Waste Management 167 (2023) 31–38

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Research Paper

Removing siloxanes and hydrogen sulfide from landfill gases with biochar
and activated carbon filters
Mikko Selenius b, *, Joonas Ruokolainen a, Joakim Riikonen b, Jimi Rantanen b, Simo Näkki b,
Vesa-Pekka Lehto b, Marko Hyttinen a
a
Department of Environmental and Biological Sciences, University of Eastern Finland, 70210 Kuopio, Finland
b
Department of Technical Physics, University of Eastern Finland, 70210 Kuopio, Finland

A R T I C L E I N F O A B S T R A C T

Keywords: Landfill gas (LFG) is formed by microorganisms within a landfill; it can be utilized as a renewable fuel in power
Landfill gas plants. Impurities such as hydrogen sulfide and siloxanes can cause significant damage to gas engines and tur­
Activated carbon bines. The aim of this study was to determine the filtration efficiencies of biochar products made of birch and
Biochar
willow to remove hydrogen sulfides, siloxanes, and volatile organic compounds from the gas streams compared
Siloxanes
to activated carbon. Experiments were conducted on a laboratory scale with model compounds and in a real LFG
power plant where microturbines are used to generate power and heat. The biochar filters removed heavier
siloxanes effectively in all of the tests. However, the filtration efficiency for volatile siloxane and hydrogen
sulfide declined quickly. Biochars are promising filter materials but require further research to improve their
performance.

1. Introduction
The motivation for this research was the need of landfill operators to
find an alternative to clean the gas of impurities that would be cheaper
and have a better carbon footprint than activated carbon has. Due to this
real need, the first experiments were carried out in landfills, followed by
studies in laboratory conditions.
Landfill gas (LFG) is a complex mixture of gases formed from
municipal solid waste by microorganisms under anaerobic conditions.
LFG consists of methane (45–60 %), carbon dioxide (30–60%), nitrogen
(2–5%), oxygen (0.1–1%), hydrogen sulfide (10–5000 ppm), siloxanes
(0–50 ppm), sulfur dioxide, and other sulfuric compounds (Manheim
et al. 2021) In addition, there is extensive variation in the amounts of
volatile organic compounds in the LFG (5–300 mg/m3) (Tchobanoglous
et al., 1993; Rasi et al., 2007; Rasi et al., 2008, Muñoz et al., 2015, Duan
et al., 2021). Kim et al. (2006) detected the presence of several BTEX
compounds (benzene, toluene, ethyl benzene and xylenes), but noted
that it was toluene that played an important role in the LFG flux when
compared to the other non-methane hydrocarbons (NMHC). Although
methane, one of the main components of LFG, is an important green­
house gas, it can be utilized as an energy source with a modern collec­
tion technique; its energy content is estimated to be 5–6 kWh/m3
(Dolgen et al., 2005). The utilization of LFG would not only decrease
greenhouse gas emissions and unpleasant odor emissions from landfills,
but it would also reduce the need to consume non-renewable resources.
In addition, the development and exploitation of LFG collection systems
would have many economic benefits for local communities through
increased employment and local sales (Ayodele et al., 2020).
LFG has been gathered from landfills by extraction wells or hori­
zontal trenches (Deublein and Steinhauser, 2008) after which it is
transmitted in pipelines to gas turbines, internal combustion (IC) en­
gines boilers, or microturbines to produce heat or electricity. Micro­
turbines are a promising choice for small and medium-sized LFG sites as
they can operate with lower LFG amounts with a reduced methane
content than demanded in gas turbines or IC engines (Deublein and
Steinhauser, 2008).
One of the main factors limiting the use of LFG is that the gas must be
purified of impurities, condensates and particulates before it can be
utilized as hydrogen sulfide (H2S) and siloxanes can cause significant
damage to gas turbines, e.g., fouling, corrosion, and a glass-like depo­
sition. (Igoe and Welch, 2015). H2S can be formed from the small pieces
of gypsum wallboards and materials containing calcium sulfate in their
structure. In a landfill environment, sulfur-reducing bacteria use sulfate
and release H2S gas. The amount of H2S emissions in a landfill depends

* Corresponding author.
E-mail address: mikko.selenius@uef.fi (M. Selenius).

https://doi.org/10.1016/j.wasman.2023.05.006
Received 22 August 2022; Received in revised form 20 April 2023; Accepted 3 May 2023
Available online 23 May 2023
0956-053X/© 2023 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M. Selenius et al.
on several factors, including sulfate quantities, the moisture content, pH,
and the quantity of degradable organic matter available. H2S and other
reduced sulfur compounds are toxic, they have an extremely low odor
threshold value and are the most common source of LFG-related un­
pleasant odors (Kim and Chang, 1991).
Siloxanes are organic compounds that contain silicon, oxygen, and
methyl groups. Siloxanes are converted during the combustion process
to silicon dioxide (SiO2) and if these compounds can gain access to the
turbines and boilers, it can be detrimental, as even trace amounts can
damage the machinery (Dewil et al., 2006; Griffin, 2007; Rücker and
Kümmerer, 2015). In 2012, the total production of organosiloxanes was
4.7 million tons (Rücker and Kümmerer, 2015). Thus, because of their
widespread use, LFG can contain high concentrations of siloxanes,
which can disturb and or seriously damage gas or microturbines. The
properties and sources of the commonly found cyclic and linear silox­
anes have been presented in several publications (US EPA, 1974; Var­
aprath et al., 1996; Kim and Chang, 1991; Cha et al., 1999; Rücker and
Kümmerer, 2015). Thus, if LFG is to be efficiently utilized, it has to be
cleansed of these impurities, and there is an urgent need for better and
cheaper solutions.
Several methods have been described for removing hydrogen sulfide
and siloxanes from the LFG. For example, they can be removed by using
biofilters, carbon adsorption, chemical, and thermal oxidation, or
scrubbing liquids (Cha et al., 1999; Shareefdeen et al., 2002; Panza and
Belgiorno, 2010). Furthermore, methods based on microbial degrada­
tion have been reported (Grumping et al., 1999). Activated carbon (AC)
filtration is a widely used technology in gas purification (Katoh et al.,
1995; Bandosz, 1999; Schweigkofler and Niessner, 2001). Since AC has a
high surface area and porosity, it removes efficiently undesirable biogas
components such as hydrogen sulfide from LFG (Gaj, 2020). Commercial
AC has often been made from coal, coconut shells, hardwood, or peat.
The activation of carbon is achieved by high-temperature heating with
the aid of an activating chemical agent. A number of studies have
evaluated the environmental impact of ACs (Arena et al., 2016; Hjaila
et al., 2013; Kim et al., 2018). Commercial AC production has been
claimed to have a high carbon footprint, although efforts have been
made to decrease it; for example, producing AC from waste wood (Kim
et al., 2018). In addition to AC, there are also other effective adsorbents
for siloxane removal e.g., silica gel, zeolite, activated aluminum oxide,
and polymer resins. An alternative method is to use biochar materials as
an adsorbent for the cleaning of impurities from the gas streams. Biochar
is a carbonaceous residue of biomass pyrolysis with a porous and
lightweight structure and it is often derived from wood, leaves or grass
(Lehmann and Joseph, 2009). Biochar materials have a high capability
of retaining water and nutrients. Biochar can also be potentially applied
in different kinds of purification applications, such as wastewater
treatment for the removal of heavy metals from aqueous solutions or air
purification systems. (Chen et al., 2007; Lehmann and Joseph, 2009;
Ahmad et al., 2014; Xu et al., 2014; Shang et al., 2015; Sun et al., 2016;
Kanjanarong et al, 2017). Biochar is a bio-based and inexpensive ma­
terial, and it can be created from industrial side-streams (Dai et al.,
2019). The forest industry produces significant amounts of side streams,
which would make sense to use for more climate-efficient uses than for
energy. An assessment has been made of the various side streams of the
Finnish forest industry sector (Hassan et al., 2019). It would be possible
to use these side streams e.g. in biochar production to replace activated
carbon, which is often made from fossil raw materials (Gu et al., 2018).
Therefore, it has a high potential to be cost-effective filter solutions and
should be investigated more carefully. Alhashimi and Aktas, 2017, have
done a meta-analysis and found that the average energy demands were
6.1 MJ/kg with biochar and 97 MJ/kg with activated carbon. The car­
bon footprint of activated charcoal is clearly worse than that of biochar.
Birch and willow are readily available tree species in Western Europe
and the northeastern part of Asia. Their diverse uses as versatile, valu­
able products and renewable fuels have been recognized (Karp, 2014;
Dubois et al., 2020). Since both tree species are fast-growing and well-
32
Waste Management 167 (2023) 31–38
adapted to climate change (Baker et al., 2022; Mao et al., 2010), their
potential exploitation as biochar material will be especially relevant in
the future.
The objective of this study was to determine the filtration efficiencies
of activated carbon and biochar filters made of birch (Betula) and willow
(Salix) to remove hydrogen sulfides, siloxanes, and volatile organic
compounds from gas streams. For this purpose, we measured the con­
centrations of siloxanes, hydrogen sulfide, and volatile organic com­
pounds (VOCs) in the biogas at a landfill.
2. Materials and methods
2.1. General description
Measurements were made in a laboratory in a small-scale dynamic
test apparatus with model compounds and on a field scale with a real
LFG power plant where microturbines were being used to generate
power and heat. The amounts of volatile organic compounds (VOCs) of
LFG were determined upstream and downstream of the filters. In addi­
tion, surface area, porosity, and chemical composition of the activated
carbon and biochar products were determined by several methods
(adsorption measurements (Tristar), thermogravimetry, x-ray fluores­
cence (XRF) powder diffraction (XRPD), and electron microscopy).
2.2. Experimental setup
The measurements were conducted in the same way in the laboratory
and field experiments (supplementary materials 1). The gas was released
into the reaction vessel containing the filter carbons being tested. The
gas flowed from the bottom up, passed through the filter material, and
exited the chamber from the top. Flows were adjusted based on the size
of the reaction vessel to match the volume, both large and small scale.
The filter chamber in use was a cylinder with the same geometric di­
mensions in both test configurations. In the experiments, we measured
the composition of the gas before and after filtration.
2.3. Activated carbon and biochar samples
The activated carbon used in the laboratory and field experiments
was the commercial product Silcarbon SC-40. The brand and quality of
activated carbon were chosen in all experiments to be the same as that
utilized in a commercial landfill to clean the gas before the turbines. The
size of the activated carbon pellet was 4 mm. The biochar samples made
from birch (Betula) and willow (Salix) were prepared by a pyrolysis
process; this was described in our previously published article (Salami
et al., 2020). The temperature was 350 ◦ C ± 20 ◦ C and the process lasted
24 h. The biochars were crushed and sieved through a 10 mm sieve. In
the experiments, the fraction of biochar with a size of less than 10 mm
was used.
2.4. Laboratory experiments
The adsorption capacities of activated carbon and biochars were
tested on a laboratory scale with four model compounds; toluene, hex­
amethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), deca­
methylcyclopentasiloxane (D5) since these selected compounds
(siloxanes) and hydrogen sulfide are the main unwanted trace materials
found in landfill gas. Toluene is also beneficial as it gives a rough esti­
mate of the behavior of other VOCs in landfill gas and filtration systems
(Kim et al., 2006). Furthermore, the concentrations of total VOCs
(TVOC) and single VOCs are often determined as toluene equivalents e.
g. in ISO 16000-6:2011. Nonetheless, while the use of toluene standards
has been shown to underestimate the true concentrations of polar
compounds (Hyttinen et al., 2007), it is still a commonly applied method
in VOC analyses where numerous organic compounds are determined in
a single analysis. In addition, measuring toluene provides useful
M. Selenius et al.
information on the differences between biochar and activated charcoal
as adsorption materials. D4 and D5 are the most often detected siloxanes
in LFG. L2 was chosen because of its small molecular size and high
volatility in comparison to the other more commonly found organic si­
loxanes (Kim and Chang, 1991; Cha et al., 1999; Rücker and Kümmerer,
2015).
The laboratory scale device consisted of a compressed air source,
mass flow meters (Bronchorst), a metal chamber for the feeding of the
model compounds, a filtration unit, which was a true scale model from
the real filtration unit being used in the LFG power plant. The volume of
the laboratory chamber was 2.8 dm3, while the field experiments uti­
lized a filter chamber sized 2.8 m3 (ratio 1:1000). The chamber used in
the laboratory had an inner diameter of 104 mm and a height of 330
mm. Compressed air/nitrogen gas flow was passed through the metal
chamber. A mixture of model compounds was added to the gas stream.
This was done by directing the gas flow through the liquid in a volu­
metric flask, which was used in these experiment as a diffusion vial. The
model compounds were constantly generated into the gas stream by
their chemical and physical properties and diffusion mechanisms.
Hydrogen sulfide was diluted with nitrogen gas to a concentration of
1000–8000 ppm before it reached the filtration unit. In this way, it was
possible to adjust the correct final concentration of hydrogen sulfide in
the gas stream. (H2S concentration in the gas cylinder was 5% and ni­
trogen 95%). Air samples were collected before and after the filtration
unit with Swagelok T-adapters and Tenax TA adsorbent tubes for VOCs
and siloxanes. The level of hydrogen sulfide was monitored with a micro
gas chromatograph (µGC) (see Section 2.6).
The temperature and humidity inside the system were measured
with a Vaisala temperature and humidity probe (HMI41).
2.5. Field experiment
The LFG power plant consists of the LFG pump station, filtration
units, compressors, and three Capstone CR-65 kW microturbines to
generate electricity and 450 kW of heat using landfill gas.
Two filtration efficiency tests were conducted in the LFG power
plant. In the first test, the filtration unit (size 2.8 m3) was filled with
biochar made from birch (Betula). Birch was chosen because it was
readily available for LFG power plant applications. The concentration of
hydrogen sulfide was monitored up- and down-stream of the filtration
units for 14 days (until the filtration efficiency declined). The levels of
volatile organic compounds were measured during the second test day.
Three repetitive Tenax TA adsorbent tubes (Tenax) samples were taken
simultaneously before and after the filtration unit.
In the second test, the filtration unit was filled with activated carbon
and the hydrogen sulfide level was monitored for over 120 days. The
amounts of volatile organic compounds were measured during test day
70. Five repetitive Tenax samples were collected simultaneously up- and
down-stream of the filtration unit.
The functionality of the microturbines in the LFG power plant was
ensured at all times with another two filtration units (size 0.5 m3) that
contained activated carbon.
2.6. Analysis of the volatile organic compounds and hydrogen sulfide in
laboratory and field experiments
Siloxanes, toluene, and other volatile organic compounds were
collected before and after the filters into glass thermal desorption tubes,
Tenax. In the laboratory tests, the sampling time varied from 15 to 30
min. Samples were collected simultaneously before and after the filter.
One to eight samples were collected per day, with samples being taken
more frequently at the beginning of the test period. The laboratory tests
lasted from 7 to 12 days per filtration material.
In field measurements, the sampling time varied from 1 to 5 min
before the filtration unit and from 2 to 20 min after filtration. The
concentration of the VOCs was high upstream of the filtration, therefore
33
Waste Management 167 (2023) 31–38
a short sampling time was used to avoid overloading of the Tenax tubes.
The Tenax samples were analyzed in an automatic Thermodesorption
system (Markes TD 100) which was connected to a gas chromatograph
(Agilent 7890A) and a mass spectrometer (Agilent 5975C). The
desorption conditions were as follows: desorption temperature for the
Tenax samples 280 ◦ C (holding time 8 min), the cold trap temperature
− 10 ◦ C (3 min), and a split-ratio of 1:8. The capillary column was HP-5
(50 m × 0.20 mm; film thickness 0.33 µm). The temperature program of
the GC oven was as follows: 38 ◦ C hold for 4 min, with an increase of
5 ◦ C/min to 210 ◦ C and 20 ◦ C/min to 280 ◦ C. The identification of the
compounds was accomplished by inclusion of standard compounds,
retention times, and GC–MS data library (NIST 02). The standards used
included L2 (Fluka Analytical, ≥ 98.5 %), D4 (Sigma-Aldrich, ≥ 98 %),
D5 (Sigma-Aldrich, ≥ 97 %) and toluene (Sigma-Aldrich, ≥ 99.9 %). The
standards were prepared in methanol (Fisher Chemical, HPLC grade)
with dilution ratios (1:2500; 1:5000; 1:10 000) and added to the Tenax
tubes. The standard tubes were analyzed in the same way as the samples.
Toluene standards were used for the determination of single and total
volatile organic compounds in the field measurements of the LFG. This
approach has been used commonly in measurements of total volatile
organic compounds (TVOC), and single VOC quantifications in cases
when the reference compounds were not available (ISO 16000-6:2004).
Hydrogen sulfide was measured on a laboratory scale using Agilent
Technologies 490 micro gas chromatograph (µGC) and in-field mea­
surements with a BIOGAS 5000 monitor (Geotechnical Instruments (UK)
Ltd.) with the devices being calibrated before the measurements. In the
laboratory tests, the hydrogen sulfide concentration before the filtration
unit was 2000–4000 ppm and the tests lasted several hours per filter
sample.
The µGC-system used had three consecutive channels, each including
one packed column. The column of channel 1 was MS5A (length 10 m),
channel 2 had a PPU column (length 10 m), and channel 3 had a 5CB
column (length 6 m). The carrier gases used in the µGC were argon
(channel 1) and helium (channels 2 and 3). The run method included a
sampling time of 200 s, 40 ms injection time (injector temperature was
110 ◦ C) for all channels, and backflush for channels 1 (15 s) and 2 (16 s).
The following column temperatures were applied: 80 ◦ C (channel 1),
60 ◦ C (channel 2), and 70 ◦ C (channel 3).
2.7. Gas adsorption and desorption / Brunauer-Emmet-Teller (BET) and
Langmuir analyses
Activated carbon and biochar samples were pretreated in a vacuum
for 2 h at 150 ◦ C and overnight at 300 ◦ C to remove volatile compounds.
All the samples were measured with the gas ad-/desorption method
(Tristar II 3020, Micromeritics) at 0 ◦ C with carbon dioxide (CO2) being
the adsorptive gas and the absolute pressure interval ranging from 0 to 1
bar. Specific surface areas were calculated from both the adsorption and
desorption branches by using Brunauer-Emmet-Teller and Langmuir-
theories. Single measurements were done, and the presented errors are
attributable to the least square fitting performed in the BET and Lang­
muir calculations.
2.8. Thermogravimetry (TG)
The activated and biochar samples from the gas ad/desorption
analysis were exploited in TG. During the TG measurements, the samples
were equilibrated at 80 ◦ C for 30 min and then ramped to 800 ◦ C at
20 ◦ C/min. Nitrogen was used as an inert gas with a 120 ml/min flow to
the sample side and an 80 ml/min flow to the reference/balance side
with each sample being measured once (supplementary materials 2).
2.9. Electron microscopy (EM)
In order to visualize the particle size and morphology of the biochar,
samples were prepared by taking a random portion of biochar. The
M. Selenius et al. Waste Management 167 (2023) 31–38

biochar particles were mounted on a double-sided carbon tape by dip­

ping them onto a SEM stub. The scanning electron microscopy (SEM)
observation was performed with SIGMA HD/VP (Carl Zeiss Ltd, Cam­
bridge, UK). An acceleration voltage of 3 kV and a secondary electron
(SE) were used during imaging.

3. Results and discussion

3.1. Laboratory experiments

The filtration efficiency for both toluene and siloxanes was very high
in the filtrations made with activated carbon and the filtration efficiency
remained high throughout the testing period (385 h, 37 samples) for all
the tested compounds. The average concentrations of siloxanes and
toluene before filtration were L2 = 1439 µg/m3, D4 = 3525 µg/m3, D5
= 1592 µg/m3 and toluene = 13183 µg/m3, and after filtration L2 = 0.7
µg/m3, D4 = 9.1 µg/m3, D5 = 18.3 µg/m3, and toluene = 14.6 µg/m3.
We calculated the following filtration efficiencies; L2 = 100 %, D4 =
99.7 %, D5 = 98.7 %, and toluene = 99.9 %. The results are presented as Fig. 2. Filtration efficiency of biochar (willow). The average concentrations
the average of 37 samples. (µg/m3) of model compounds before filtration were as follows; L2 = 1750
Fig. 1 shows the filtration efficiency of biochar (birch) for siloxanes (standard deviation 610), Toluene = 9200 (standard deviation 1170), D4 = 440
(standard deviation 550), and D5 = 210 (standard deviation 470).
and toluene. The heavier siloxanes (D4 and D5) were filtrated effectively
during the whole test period. Instead, the filtration efficiency for L2
decreased rather rapidly, being less than 50 % within 100 h with almost
all of the material passing unbound through the filter at the end of the
test (at around 250 h after the beginning). In addition, the filtration
efficiency towards toluene decreased almost linearly throughout the
whole test period.
Fig. 2 shows the filtration efficiency of the biochar made of willow
for the tested compounds. The filtration efficiency for L2 declined
rapidly fast, within 30 h it completely vanished until after 70 h when it
started to become active again; filtration efficiency remained between
30 % and 50 % for the remainder of the test period. D5 and D4 were
removed rather well despite the sudden decline in D5′ s filtration effi­
ciency at around 55 h; otherwise, the filtration efficiency was over 90 %.
The reason for the decrease and increase of the L2′ s filtering power was
not clear in these experiments. Since the behavior of the other longer
siloxanes in the test was normal, no problems were attributable to the
experimental setup. The filtration efficiency for toluene decreased
slowly to around 80 % at the end of the test.
Fig. 3. Filtration efficiency of activated carbon and birch/willow biochar for
Fig. 3 illustrates the filtration efficiencies for the biochars made of
hydrogen sulfide. The mean H2S concentration before the filters varied in a
willow and birch and activated carbon for hydrogen sulfide. Activated range from 2900 to 3200 µg/m3.
carbon removed nearly 100 % of hydrogen sulfide during the whole test
period. Instead, both tested biochars started to lose their filtration effi­
ciency rather quickly. In both cases, the filtration efficiency had declined
to around 80% within 3 h and after that, it decreased further to 60 %.

3.2. Field experiments

Fig. 1. Filtration efficiency of biochar (birch). Mean concentrations (µg/m3) of
model compounds before the filtration unit were as follows; L2 = 1800 (stan­
dard deviation 310); Toluene = 7510 (standard deviation 890), D4 = 330
(standard deviation 470), and D5 = 150 (standard deviation 460).
The filtration unit contained 2.8 m3 biochar made of birch. The LFG
contents during the two weeks measuring period were as follows: before
the filters, methane = 49.0 ± 8.1%, carbon dioxide = 32.9 ± 2.5%,
oxygen = 1.4 ± 0.7%, and hydrogen sulfide = 756.2 ± 18.0 µg/m3 and
after the filter: methane = 49.0 ± 8.6%, carbon dioxide = 32.7 ± 2.3%,
oxygen = 1.4 ± 0.7%, and hydrogen sulfide = 253.2 ± 136.9 µg/m3.
Fig. 4 presents the filtration efficiency for hydrogen sulfide during that
time. The filtration efficiency decreased below 50 % within six days and
below 20 % within 14 days. One change in filtration efficiency can be
seen during test day 5 after the filtration unit was shaken but the rear­
rangement of biochar exerted only a temporary influence on the filtra­
tion efficiency. We tested the effect of shaking because the staff using the
turbine at the landfill knew from experience that this procedure has a
positive effect on the filtration efficiency. The phenomenon may be due
to the new uncontaminated sites opening up after shaking, i.e. the
filtration releases a new active surface that had not been available to the

34
M. Selenius et al. Waste Management 167 (2023) 31–38

Table 1
Concentrations of VOC compounds before and after filtration (Pre-filter filled
with birch biochar. The gases were led to a delicate and expensive electricity-
generating turbine, so the purity of the gas was ensured with an actual filter
located after the test filter used in this study). (Test day 2, Power plant used for
40 h).
Compound CAS RN RT Q Conc. Conc.
(min) (%) before after (µg/
(µg/m3) m3)

TVOC (total volatile 76,758 5811

organic compounds) filtrated
92%
Cyclotetrasiloxane, 556- 19.235 91 3006 2
octamethyl- (D4) 67-2
Cyclopentasiloxane, 541- 24.309 91 2011 6
decamethyl- (D5) 02-6
Disiloxane, hexamethyl- 107- 8.023 90 207 30
46-0
Fig. 4. Filtration efficiency of the biochar filter (made of birch) for H2S in the Toluene 108- 11.019 91 2049 90
LFG power plant (before the microturbine facility). The filtration unit was 88-3
shaken on test day 5. The H2S concentration before the filtration unit was 680 Ethylbenzene 100- 14.661 91 8660 427
41-4
± 110 ppm.
p-Xylene 106- 14.928 94 8397 279
42-3
gas molecules. An alternative explanation is that the biochar structure o-Xylene 95-47- 15.832 95 3612 154
had collapsed, resulting in the opening of new active adsorption sites. 6
Benzene, 1,2,3-trimethyl- 526- 18.526 95 2788 61
Nonetheless, the re-arrangement only produced that new adsorption
73-8
area for a short time. By measuring the concentrations of methane, Benzene, 1-methyl-2-(1- 527- 20.365 95 2329 81
carbon dioxide, and oxygen, we were able to estimate the landfill’s methylethyl)- 84-4
methane production level, which affects the amount of hydrogen sulfide Hexane, 2-methyl- 591- 7.559 50 1996 101
and its formation. The measured values remained rather constant 76-4
1S-.alpha.-Pinene 7785- 17.348 97 1913 –
throughout the experiment. 26-4
Table 1 shows the most important volatile organic compounds Benzene, 1-ethyl-2- 611- 18.251 74 1712 –
detected in waste gas before and after filtration during test day 2. The methyl- 14-3
biochar filtrated siloxanes relatively well during the first field test days: Octane, 2,6-dimethyl- 2051- 17.169 93 1520 204
30-1
filtration efficiencies were as follows; for D4, 99.7 %; for D5, 99.9 %; for
Decane 124- 19.5 94 1426 86
L2, 85.5 %, and for TVOC, 92 %. Biochar behaved in the same way as in 18-5
laboratory tests i.e. it filtrated heavier siloxanes more efficiently than Heptane 142- 8.59 91 1394 118
the lighter compounds. 82-5
Biochar was replaced with activated carbon because the filtration Nonane 111- 15.937 91 1336 108
84-2
efficiency for hydrogen sulfide declined dramatically within two weeks. Cyclohexane, 1-ethyl-4- 4926- 15.641 91 1086 –
Subsequently, the LFG content (including hydrogen sulfide) was moni­ methyl-, cis- 78-7
tored during the normal use of the power plant. The activated carbon Bicyclo[4.1.0]heptane, 18968- 19.061 90 1079 133
efficiently filtrated hydrogen sulfide for the first 70 days but after that 3,7,7-trimethyl-, (1. 23-5
alpha.,3.alpha.,6.
time point, the filtration efficiency started to decline, Fig. 5.
alpha.)-
The volatile organic compounds were collected twice during the Heptane, 2,4-dimethyl- 2213- 12.143 64 1035 43
normal use of the power plant with the results taken on test day 70 being 23-2
presented in Table 2. Activated carbon filtrated siloxanes very efficiently Cyclohexane, methyl- 108- 9.431 94 1017 160
(D4: 99.3 %; D5: 98.8 %, and L2: 100 %) and 98.8% for TVOC. 87-2
Pentane 109- 4.445 72 986 134
66-0
Hexane, 3-methyl- 589- 7.809 95 973 117
3.3. Physical properties of the tested activated carbon and the biochars 34-4
Octane, 4,5-dimethyl- 15869- 18.111 38 968 119
96-2
All samples were measured for isotherms (adsorption and desorp­
Camphene 79-92- 17.875 97 793 113
tion) in order to calculate their surface areas. Gas adsorption/desorption 5
isotherms were measured for unused samples activated carbon, birch Cyclohexane, 1,2,4- 2234- 14.32 90 693 102
biochar, and willow biochar. The measurement settings included CO2 as trimethyl- 75-5
the adsorptive, the temperature fixed to 0 ◦ C, with a pressure interval of Heptane, 3-ethyl-2- 14676- 17.42 68 652 91
methyl- 29-0
0–1 bar, which corresponds to relative pressures 0–0.03 bar. The iso­ Alpha.-Pinene 7785- 17.305 97 576 263
therms are of type 1, implying the presence of micropores (less than2 70-8
nm). The samples exhibited minor or negligible evidence of hysteresis, 1-Ethyl-3- 3728- 15.531 95 530 103
stressing the absence of mesopores. The calculated BET surface areas methylcyclohexane (c,t) 55-0
Butane, 2-methyl- 78-78- 4.237 91 373 98
(±S.D.) were as follows: activated carbon = 528 ± 8 m2/g, birch = 220
4
± 3 m2/g, and willow = 202 ± 1.5 m2/g. The Langmuir surface areas 1-Pentene 109- 5.329 58 – 133
were; activated carbon = 597 ± 11 m2/g, birch = 234 ± 3 m2/g, and 67-1
willow = 214 ± 2 m2/g. The surface areas obtained with BET- and 1-Cyclobutanone,2-(2- 91531- 16.758 58 – 102
Langmuir-theories were all within similar size ranges although the areas methyl-1-propenyl) 45-2

obtained with Langmuir were slightly higher. However, it must be stated

that the values of the surface area for activated carbon were about half of

35
M. Selenius et al. Waste Management 167 (2023) 31–38

CAS RN: Chemical Abstracts Service Registry Number; RT: Retention Time; Q: Table 2
Quantification (%). Concentration of VOC-compounds before and after filtration (Pre-filter filled
with active carbon. The gases were led to a delicate and expensive electricity-
generating turbine, so the purity of the gas was ensured with an actual filter
located after the test filter used in this study). Test day 70.
Compound CAS RT Conc. Conc. after
RN (min) before prefilter (µg/
(µg/m3) m3)
Filtrated
98.8%

TOTAL 76,548 956

(527–1384)
TVOC 70,351 551
(131–972)
Disiloxane, hexamethyl- 107- 7.984 247 N.D.
46-0
Cyclotrisiloxane, hexamethyl- 541- 12.861 543 12 (7–16)
05-9
Trisiloxane, octamethyl- 107- 15.101 97 N.D.
51-7
Cyclotetrasiloxane, octamethyl- 556- 19.150 913 6 (3–10)
67-2
Cyclopentasiloxane, 541- 24.243 423 5 (1–9)
Fig. 5. Filtration efficiency of activated carbon filter for H2S in the LFG power decamethyl- 02-6
plant (before the microturbine facility). The H2S concentration before the Cyclohexasiloxane, 540- 29.304 23 2 (1–3)
filtration unit was 1260 ± 50 ppm. dodecamethyl- 97-6
1,3,5,7,9-Pentaethylbicyclo 73420- 37.900 32 2 (2)
[5.3.1]pentasiloxane 26-5
the value obtained with N2 (data not shown). This effect could be
2-Isopropyl-5-methyl-1- 91337- 18.051 744 N.D.
explained by the different interaction mechanisms between CO2 and the heptanol 07-4
sample in comparison to that obtained with the N2 measurement Acetic acid 64-19- 5.548 455 57 (7–106)
(Maziarka et al., 2021). For example, it is known that thse measurements 7
can be influenced by the degassing temperature (Sigmund et al., 2017). alpha-Pinene 80-56- 17.234 2685 11 (4–19)
8
Benzene 71-43- 7.464 990 7 (7)
3.4. Thermogravimetry 2
Benzene, 1,3,5-trimethyl- 108- 19.340 714 12 (12)
67-8
Thermogravimetric measurements were performed to analyze the
Benzene, 1-ethyl-2,3-dimethyl- 933- 20.390 1706 39 (39)
levels of volatiles in the original samples. All samples behaved in the 98-2
same way up to 400 ◦ C without losing mass. Biochars lost 15–17% of Benzene, 1-ethyl-2-methyl- 611- 18.181 1448 13 (13)
their mass between 400 and 800 ◦ C. From the TGA measurements, it can 14-3
be confirmed that both biochars were produced at the same temperature Butane, 2-methyl- 78-78- 4.217 1230 8 (7–8)
4
(400 ◦ C) because the mass loss started at the same temperature (Conti
Cyclohexane, 1,3-dimethyl-, 2207- 18.955 768 N.D.
et al., 2016). The willow biochar released mass slightly faster than its trans- 03-6
birch counterpart. It is known that at temperatures above 400 ◦ C, the Cyclohexane, 1-methyl-4-(1- 6069- 18.598 1008 N.D.
leaving structures are mainly annular hydrocarbon compounds (Conti methylethyl)-, cis- 98-3
Cyclohexane, methyl- 108- 9.375 1653 2 (2)
et al., 2016; Kaal et al., 2012).
87-2
Activated carbon did not lose any mass during the measurement even Cyclopentane 287- 5.299 1555 172
when the temperature was raised to 800 ◦ C. 92-3 (166–178)
Decane 124- 19.383 1850 26 (26)
18-5
3.5. SEM images and observations
Ethylbenzene 100- 14.495 6186 68 (68)
41-4
The images in Fig. 6 show the fine-grained but also the rough surface Heptane 142- 8.520 1609 2 (2)
of the activated carbon. Based on the images, the larger surface area of 82-5
activated carbon can be also observed when compared to inactivated Hexane, 2,2-dimethyl- 590- 8.157 761 N.D.
73-8
biochar. The cellular structure of wood can be detected in biochar,
Hexane, 2-methyl- 591- 7.502 1514 N.D.
which correspondingly was responsible for the surface area of the 76-4
biochar. Hexane, 3-methyl- 589- 7.773 1378 N.D.
The structure of biochar was mechanically weaker than that of the 34-4
Nonane 111- 15.816 1190 9 (9)
dense activated carbon extrudates. This weakness in the biochar’s
84-2
structures could lead to the material being crushed under pressure. Octane, 2,6-dimethyl- 2051- 17.061 1350 9 (9)
30-1
4. Conclusion Pentane 109- 4.422 1800 N.D.
66-0
Toluene 108- 10.939 2903 24 (24)
In field tests, activated carbon removed hydrogen sulfide for 70 days, 88-3
after which the filtration efficiency declined dramatically. The filtering Trichloromonofluoromethane 75-69- 4.330 346 96 (64–127)
power of the birch biochar showed a tendency to decrease steadily, i.e. it 4
had lost more than half of its capacity after 8 days. The surface of Xylene 108- 14.793 9399 128 (128)
38-3
activated carbon was rougher than biochar, which displayed a tubular
structure in the SEM images. Based on adsorption and desorption mea­ CAS RN: Chemical Abstracts Service Registry Number; RT: Retention Time.
surements, the surface area of activated carbon was approximately

36
M. Selenius et al. Waste Management 167 (2023) 31–38

Fig. 6. Scanning electron microscope images, A, B activated carbon, C, D birch biochar, and E, F willow biochar.

double that of the biochars. The active adsorption sites activated carbon
are located on the surface and not in its internal structures, as is the case
of the tubular structures present in biochar. Gases travel more easily on
surfaces and have more difficulty in gaining access to internal structures.
These factors contribute to the fact that the activated carbon worked
longer because there were more active adsorption sites available. The
study showed that biochar adsorbed to some extent siloxanes, hydrogen
sulfide, and VOC compounds. The laboratory tests conducted with
small-scale filtration units and model compounds showed that the bio­
char was effective in removing pollutants. Birch removed efficiently
octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane com­
pounds throughout the laboratory test. The greatest difference between
birch and willow in filtration efficiency was noted in the adsorption of
hexamethylsiloxane, where birch was better than willow.
The present study revealed that as such biochar made of birch or
willow is not efficient enough to compete with commercial AC appli­
cations. Therefore, more research is needed to improve the filtrating
properties of biochar e.g. structural modifications.
5. Recommendation for future research
It would be beneficial to study how to improve the filtration prop­
erties of a biochar made of birch or willow while having a minimal
environmental impact. For example, it may be advisable to process the
biochar into pellets similar to the commercially available activated
carbon. In this way, the differences in the chemical properties of carbon
in filtering harmful substances could be compared. In addition, further
research should clarify the reasons for the differences between birch and
willow.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability

The data that has been used is confidential.

37
M. Selenius et al. Waste Management 167 (2023) 31–38

Acknowledgements Kaal, J., Cortizas, A.M., Reyes, O., Soliño, M., 2012. Molecular characterization of Ulex
europaeus biochar obtained from laboratory heat treatment experiments – A
pyrolysis–GC/MS study. J. Anal. Appl. Pyrol. 95, 205–212.
We thank SIB Labs unit of University of Eastern Finland for their Kanjanarong, J., Giri, B.S., Jaisi, D.P., Oliveira, F.R., Boonsawang, P., Chaiprapat, Singh,
support in terms of equipment and facilities, as well as the skilled staff. R.S., Balakrishna, A., Khanal, S.K., 2017. Removal of hydrogen sulfide generated
during anaerobic treatment of sulfate-laden wastewater using biochar: Evaluation of
efficiency and mechanisms. Bioresource Technology 234, 115–121.
Appendix A. Supplementary data Karp A. 2014. Willows as a Source of Renewable Fuels and Diverse Products. In: Fenning,
T. (eds) Challenges and Opportunities for the World’s Forests in the 21st Century.
Supplementary data to this article can be found online at https://doi. Forestry Sciences, vol 81. Springer, Dordrecht. https://doi.org/10.1007/978-94-
007-7076-8_27.
org/10.1016/j.wasman.2023.05.006. Katoh, H., Kuniyoshi, I., Hirai, M., Shoda, M., 1995. Studies of the oxidation mechanism
of sulphur-containing gases on wet activated carbon fibre. Appl. Catal. B 6 (3),
References 255–262.
Kim, B.W., Chang, H.N., 1991. Removal of hydrogen sulfide by Chlorobium
thiosulfatophilum in immobilized cell and sulfur settling free-cell recycle reactors.
Ahmad, M., Rajapaksha, A.U., Lim, J.E., Zhang, M., c, Bolan, N., Mohan, Vithanage, M.,
Biotechnol. Prog. 7, 495–500.
Lee, S.S., Ok, Y.S., 2014. Biochar as a sorbent for contaminant management in soil
Kim, K.H., Baek, S.O., Choi, Y.J., et al., 2006. The Emissions of Major Aromatic VOC as
and water: A review Chemosphere 99, 19–33.
Landfill Gas from Urban Landfill Sites in Korea. Environ. Monit Assess. 118,
Alhashimi, H.A., Aktas, C.B., 2017. Life cycle environmental and economic performance
407–422.
of biochar compared with activated carbon: A meta-analysis. Resour. Conserv.
Kim, M.H., Jeong, I.T., Park, S.B., Kim, J.W., 2018. Analysis of environmental impact of
Recycl. 118, 13–26.
activated carbon production from wood waste. Environmental Engineering
Arena, N., Lee, J., Clift, R., 2016. Life Cycle Assessment of activated carbon production
Research. [Online journal]. Vol. 24:1. pp. 117—126. Available: DOI: 10.4491/
from coconut shells. Journal of Cleaner Production. [Online Journal]. 125. 68—77.
eer.2018.104. ISSN 1226-1025.
Available: DOI: 10.1016/j.jclepro.2016.03.073. ISSN 0959- 6526.
Lehmann, J., Joseph, S., 2009. Biochar for environmental management Science and
Ayodele, T.R., Alao, M.A., Ogunjuyigbe, A.S.O., 2020. Effect of collection efficiency and
Technology. Earthscan, London, p. 405.
oxidation factor on greenhouse gas emission and life cycle cost of landfill distributed
Manheim, D.C., Yeşiller, N., Hanson, J.L., 2021. Gas Emissions from Municipal Solid
energy generation. Sustain. Cities Soc. 52, 101821.
Waste Landfills: A Comprehensive Review and Analysis of Global Data. J. Indian
Baker, P., Charlton, A., Johnston, C., Leahy, J.J., Lindegaard, K., Pisano, I.,
Inst. Sci. 101, 625–657.
Prendergast, J., Preskett, D., Skinner, C., 2022. A review of Willow (Salix spp.) as an
Mao, Q., Watanabe, M., Koike, T., 2010. Growth Characteristics of Two Promising Tree
integrated biorefinery feedstock. Ind. Crop. Prod. 189, 115623.
Species for Afforestation, Birch and Larch in the Northeastern Part of Asia. Eurasian
Bandosz, T.J., 1999. Effect of pore structure and surface chemistry of virgin activated
J. For. Res. 13–2, 69–76.
carbons on removal of hydrogen sulfide. Carbon 37 (3), 483–491.
Maziarka, P., Wurzer, C., Arauzo, P.J., Dieguez-Alonso, A., Mašek, O., Ronsse, F., 2021.
Cha, J.M., Cha, W.S., Lee, J.H., 1999. Removal of organosulphur odour compounds by
Do you BET on routine? The reliability of N2 physisorption for the quantitative
hiobacillus novellas SRM, sulphur-oxidizing microorganisms. Process Biochem. 34
assessment of biochar’s surface area. Chem. Eng. J. 418, 129234.
(6–7), 659–665.
Muñoz, R., Meier, L., Diaz, I., Jeison, D., 2015. A review on the state-of-the art of
Chen, J., Zhu, D., Sun, C., 2007. Effect of Heavy Metals on the Sorption of Hydrophobic
physical/chemical and biological technologies for biogas upgrading. Rev. Environ.
Organic Compounds to Wood Charcoal Environ. Sci. Technol. 41 (7), 2536–2541.
Sci. Bio/Technology 14, 727–759.
Conti, R., Fabbria, D., Vassuraa, I., Ferroni, L., 2016. Comparison of chemical and
Panza, D., Belgiorno, V., 2010. Hydrogen sulphide removal from landfill gas. Process Saf.
physical indices of thermal stability of biochars from different biomass by analytical
Environ. Prot. 88 (6), 420–424.
pyrolysis and thermogravimetry. J. Anal. Appl. Pyrol. 122, 160–168.
Rasi, S., Veijanen, A., Rintala, J., 2007. Trace compounds of biogas from different biogas
Dai, Y., Zhang, N., Xing, C., Cui, Q., Sun, Q., 2019. The adsorption, regeneration and
production plants. Energy 32, 1357–1380.
engineering applications of biochar for removal organic pollutants: A review.
Rasi, S., Läntelä, J., Veijanen, A., Rintala, J., 2008. Landfill gas upgrading with
Chemosphere 223, 12–17.
countercurrent water wash. Waste Manage. 28, 1528–1534.
Deublein D. and Steinhauser A., 2008. Biogas from waste and renewable sources An
Rücker, C., Kümmerer, K., 2015. Environmental Chemistry of Organosiloxanes. Chem.
introduction. Second, Revised and Expanded Edition. Wiley-VCH, John WileySons.
Rev. 115, 466–524.
Dewil, R., Appels, L., Bayens, J., 2006. Energy use of biogas hampered by the presence of
Salami, A., Raninen, K., Heikkinen, J., Tomppo, L., Vilppo, T., Selenius, M.,
siloxanes. Energ. Convers. Manag. 47, 1711–1722.
Raatikainen, O., Lappalainen, R., Vepsäläinen, J., 2020. Complementary chemical
Dolgen, D., Sarptas, H., Alpaslan, N., Kucukgul, O., 2005. Energy Potential of Municipal
characterization of distillates obtained from industrial hemp hurds by thermal
Solid Wastes. Energy Source 27 (15), 1483–1492.
processing. Ind. Crops Prod. 155, 112760.
Duan, Z., Scheutz, C., Kjeldsen, P., 2021. Trace gas emissions from municipal solid waste
Schweigkofler, M., Niessner, R., 2001. Removal of siloxanes in biogases. J. Hazard.
landfills: A review. Waste Manag. 119, 39–62.
Mater. 83 (3), 183–196.
Dubois, H., Verkasalo, E., Claessens, H., 2020. Potential of Birch (Betula pendula Roth
Shang, G., Li, Q., Liu, L., Chen, P., Huang, X., 2015. Adsorption of hydrogen sulfide by
and B. pubescens Ehrh.) for Forestry and Forest-Based Industry Sector within the
biochars derived from pyrolysis of different agricultural/forestry wastes. J. Air
Changing Climatic and Socio-Economic Context of Western Europe. Forests 11 (3),
Waste Manag. Assoc. 66 (1), 8–16.
336. https://doi.org/10.3390/f11030336.
Shareefdeen, Z., Herner, B., Wilson, S., 2002. Biofiltration of nuisance sulfur gaseous
Gaj, K., 2020. Adsorptive Biogas Purification from Siloxanes-A Critical Review. Energies
odors from a meat rendering plant. J. Chem. Technol. Biotechnol. 77, 1296–1299.
13 (10), 2065.
Sigmund, G., Hüffer, T., Hofmann, T., Kah, M., 2017. Biochar total surface area and total
Griffin, P., 2007. Biogas treatment. Presentation at Cranfield University, 18th September.
pore volume determined by N2 and CO2 physisorption are strongly influenced by
Grumping, R., Michalke, K., Hirner, A.V., Hensel, R., 1999. Microbial degradation of
degassing temperature. Sci. Total Environ. 580, 770–775.
Octamethylcyclotetrasiloxane. Appl. Environ. Microbiol. 65 (5), 2276–2278.
Sun, J., Zhang, J.P., Wen, C., Zhang, L., 2016. An enhanced approach for biochar
Gu, H., Bergman, R., Anderson, N., Alanya-Rosenbaum, S., 2018. Life-cycle assessment of
preparation using fluidized bed and its application for H2S removal Chemical. Eng.
activated carbon from woody biomass. Wood Fiber Sci. 50 (3), 229–243.
Process. 104, 1–12.
Hassan, M.K., Villa, A., Kuittinen, S., Jänis, J., Pappinen, A., 2019. An assessment of side-
Tchobanoglous, G., Theisen, H., Vigil, S.A., 1993. Integrated solid waste management:
stream generation from Finnish forest industry. J Mater Cycles Waste Manag. 21,
engineering principles and management issues. McGraw-Hill.
265–280. https://doi.org/10.1007/s10163-018-0787-5.
US EPA, 1974, Environmental Hazard Assessment of Liquid Siloxanes (Silicones); U.S.
Hjaila, K., Baccar, R., Sarrà, M., Gasol, C.M., Blánquez, P., 2013. Environmental impact
Environmental Protection Agency: Washington, DC: http://nepis.epa.gov/Adobe/
associated with activated carbon preparation from olive-waste cake via life cycle
PDF/9100368J.PDF.
assessment. J Environ Manage. 30, 242–247. https://doi.org/10.1016/j.
Varaprath, S., Frye, C.L., Hamelink, J., 1996. Aqueous solubility of permethylsiloxanes
jenvman.2013.08.061. Epub 2013 Oct 1 PMID: 24091159.
(silicones). Environ. Toxicol. Chem. 15, 1263–1265.
Hyttinen, M., Pasanen, P., Björkroth, M., Kalliokoski, P., 2007. Odors and volatile
Xu, X., Cao, X., Zhao, L., Sun, T., 2014. Comparison of sewage sludge- and pig manure-
organic compounds released from the ventilation filters. Athmospheric Environment
derived biochars for hydrogen sulfide removal. Chemosphere 111, 296–303.
41, 4029–4039.
Igoe, B.M., Welch, M.J., 2015. Impact of Fuel Contaminants on Gas Turbine peration. In
21st Symposium of the Industrial Application of Gas Turbines Committee, Banaff,
Alberta, Canada.

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