syringic acid μg MJ−1 0.91 0.17 0.10 0.11 0.50a 0.12
Homosyringic acid μg MJ−1 0.12 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Sinapylaldehyde μg MJ−1 0.62 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
3,5-Dimethoxy-4,4′-dihydroxystilbene μg MJ−1 0.95 b.l.q. b.l.q. b.l.q. b.l.q. b.l.q.
Sum phenolic species μg MJ−1 72.1 20.4 8.42 0.59 504a 15.8

Particle-bound resin constituents

Pimaric acid μg MJ−1 b.l.q. b.l.q. 0.06 b.l.q. b.l.q. b.l.q.
Isopimaric acid μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. 73a b.l.q.
Abietic acid μg MJ−1 b.l.q. b.l.q. b.l.q. b.l.q. 440a b.l.q.
6-Dehydrodehydroabietic acid μg MJ−1 b.l.q. b.l.q. 1.1 b.l.q. b.l.q. b.l.q.
Dehydroabietic acid μg MJ−1 b.l.q. 8.6 42 b.l.q. 710a b.l.q.
7-Oxodehydroabietic acid μg MJ−1 b.l.q. b.l.q. 0.08 b.l.q. b.l.q.a b.l.q.
 H. Czech et al. / Science of the Total Environment 612 (2018) 636–648 647

Table 2 (continued)

Unit Beech Birch Spruce Pellet Spruce* Birch*

Number of experiments n 4 4 3 3 1 1

6-Dehydrodehydroabietic acid, methyl ester μg MJ−1 b.l.q. b.l.q. 0.09 b.l.q. b.l.q. b.l.q.
Dehydroabietic acid, methyl ester μg MJ−1 b.l.q. 0.16 0.82 0.01 7.33a b.l.q.
7-Oxodehydroabietic acid, methyl ester μg MJ−1 b.l.q. b.l.q. 0.09 b.l.q. b.l.q. b.l.q.

Particle-bound phytosterols
β-Sitosterol μg MJ−1 b.l.q. b.l.q. b.l.q. 10 b.l.q. b.l.q.
Stigmasta-3,5-dien-7-one μg MJ−1 170 5.4 b.l.q. b.l.q. b.l.q. b.l.q.
Lupa-2,22(29)-dien-28-ol μg MJ−1 b.l.q. 29 4.6 b.l.q. b.l.q. b.l.q.
a
Significant outlier from Dean-Dixon test at 0.05 significance level in comparison to regular combustion experiments.

Table 3
Emission factor of total phenolic species and their normalisation to OC from modern masonry heater (beech, birch and spruce logs) and pellet boiler (softwood pellets) compared to con-
ventional logwood and pellet combustion from Orasche et al. (2012).

Beech Birch Spruce Pellet

μg mg/gOC μg mg/gOC μg mg/gOC μg mg/gOC

MJ−1 MJ−1 MJ−1 MJ−1

This study 72 3.7 20 3.4 8.4 1.4 0.59 3.4

Orasche et al., 2012a 2220 150 – – 690 62 18 26
a
“PB spruce”, “LS beech” and “LS spruce”.

exposure conditions, e.g. with lung cells in an air-liquid interface
(Kanashova et al., 2017; Paur et al., 2011), may support a full assessment
of improvements in stove construction as well as the influence of com-
bustion condition and wood type.
Acknowledgement
The measurements were carried out at the University of Eastern
Finland (UEF), Department of Environmental and Biological Science, in
cooperation with the Helmholtz Virtual Institute of Complex Molecular
Systems in Environmental Health (HICE), funded by The Helmholtz Im-
pulse and Network Fund of the Helmholtz Association (Germany), the
DACH-project WooShi (grant ZI 764/5-1), the Academy of Finland
(grants 296645 and 304459) and the University of Eastern Finland for
the project “sustainable bioenergy, climate change and health”.
Appendix A. Supplementary data
The supplementary data involves the ICP-OES method, minimum
and maximum EF for experimental repetitions of the same conditions,
volcano diagrams of ANOVA post-hoc tests, REMPI mass spectra of
OC3 and REMPI spectra of OC1 + OC2 with logarithmic y-scale. Supple-
mentary data associated with this article can be found in the online ver-
sion, at http://dx.doi.org/10.1016/j.scitotenv.2017.08.263.
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