Accepted Manuscript

Polycyclic aromatic hydrocarbons (PAHs) in biochar – Their formation, occur-

rence and analysis: A review

Congying Wang, Yingdi Wang, H.M.S.K. Herath

PII: S0146-6380(16)30306-0
DOI: http://dx.doi.org/10.1016/j.orggeochem.2017.09.001
Reference: OG 3613

To appear in: Organic Geochemistry

Received Date: 4 November 2016

Revised Date: 27 August 2017
Accepted Date: 4 September 2017

Please cite this article as: Wang, C., Wang, Y., Herath, H.M.S.K., Polycyclic aromatic hydrocarbons (PAHs) in
biochar – Their formation, occurrence and analysis: A review, Organic Geochemistry (2017), doi: http://dx.doi.org/
10.1016/j.orggeochem.2017.09.001

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 Polycyclic aromatic hydrocarbons (PAHs) in biochar – Their formation,

occurrence and analysis: A review

Congying Wanga *, Yingdi Wanga, H.M.S.K. Herathb

a
College of Environmental & Resource Sciences, Shanxi University, Taiyuan 030006,

China

b
Department of Export Agriculture, Faculty of Animal Science and Export

Agriculture, Uva Wellassa University, Passara Road, Badulla 90 000, Sri Lanka

*
Corresponding authors Email addresses: wangcongying@sxu.edu.cn

Tel: +86 351 7010393; fax: +86 351 7010393.

1
ABSTRACT

Application of biochar for soil development has been increasingly practiced over

the last decade. However, during the pyrolytic production of biochar, polycyclic

aromatic hydrocarbons (PAHs) can form and are present on the surface of biochar.

Consequently, there may be a potential risk for human health as well as the

environment. In the present paper, research progress related to PAHs in biochar with

respect to their formation mechanisms, factors that influence their formation, and the

methods used to determine the total and bioavailable PAHs are discussed. The

pyrolysis process is the key factor responsible for the yield of PAHs in biochar. Slow

pyrolysis and longer residence time result in lower PAHs yield than the fast pyrolysis

and shorter residence time. Temperature is also another significant determinant

affecting the formation and yield of PAHs. Low molecular weight PAHs are usually

formed at low temperature (< 500 °C) whereas the high molecular weight PAHs

commonly appear under high temperature (> 500 °C). Original composition, mineral

and moisture content of feedstock, appearance of O2 during pyrolysis or after some

treatments also have a considerable effect on the yield of PAHs. Analytical methods

for extraction of PAHs from biochar mainly include Soxhlet extraction and

accelerated solvent extraction. However, the extraction efficiency depends both on the

extractant method and the type of biochar. This review of the literature has noted that

future studies should focus on (i) development of a standard protocol for quantifying

total and bioavailable PAHs in biochar, (ii) revealing the effect of key chemical

components of feedstock and high temperature on the formation of PAHs, and (iii)

2
carrying out eco-toxicological studies at long timescale to evaluate the environmental

risk of biochar application.

Keywords: Extraction method; Total concentration; Bioavailability; Pyrolysis process;

Temperature

1. Introduction

Biochar is a product resulting from thermal conversion of biomass under

O2-limited conditions (Antal and Grønli, 2003). It has recently received increased

attention due to its broad potential use in both agronomic and environmental fields.

Biochar is used as a soil amendment to mitigate greenhouse gas emission (Troy et al.,

2013). It also improves soil physico-chemical and biological properties, including

nutrient status, soil structure, and water holding capacity (Karhu et al., 2011;

Lehmann et al., 2011; Herath et al., 2013), and modifies microbial community

abundance and soil enzyme activity (Paz-Ferreiro et al., 2012; Gomez et al., 2013).

These benefits may ultimately help increase crop yield. Other applications of biochar

include the potential use as a sorbent for removing and immobilizing various

contaminants from water or soil (Shimabuku et al., 2016; Ahmad et al., 2017).

However, all these functions of biochar depend on the conditions during biochar

production and the type of feedstock used (Jeffery et al., 2015; Tag et al., 2016).

Polycyclic aromatic hydrocarbons (PAHs) are a group of persistent organic

contaminants with ≥ 2 aromatic rings (Rehmann et al., 2008; Mahler et al., 2012).

PAHs are mainly derived from incomplete combustion of biomass or fossil fuel

(Glaser et al., 2005). A significant proportion of PAHs could be inevitably formed

3
during biochar production (Garcia-Perez, 2008; Hilber et al., 2012; Schimmelpfennig

and Glaser, 2012; Dutta et al., 2016), and in turn pose a threat to the natural

environment due to the increased rate of biochar application. They have drawn the

attention of both the general public and scientists because of their persistence in the

environment and their carcinogenic, mutagenic and teratogenic effects on human

health (Rehmann et al., 2008; Mahler et al., 2012). Previous studies have mainly

focused on the benefits of biochar and have ignored the possible negative effects. The

potential risk of biochar should be estimated, and quantification of toxic compounds

such as PAHs by laboratory analyses is required. Thus far, a small number of studies

have measured the total amount of PAHs or other toxic compounds such as dioxin in

biochar (Singh et al., 2010; Hale et al., 2012; Hilber et al., 2012; Bucheli et al. 2015;

Buss et al. 2015; De la Rosa et al., 2016; Mayer et al., 2016). In those studies, Soxhlet

extraction, ultrasonication extraction and accelerated solvent extraction (ASE) were

employed. The efficiency of these methods varies significantly depending on the

particular type of biochar and the type of solvent used (Bucheli et al., 2015). Hence,

the reliability of these methods may also differ for various products.

Before contaminants are harmful to the environment, they must be bioavailable.

Therefore, it is important to quantify the amount of bioavailable PAHs in biochar. A

few studies have examined this to the date (Hale et al., 2012; Mayer et al., 2016;

Zielińska and Oleszczuk, 2016). In the current work, research progress on PAHs in

biochar including their formation mechanisms during biochar production, factors that

influence on the amount of PAHs in biochar and the extraction methods used to

4
determine the total and bioavailable PAHs in biochar are reported. The objective is to

provide some suggestions on how to produce biochar with lower PAH, due to the

concern of PAHs on human and environmental health, while reporting important

information related to the above aspects.

2. Formation mechanism of PAHs in biochar

Syngas, bio-oil and biochar are produced as the major products in the

thermochemical process of biomass (Fig.1). The yield of each product depends on the

type of biomass and the processing conditions (i.e. maximum pyrolysis temperature,

heating rate and residence time of the process, etc.). In a high temperature (ca. 500

°C), fast pyrolysis system, where the reactor heats to the target temperature within

0.5–2 s, and has a heating rate up to 1000 °C/s (Brewer et al., 2009; Brown et al.,

2011), a large amount of bio-oil (ca. 60% of mass) is produced, and relatively small

amounts of syngas (ca. 20%) and biochar (ca. 20%; Brown, 2003; Laird, 2008). Under

a low temperature (ca. 300 °C), slow pyrolysis system, in which the system heats the

reactor to the target temperature in few hours or days with a heating rate of 1–20

°C/min (Brewer et al., 2009; Brown et al., 2011). This system produces a relatively

higher yield of biochar (ca. 35–50%; Tan et al., 2015). Fig. 2 shows the effect of

pyrolysis temperature and heating rate on the yield of three bio-products described

above. It is vital that a slow pyrolysis system be employed if the primary objective is

to obtain more biochar. Importantly, a slow pyrolysis system produces a lower yield

of PAHs (Quilliam et al., 2013) as illustrated in detail in Section 4.1.

Studies on the mechanisms of PAHs formation during biomass pyrolysis have

5
been carried out since the 1950s. While the knowledge on PAHs formation is still

limited, some important findings are well summarized in recent studies (Keiluweit et

al. 2012; Bucheli et al. 2015). As reported by Keiluweit et al. (2012), PAHs are

produced via two principal pathways:

(i) At temperatures < 500 °C, PAHs form via direct carbonization and

aromatization transforming feedstock to carbonaceous material (Bucheli et al., 2015).

During the process, unimolecular cyclization, dehydrogenation, dealkylation and

aromatization of lignin and cellulose, as well as lipids (i.e. resins and steroids) occur

(Simoneit, 1998; Kuśmierz and Oleszczuk, 2013). The process eliminates

functionalities in the native compounds such as H2O, CO2, CH4, and H2S, leaving

behind aromatized structures. Under this temperature regime, most PAHs that are

formed have low molecule weight (LMW; Brown et al., 2006). However, some high

molecular weight (HMW) compounds, such as benzo(a)pyrene, are also expected to

be formed (McGrath et al., 2001, 2003, 2007). Some studies have shown more details

on PAHs composition related to this temperature range. For example, by applying

online laser-induced fluorescence, Dieguez-Alonso et al. (2013, 2015) characterized

PAHs in gas and tar, which evolved from the pyrolysis of wood, holocellulose and

lignin, and found that the aromatic compounds were mainly small PAHs (such as

phenolics, naphthalene and compounds with carbonyl groups) in the primary phase (<

300 °C). However, PAHs with three or four rings appeared at the second phase with

higher temperature (300–600 °C).

(ii) At temperatures > 500 °C, PAHs are formed through a free radical pathway

6
which is followed by pyrosynthesis into larger aromatic structures (Lee et al., 1981;

Simoneit, 1998; Bucheli et al., 2015). At first, organic compounds are partially

cracked into small hydrocarbon radicals (e.g. ethynyl, HC≡C• and 1, 3-butadiene

radicals, H2C＝CH−CH＝C•H). Then, a pyrosynthesis reaction occurs and these

radicals fuse into unsubstituted and thermodynamically more stable LMW PAHs such

as naphthalene (Simoneit and Fetzer, 1996). With increasing temperature and

residence time, these LMW PAHs are thought to grow via a “zig-zag addition

process” into tertiary HMW PAHs such as benzo(a)pyrene and benzo(g,h,i)perylene

(Sullivan et al., 1989), which are more toxic in nature. In this scheme, the building-up

of rings occurs through H abstraction and an C2H2 addition reaction (Bucheli et al.,

2015). These tertiary pyrolysis products are expected to become significant at the

temperature > 650 °C (Stein, 1978; Ledesma et al., 2002; Morf et al., 2002).

The two pathways described above demonstrate the complexity of PAHs

formation. Overall, temperature is one of the key factors that influences the final

amount of PAHs in biomass pyrolysis. The effect of temperature on PAHs yield is

illustrated in Section 4.2.

3. Methods for analysis of PAHs in biochar

There are 16 PAHs that are listed as priority pollutants by the United States

Environmental Protection Agency (from here on referred to as “the 16 EPA PAHs”;

the structures and physicochemical properties of these compounds are shown in Table

S1 in the Supporting Information). Previous studies have considered these compounds

and investigated the analysis method as regard to biochar. However, it should be

7
noted that information obtained from only these compounds (16 EPA PAHs) may be

too limited to fully assess the negative effect of biochar on the environment

(Andersson and Achten, 2015). For example, high yield of various alkylated PAHs

can be formed at lower temperatures (<300 °C) during biomass pyrolysis (Hautevelle

et al., 2006). Some alkylated PAHs such as 1-methyl- and 2-methyl-naphthalene

should be considered in future studies because of their toxicological relevance

(El-Masri et al., 2005; Renegar et al., 2017).

The analyzing procedures for PAHs in biochar generally include three steps:

extraction using proper methods and solvents, followed by cleaning up the extracts,

and lastly, the quantitative analysis using high performance liquid chromatography

(HPLC) or gas chromatography-mass spectrometry (GC-MS; Hale et al., 2012; Hilber

et al., 2012; Rey-Salgueiro et al., 2016). During the extraction process, various

extraction techniques accompanied by different organic solvents have been employed

and thus, different extraction efficiencies in the first step (i.e. extraction) are reported.

Extraction techniques are included Soxhlet extraction, accelerated solvent extraction

(ASE), thermal extraction, ultrasonication extraction, microwave-assisted extraction

and reflux extraction. These techniques are often used for extracting semi-volatile

organic compounds from solid matrices such as soil or sediment, but with some

modifications. The techniques are listed in Table 1 and 88% of the literature is about

biochar methods. Soxhlet extraction and ASE are the most common methods for

extracting PAHs from biochar, because they have high extraction efficiency and good

repeatability, especially with soil or sediments. In the context of biochar analysis,

8
however, their efficiency depends heavily on the solvent (Jonker and Koelmans, 2002;

Hilber et al., 2012; Bucheli et al., 2015; Bachmann et al., 2016). With regards to

PAHs extraction, five different major methods and their coupling solvents are

discussed below.

3.1. Soxhlet extraction

A large volume of solvent (100–400 ml) and a relatively long time (6–48 h) are

needed to complete a conventional Soxhlet extraction ( u ue de Castro and

arc a-Ayuso, 1998; Lau et al., 2010; Zuloaga et al., 2012). However, this classical

method is not matri dependent, and no iltration is re uired a ter e traction ( u ue

de Castro and arc a-Ayuso, 1998). As investigated by Jonker and Koelmans (2002),

the efficiency is coupled with seven solvents used in extracting 13 EPA PAHs from

soot, coal and charcoal; however, large differences in extraction recovery have been

observed among solvents (Table 1). Among the given solvents, the best extractant was

toluene/methanol (MeOH) (1:6), which gave an average PAHs recovery ranging

between 61 and 100%. The other solvents such as dichloromethane (DCM), toluene,

MeOH, etc., or a mixture of these (with different volume ratios), have yielded poor

results. It was also noted that DCM, which averages PAHs recovery ranging from 38

to 93%, appeared to be the overall worst extractant, although it is the most widely

used solvent for extracting organic pollutants from soot, soils and sediments

(Hannigan et al., 1998; Sojinu et al., 2009; Cébron et al., 2013). As detected by Hilber

et al. (2012), toluene was the best extractant compared to the other individual solvents

or mixtures of toluene/ethanol (2:1), toluene/propanol (2:1), toluene/hexane (2:1),

9
toluene/heptane (2:1), toluene/DCM (2:1), hexane (100%) and heptane (100%) of

which the recovery of the 16 EPA PAHs by toluene was highest, ranging between 75

and 105% (Table 1). Kloss et al. (2012) used acetonitrile (MeCN) to extract PAHs

from nine biochars produced from three parent materials. They showed that the

recovery of the 16 EPA PAHs could reach as high as 88–105% (Table 1). However,

Fabbri et al. (2013) observed that acetone (Me2CO)/cyclohexane (1:1) showed better

extraction efficiency, especially for the LMW PAH, naphthalene. These results

showed that the best extractant which yielded the highest PAHs recovery varied in

different studies and the conditions applied during the extraction.

Prolonging extraction time may increase the extraction efficiency. However,

some studies have showed that after the extraction time exceeds a certain threshold,

the PAHs recovery did not increase, and therefore, 36 h of extraction time is noted to

be the most efficient (Hilber et al., 2012; Fabbri et al., 2013).

3.2. Accelerated solvent extraction (ASE)

The whole process of ASE can be automated. This method has advantages

compared to the Soxhlet extraction method due to the convenience of the operation,

shorter extraction time and lower solvent consumption. This method is also suitable

for processing a large number of samples. When used for soils and sediments, the

recovery of PAHs is 2x higher than the Soxhlet extraction (Wang et al., 2007).

However, in biochar processing, the efficiency still varies with different solvents. For

example, in a study by Freddo et al. (2012), DCM was superior to acetone

(Me2CO)/hexane (1:1) and DCM/Me2CO (1:1) in testing nine dissimilar biochars. The

10
results showed that 56% of the 16 EPA PAHs were below the detection limit with

DCM, while 88 and 81%, were below the detection limit with Me2CO/hexane (1:1)

and DCM/ Me2CO (1:1), respectively (Table 1). Machesky and Holm (2011) showed

that with extractions using Me2CO/hexane (1:1), the recovery of the 16 EPA PAHs

from biochar could be as high as 72–102 %, but were lower for naphthlene (26.2%;

Table 1). According to Hilber et al. (2012), none of DCM/ Me2CO (1:1), toluene and

toluene/MeOH (1:6) in ASE was able to extract any of the PAHs heavier than

chrysene (MW 228; Table 1). The ASE is not used as commonly as Soxhlet extraction

for PAH extractions from biochar.

3.3. Ultrasonication extraction

Some literature reported that ultrasonication extractions could provide a

comparable or even beter extraction efficiency than Soxhlet extractions (Sun et al.,

1998; Guerin, 1999). However, the efficiency of ultrasonication extraction is observed

to be highly dependent on the sample matrix and the content of contaminants in the

sample (Lau et al., 2010). In this method, centrifugation or filtration is required after

extraction. Similar to the methods described above, the extractant is an important

factor that affects extraction efficiency. As experienced by Fernandes and Brooks

(2003), with hexane, the recovery of internal standards (perdeuterated tetradecane,

phenanthrene and pyrene) from biochar was > 70%. Although Me2CO/cyclohexane

(1:1) was regarded as a relatively better extractant with higher PAHs recovery for

Soxhlet extraction in a biochar study, it did not show any superiority in

ultrasonic-assisted extraction. For example, the recovery of acenaphthene-d10,

11
phenanthrene-d10, chrysene-d12 from biochar was poor (0.4–9.0%; Fabbri et al., 2013).

However, it should be noted that various target compounds tested in the literature may

partly contribute to the differences in extraction recovery.

3.4. Thermal extraction

A combination of thermal extraction and gas chromatography-mass spectrometry

(TE-GC-MS) is also a powerful tool for quantifying PAHs in a solid matrix (Liu et

al., 2002; Zou et al., 2003; Tsytsik et al., 2008). The process of TE-GC-MS is time

efficient becuase it does not require solvent to pretreat samples. TE-GC-MS has been

widely employed to analyze PAHs/polychlorinated biphenyls in various sample types

including ambient air particulate matter, creosote and petroleum contaminated soils

(Environmental Protection Agency (EPA), 1996; Lau et al., 2010), and fly ash – a

kind of carbonaceous material (Liu et al., 2002; Zou et al., 2003; Tsytsik et al., 2008).

However, its application in biochar has not yet been reported. It is expected that

TE-GC-MS may play an important role in PAHs determination in biochar in the

future.

3.5. Microwave-assisted extraction

Microwave-assisted extraction is commonly used to extract target compounds

from solid matrices (Lopez-Avila et al., 1994; Losier and Girard, 2001). Unlike

classical conductive heating methods, microwaves heat the whole sample rapidly and

simultaneously, thereby reducing extraction time and solvent usage (Kaufmann and

Christen, 2002). Additionally, this unique heating mechanism provides selective

interaction with polar molecules, which greatly enhances the extraction efficiency of

12
PAHs (Letellier and Budzinski, 1999; Letellier et al., 1999). However, despite the

obvious advantages, only one study has employed this method for extracting PAHs

from biochar and biochar amended soil (Quilliam et al., 2013). Similar limited use has

been reported with reflux extraction (Fabbri et al., 2013).

Regardless of the method, solvent is the crucial factor that impacts on the

efficiency of extraction. Various solvents have been used in different extraction

methods, as discussed above, but only a few studies have compared their efficiency.

Therefore, it is difficult to decide the best method for a given purpose. For example,

toluene has been suggested as the best solvent in Soxhlet extraction, however, it did

not preform as well as expected in ASE (Hilber et al., 2012). This outcome may have

been due to the fact that each biochar possesses unique properties in terms of

composition. According to Keiluweit et al. (2012), extraction efficiency of different

methods was mainly controlled by the feedstock used in producing a particular

biochar and the temperature at which its production is carried out. Therefore, the

optimal solvent for one biochar might not be the best for another (Spokas, 2012b).

Overall, microwave-assisted extraction and reflux extraction have only been used

in a limited number of studies (Fabbri et al., 2013; Quilliam et al., 2013). Soxhlet

extraction is frequently applied and has a better extraction efficiency than ASE and

ultrasonication extraction (Hilber et al., 2012; Fabbri et al., 2013). Soxhlet extraction

coupled with 100% toluene has been recommended to extract PAHs from biochar by

the European Biochar Certificate (EBC) and the International Biochar Initiative (IBI,

2014). Despite this recommendation, different researchers will use different methods

13
for PAHs analysis. This is acceptable if the method used can demonstrate that it is fit

for purpose (Bucheli et al., 2015).

To obtain a set of standardized protocols for quantitative analysis of PAHs or

other toxic organic compounds in biochar, further research should give greater

emphasis to biochar properties. Reducing biochar particle size and simultaneously

increasing the extraction time may help enhance extraction efficiency (Machesky and

Holm, 2011; Hale et al., 2012; Hilber et al., 2012). Usage of sufficient number of

biochar samples and suitable reference materials should be adopted in order to obtain

a reliable outcome. As suggested by Bucheli et al. (2015), isotopically labelled

analogues for each of the target analytes should be used as surrogate standards, added

before extraction, and their recovery reported. Factors such as feedstock resource,

conditions applied in biochar production, and biochar particle size should be

considered when comparing differences of various methods.

3.6 Cleaning up and quantitative analysis

The above details summarized the methods used in the“extraction” step for

analyzing PAHs in biochar. There are different methods could be used in this stage.

For the the steps of cleaning up and quantitative analysis of PAHs in biochar, some

simple procedures are practiced. For example, a silica gel column is often used to

clean up the extract whereas in the quantitative analysis, chromatographic columns

such as the PAHs special C18 and a fluorescence/ultraviolet detector are commonly

used in the HPLC. Further to this, a gas chromatography equipped with a fused silica

capillary column for separation and a mass spectrometer coupled with an ionization

14
source, mass analyzer and detector are jointly applied in the GC-MS system. In the

quantitative analysis, deuterated compounds such as the naphthalene-d8,

phenenthrene-d10, and benzo[a]anthracence-d12 are used as the internal standard

compounds.

4. PAHs content in biochar and impact factors

It is important to know the amount of PAHs present in biochar before it is applied

to the soil or used for any other applications. Therefore, total concentrations of PAHs

in biochar have been the focus of many studies. Recently, the International Biochar

Initiative (IBI) set the threshold values of the ∑16 EPA PAHs in safe biochar to 6–20

mg/kg (IBI, 2013), and the EBC requires the ∑16 EPA PAHs to be below 4 and 12

mg/kg in premium and basic grade biochar, respectively (EBC, 2016). However, PAH

concentrations in biochar in current studies shows a wide variation from < 0.1 to >

10,000 mg/kg (Table 1). This is why some researchers deem that PAHs content of

biochar is too low to pose any substantial ecotoxicological risk to soil environments

(Fernandes and Brooks, 2003; Singh et al., 2010; Hale et al., 2012). Hale et al. (2012)

quantified the total PAHs concentration in 50 different biochars, which were produced

between 250 and 900 °C, using various biomass substrates including manure, paper

mill waste, pine wood, and corn straw. The results showed that the concentrations of

the ∑16 EPA PAHs were between 0.07 and 3.27 mg/kg. Singh et al. (2010) have

measured PAH concentrations in 11 biochar types made from five biomass substrates

such as wood, tree leaves, papermill sludge, poultry litter and cow manure, with a

pyrolysis temperature o 400 and 550 °C. According to their results, the ∑16 EPA

15
PAHs values were below the health investigation level (< 0.5 mg/kg; NEPM, 1999).

Similarly, Fernandes and Brooks (2003) found that carbon black, vegetation fire

residues, and straw and wood charcoal had only residual concentrations of the ∑16

EPA PAHs (< 0.2 mg/kg). However, other studies have noted higher PAH

concentrations in biochars (Zhurinsh et al., 2005; Fabbri et al., 2013; Quilliam et al.,

2013). According to Fabbri et al. (2013), total 16 EPA PAHs concentrations ranged

between 1.2 and 19 mg/kg in 11 biochar samples made from sawdust, corn stover,

wood waste, etc. with a pyorlysis temperature range of 350 to 850 °C. Meanwhile,

Quilliam et al. (2013) has determined a high ∑16 EPA PAHs value of 64.65 mg/kg

for rice husk biochar pyrolysed at 300–600 °C. A higher value of 145 mg/kg has been

reported for pinewood charcoal by Zhurinsh et al. (2005). The highest PAHs content

reported is 2945 mg/kg o ∑16 EPA PAHs, which was measured in a wood gasifier

system (Schimmelpfennig and Glaser, 2012). Nevertheless, current technology has

been able to produce the products with PAHs below detection limit as well

(Yargicoglu et al., 2015). The above studies show that PAHs content is strongly

dependent on the type of feedstock and the conditions applied in biochar production.

In addition to the total PAHs content of biochar, abundance of individual PAH is

of concern because the toxicity of each is distinctly different. Many recent studies

have shown naphthalene to be the major hazadous compound (Morf et al., 2002;

Spokas et al., 2011; Freddo et al., 2012; Hale et al., 2012; Hilber et al., 2012; Kloss et

al., 2012; Schimmelpfennig and Glaser, 2012; Fabbri et al., 2013; Bachmann et al.,

2016). Fabbri et al. (2013) has determined the highest value for naphthalene with a

16
concentration ranging from 1.75 to 3.36 mg/kg, followed by phenanthrene (0.25–3.88

mg/kg). However, different results were obtained by Nakajima et al. (2007) where the

highest PAH concentrations were found with fluorene (ca. 2.09–3.74 mg/kg),

followed by phenanthrene (ca. 1.43–3.39 mg/kg) and anthracene (ca. 0.81–1.62

mg/kg). Among the given 16 EPA PAHs, benzo[a]pyrene is of the greatest concern

due to its high carcinogenicity. Fortunately, the available data shows that

benzo[a]pyrene is less available in biochars. Fabbri et al. (2013) detected

benzo[a]pyrene in all tested biochar samples, however, the concentration ranged only

from 0.01 to 0.67 mg/kg, which is similar to the results obtained by Brown et al.

(2006).

Factors that influence PAH yield include pyrolysis process, pyrolysis

temperature, biochar feedstock resources, and treatment during and after pyrolysis

(Bucheli et al., 2015; Buss et al., 2016; Buss and Mašek, 2016). In addition, O2/CO2

content during and after pyrolysis, water content of feedstock can also have some

effect on PAHs yield in biochar (Keiluweit et al., 2010; Machesky and Holm, 2011;

Keiluweit et al., 2012; Kwon et al., 2012, 2013, 2015; Cho et al., 2015a, b;). Details

related to each of these factors are discussed below.

4.1. Pyrolysis process

The pyrolysis process, including pyrolysis style and heating rate, and the

residence time, is the most important factor responsible for PAHs yield in biochar.

The total PAHs in 102 biochars (or carbonaceous material) produced from different

pyrolysis styles are shown in Fig. 3, and biochars (or carbonaceous material)

17
produced from traditional kiln or soil mound and fast pyrolysis have yielded greater

amount of PAHs than from other pyrolysis styles. Specifically, most biochars

produced from slow pyrolysis contained a lower concentration of PAHs (< 0.7 mg/kg,

with one exception of 83 mg/kg; n=53) than those produced from fast pyrolysis

(0.01–74 mg/kg; n=10). The PAHs are more likely to escape to the atmosphere in

gaseous form during the process of slow pyrolysis with a long residence time

(Garcia-Perez, 2008). On the other hand, during fast pyrolysis, they are more likely to

condense back onto the biochar surface (Hale et al., 2012; Quilliam et al., 2013).

Nevertheless, various maximum reaction temperatures have been reported in slow and

fast pyrolysis (Septien et al., 2012; Song and Guo, 2012; Ronsse et al., 2013).

Therefore, it is necessary to consider reaction temperature when comparing PAHs

concentrations in these studies. Usually modern pyrolysis reactors are able to produce

biochar with sufficiently low PAHs concentrations. In these reactors, control of

volatiles and avoidance of re-condensation of tars have been critical to achieve

compliance with the IBI or EBC thresholds for high quality biochars (Buss et al.,

2016; Madej et al., 2016).

4.2 Pyrolysis temperature

Pyrolysis temperature is also one of the key factors influencing PAH yield in

biochar. However, a consensus has not yet emerged regarding the relationship.

According to certain investigations, the yield of PAHs increased with increased

pyrolysis temperature (McGrath et al., 2001; Nakajima et al., 2007; Keiluweit et al.,

2012). However, an opposite conclusion was obtained by some other research (Brown

18
et al., 2006; Hale et al., 2012; Keiluweit et al., 2012; Spokas, 2012a; Devi and Saroha,

2015). It is interesting to note that in some recent studies, a moderate temperature,

generally in the range of 400–550 °C, was found to produce higher PAHs content. For

example, Keiluweit et al. (2012) and Devi and Saroha (2015) quantified PAH content

in biochar pyrolysed over a range of 100–700 °C and found that biochar produced at

400 and 500 °C had significantly higher PAHs content than that produced at other

temperatures. Among the 40 biochar samples investigated by Brown et al. (2006), the

biochars produced at 450 and 525 °C had higher PAH contents of 16 and 7 mg/kg,

respectively, which were significantly higher than in biochar made at 1000 °C (only 3

mg/kg). High temperature ( ≥ 500 °C) minimises the concentration of extractable

PAHs, possibly due to volatilization of the amorphous phases, nuclear condensation

into larger non-extractable sheets (Keiluweit et al., 2010), and strong sorptive

retention by more condensed biochars (Sun and Zhou, 2008). Even so, it is not proven

that high charring temperature results in a low PAHs content in biochar.

Pyrolysis temperature influences not only the total yield of PAHs, but also their

composition. As mentioned in section 2, low temeperature produces LMW PAHs and

vice versa. Garcia-Perez (2008) confirmed that biochar produced at low temperature

(350–600 °C) contains a lower content of PAHs, dominated by alkylated PAHs with

lower toxicity. In an investigation of cellulose pyrolysis, McGrath et al. (2003) found

that a lower toxicity of 2–4 ring PAHs was observed at and above 400 °C.

Benzo[a]pyrene and benz[a]anthracene, which had a greater toxicity, were observed at

and above 500 °C.

19
 It is difficult to decide exactly which temperature is optimal for producing the

safest biochar for envionmental application. We suggest that high temperature

biochars are more suitable for application as (i) even if they have more PAHs than

low temperature biochars, most of these PAHs are not extractable and are thus not

released into the environment, and (ii) they have a greater capacity to immobilize or

remove various organic and inorganic pollutants present in soil or in an aqueous phase

(Keiluweit et al., 2012).

4.3. Treatment during and after pyrolysis

Recent research on the biochars with high volatile organic compounds (VOC)

revealed the importance of some treatments on reducing PAHs concentration (Buss et

al., 2015, 2016; Buss and Mašek, 2016). As in some pyrolysis units, or under specific

conditions (such as fast pyrolysis), pyrolysis vapour can deposit on biochar in

significant amounts, resulting in high PAHs biochar. In such a case, outgassing,

namely diverting and collecting pyrolysis gases separately during pyrolysis or cooling

process, is a vital measure for producing low-PAH biochar (Bucheli et al., 2015).

Increasing carrier gas flow rate facilitates removal of pyrolysis gas which can

therefore reduce the adsorption and recondensation of PAHs into the biochar porous

structure (Buss et al., 2016; Madej et al., 2016). In addition, thermal treatment has

been proven to be an effective way for reducing PAHs contamination. As reported

above, drying biochar at 100 °C for 24 h caused a reduction in the ∑16 EPA PAHs

content to a level of 33.8–88.1% (Kołtowski and Oleszczuk, 2015) while drying at

200 °C for 20 h resulted in a reduction in ∑16 EPA PAHs content up to 70.6–95.7%

20
and a reduction in water-extractable PAH nearly 100% (Buss and Mašek, 2016).

4.4. Feedstock resources

Feedstock may be the primary factor that influences PAHs content in biochar.

For example, some intrinsic properties such as plant species (Zhurinsh et al., 2005)

and their chemical composition (Hale et al., 2012; Quilliam et al., 2013) may

contribute to the concentrations of different PAHs. Generally, cellulose, hemicellulose

and lignin are noted to be the the major PAHs precursors (McGrath et al., 2007). In

some studies, lignin-rich feedstocks have been observed to produce biochar with

lower PAHs concentrations than those which are comprised mainly of pectin and

cellulose (Sharma and Hajaligol, 2003; Sharma et al., 2004). In contrast, Keiluweit et

al. (2012) found that there was no significant correlation between lignin content and

PAHs concentration, with exception of biochars prepared at 500 °C. McGrath et al.

(2003) found that the yield of PAHs with 2–5 rings obtained from the pyrolysis of

lignin were more or less similar to those obtained from D-glucose and sucrose. Beside

lignin content, the composition of lignin, the C, H, N, and O elemental contents, and

cellulose and hemicellulose content of the feedstocks, which vary greatly, may

together explain the different PAHs concentrations and their quality (Buss et al.,

2016). These conflicting results are a clear indication of the research gap that exists

between primary feedstock and final PAHs content in biochar. More research is

needed on this topic.

4.5. Other factors

Other factors that influence PAHs yield in biochar include (i) mineral content and

21
moisture content of feedstock (Bignal et al., 2008; Qiu et al., 2015), and (ii)

appearance of O2 during the process of pyrolysis or the post-pyrolysis cooling process.

Some evidence suggests that biomass high in ash and moisture content facilitates

formation of a greater amount of PAHs in biochar (Bignal et al., 2008;

Dieguez-Alonso et al., 2015; Qiu et al., 2015). McGrath et al. (2007) showed that the

presence of inorganic salts in a cellulose matrix could shift the maximum evolution of

PAHs to a lower temperature.With respect to O2 content during pyrolysis,

contradictory results have been reported. According to McGrath et al. (2003),

presence of 5–10% O2 in the carrier gas during pyrolysis reduces the PAH yield. Yet,

Rey-Salgueiro et al. (2004) report by limiting the O2 input to a minimum, no PAHs

were observed in oven combustion ashes. After pyrolysis, cooling biochar in an

anaerobic environment is necessary for lower PAHs content (Spokas, 2012a). In

addition, several studies have indicated that the presence of CO2 enhanced thermal

cracking and blocked the pathway to the formation of PAHs (Kwon et al., 2012, 2013,

2015; Cho et al., 2015a, b). These results provide important clues regarding how to

produce biochars with lower PAHs yield. However, these observations need to be

validated using a wide array of feedstocks and biochar manufacturing conditions.

5. Bioavailable PAHs in biochar

It is important to know the bioavailable fraction of pollutants as well as their total

concentration when assessing their risk to the environment. Therefore, some research

has been initiated to investigate the bioavailability of PAHs in biochar. To the best of

our knowledge, Hale et al. (2012) were the first to measure bioavailability of PAHs in

22
biochar. In their study, a passive sampler of polyoxymethylene (POM) was employed

to investigate bioavailable PAHs in a suite of over 50 biochars. The recovery for this

method ranged from 70 to 130% and the bioavailable PAHs, which accounted for

1–10% of the total PAHs concentration, ranged between 0.17 and 162 ng/l. Zielińska

and Oleszczuk (2016) also used POM to extract PAHs from sewage sludge-derived

biochar produced at 500–700 °C. Their results showed that bioavailable PAHs were in

the range of 86–216 ng/l. A significant positive relationship between the bioavailable

concentrations of PAHs and the degree of aromaticity of biochar, as indicated by the

H/C ratio, was also found (P=0.05). Other chemical approaches such as Tenax

extraction, hydroxypropyl-β-cyclodextrin extraction (HPCD) and solid phase

microextraction (SPME), which are commonly used to quantify the bioavailability of

organic pollutants in soils/sediments, have not been extensively applied to biochar.

However, Mayer et al. (2016) pointed out that none of Tenax extraction, HPCD

extraction, and sorptive bioaccessibility extraction (HPCD combined silicone rod and

POM) were suitable for the direct measurement of the bioaccessibility of PAHs due to

the strong sorption of PAHs onto biochar. Therefore, extensive studies should be

conducted to prove their feasibility in predicting PAHs bioavailability in biochar.

To summarize the above research, despite high concentrations of total PAHs of

some biochars (more than hundreds of mg/kg), these biochars resulted in limited

PAHs exposure, and most often would act as a sorption sink rather than as a source for

PAHs (Hale et al., 2012; Mayer et al., 2016). However, the environmental risk of high

total PAHs on biochar still has to be considered when biochar is used as a soil

23
amendment because the bioavailability of PAHs in soil can be influenced by several

factors. First, the dissolved organic matter in soil or the dissolved organic carbon

content in biochar (especially low temperature biochar) could enhance the leaching of

PAHs through soil (Dutta et al., 2016). Secondly, microbes or plant roots in soil might

facilitate the desorption of PAHs from biochar, either by producing biosurfactants or

by secreteing organic acids (An et al., 2011; Gao et al., 2015), thereby increasing

PAHs bioavailability. Since the activity of microbes and plant roots is controlled by

soil conditions (such as the soil type, nutrients, humidity, temperature and pH), these

factors together decide the fate of a variety of PAHs in biochar amended soil and are

thus worthy of full investigation. In such a case, laboratory and field research should

be carried out jointly.

7. Conclusions

Biochar application is becoming increasingly popular as a promising approach to

improve soil physico-chemical and biological properties. However, the potential

negative effect of PAHs in biochar has not yet been properly considered due to the

scarcity of knowledge about their formation and the factors that impact on PAHs yield

and quality, as well as a lack of conformity with respect to the most accurate and

efficient analytical methods to measure total and bioavailable PAHs. To minimize the

environmental risk of PAHs in biochar, it is recommended firstly that feedstock

without PAHs contamination be chosen. Secondly, adopting slow pyrolysis with lower

temperature (< 500 °C) could decrease total PAHs concentration and reduce highly

toxic PAHs species in biochar. However, highly condensed biochar produced at high

24
temperature may have a wider range of uses in environmental management due to

their greater capacity to immobilize or remove pollutants from soil and water, and due

to their non-extractable and hardly “releasable” PAHs.

Future research should take into the account: (i) The need for the development of

standard methods for quantifying total and bioavailable PAHs in biochar. During this

process, some factors including the number of biochar samples, feedstock resources,

pyrolysis conditions, particle size of biochar, etc. should be considered. (ii) The need

to clearly understand the relationship between the key chemical components in

feedstock and PAHs formation, and reveal how pyrolysis temperature (especially high

temperature) influences PAH yield in biochar. (iii) The need to carry out studies on

the impact of biochar on the ecological environment at long timescales. Both

laboratory and field research should be undertaken to deepen the understanding of

how various biological factors and non-biological factors influence the environmental

behavior of PAHs (especially their bioavailability) in biochar. In these studies,

ecotoxicological tests including bioavailability tests with organisms should play an

important role, which will help assess the environmental risk of biochar application.

Acknowledgements

This research was supported by the Top Young Academic Leaders of Higher

Learning Institutions of Shanxi [The No. 3 document approved by Shanxi Provincial

Education Department in 2016], the National Natural Science Foundation of China

[No. 41101297 and 21507077] and the State Key Laboratory of Soil and Sustainable

25
Agriculture, Institute of Soil Science, Chinese Academy of Sciences [Y412201451].

The authors gratefully acknowledge Prof. Dr. Erdem Idiz, Prof. Dr. James Maxwell,

Prof. Dr. Ingrid Koegel-Knabner and the anonymous reviewers for their valuable

comments and constructive suggestions.

26
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43
 List of Tables

Table 1 Methods for extracting total PAHs from biochar and carbonaceous material.

44
 List of Figures

Fig. 1. Products from the pyrolysis process.

Fig. 2. Effect of pyrolysis temperature and heating rate on the yield of three

bio-products.

Fig. 3. Total PAHs in biochar produced from different pyrolysis styles.

45
Fig. 1. Products from the pyrolysis process as adapted from Zheng et al. (2011)

46
 a: fast pyrolysis b: slow pyrolysis
100 100

80 80
Product yield (%)

Product yield (%)

60 60
bio-gas bio-gas
40 40
bio-oil bio-oil
20 biochar 20 biochar

0 0
350 400 450 500 550 350 400 450 500 550
Temperature ( C) Temperature ( C)

Fig. 2. Effect of pyrolysis temperature and heating rate on the yield of three

bio-products: a, fast pyroysis (data are collected from Garcia-Perez et al. (2008).

Biomass of mallee woody was fed directly into the reaction bed 5 min after the

desired temperature was achieved); b, slow pyrolysis (biomass including corn cobs,

corn stover, walnut shells, wood chips and defatted dried distiller grains were

pyrolyzed with a heating rate of 7 °C/min (data are taken from Zheng et al. (2011).

47
 100.0 Traditional Kiln/Soil Mound
3.0
2.5 Slow Pyrolysis
90.0
Fast Pyrolysis
2.0
80.0 Microwave Assisted Pyrolysis
1.5
Hydrothermal
70.0 1.0
Unknown
Total PAHs (mg/ kg)

0.5
60.0
0.0
50.0 0 50 100

40.0

30.0

20.0

10.0

0.0
0 20 40 60 80 100
Biochar and carbonaceous material

Fig. 3. Total PAHs in biochar produced from different pyrolysis styles. The data are

collected from Spokas (2012b).

48
Table 1

Methods for extracting total PAHs from biochar and carbonaceous material (n.a., not

available).
Tempe Nu
rature mbe Total
Meth Feed Sam Extractant Detail Recov Refere
(°C); r of g PAHs
od stock ple information ery nce
residen sam mg/kg
ce time ples
8.1-84.
9 (for
Dies soot
el and
soot, dust)
(Ferna
urba < 0.2
Stra 450; 1h 70 ml ndes
n (for
Ultras w for extractant, > and
dust, 7 Hexane charco
onic a woo charco 0.024 g 70% Brook
chim al,
d al sample, 1 h s,
ney carbon
2003)
soot, black
charc and
oal fire
residu
es) h
20 ml
350-85 Me2CO/cy (Fabbr
Ultras Vario Bioc extractant, 0.4-9
0; 20 clohexane 1.2-19 i et al.,
onic b us har 1.0 g biochar, %
n.a. （1:1） 2013)
30 min
Woo
d,
grass 600-75 (Hilbe
Soxhl Bioc 0.1-1.0 g 71-10 9.1-35
or 0 4 Toluene r et al.,
et c har biochar, 36 h 5% 5.2
their n.a. 2012)
resid
ues
Woo (Schi
350-80
d and mmelp
0 (200
Soxhl orga Bioc 0.8-11, fennig
for 66 Hexane 8h n.a.
et nic har 103 and
hydroc
lefto Glaser,
har)
vers 2012)
Soxhl Vario Bioc 350-85 20 Me2CO/cy 160 ml 67-88 1.2-19 (Fabbr

49
 et b us har 0; clohexane extractant, % i et al.,
n.a. (1:1) 1.0 g biochar, 2013)
36 h
39-84
Me2CO
%
Me2CO/cy 160 ml
10-76
clohexane extractant,
%
(5:1) 1.0 g biochar,
Me2CO/cy 18 h
29-75
clohexane
%
(1:1)
Cypr
ess, (Nakaj
Toluene
Soxhl chest Bioc 400-10 0.06-0. ima et
12 /EtOH 16 h n.a.
et nut, har 00; 1h 15 al.,
(3:7)
bam 2007)
boo
Woo
d,
leave
s,
pape
r
400-55 (Singh
Soxhl sludg Bioc
0; 40 11 DCM 16 h n.a. <0.5 et al.,
et e, har
min 2010)
poult
ry
litter,
cow
man
ure
Pulv Toluene/M 61-10
erize eOH (1:6) 0%
d Toluene/Et 65-97
charc OH (1:4) %
oal, Benzene/1- (Jonke
70 ml 45-94
coal, propanol r and
Soxhl extractant, %
traffi Soot n.a. 6 (3:1) n.a. Koelm
et d 10-40 mg
c Benzene/Et 61-91 ans,
soot, 16 h
soot, OH (3:2) % 2002)
woo Hexane/M 61-81
d e2CO (3:1) %
soot, 16-10
Toluene
oil 0%
50
 soot,
and 38-93
DCM
coal %
soot
0.1-3.3
for
slow
pyroly
sis
biocha
r,
90 ml
250-90 0.3 for (Hale
Soxhl Vario Bioc extractant, 56-79
0; 50 Toluene fast et al.,
et e us har 0.5 g biochar, %
0.5-8 h pyrolys 2012)
160 °C, 6 h
is
biochar
and 45
for
gasific
ation
biochar
Whe
at
400-52
straw
5; 5h
, 150 ml
for (Kloss
Soxhl woo Bioc extractant, 85-10 1.8-33.
straw 9 MeCN et al.,
et c d and har 5.0 g biochar, 5% 7
and 2012)
needl 195 °C, 1.5 h
10h for
e
wood
mixt
ure
350-75 50 ml
(Buss
Soxhl Vario Bioc 0; extractant, 1.2-10
46 Toluene n.a. et al.,
et c us har 10-40 1.0 g biochar, 0
2016)
min 36 h
Woo
d
chips
De la
, 500-62
Soxhl Bioc 0.2-0.4 mg 0.9-15. Rosa
paper 0; 4 Toluene n.a.
et f har biochar, 36 h 4 et al.,
sludg 20 min
2016)
e,
and
sewa

51
 ge
sludg
e
Me2CO/cy
7-80
clohexane
%
(1:1)
Me2CO/cy 80 ml
350-85 7-56 (Fabbr
Reflu Vario Bioc clohexane extractant,
0; 20 % 1.2-19 i et al.,
xb us har (1:5) 2.0 g biochar,
n.a. 2013)
4h 11-83
DCM
%
58-68
Toluene
%
5-94
%,
highly
varied
depen
Stra
3×10 ml ding
w (Keilu
Toluene/M extractant, upon
and Bioc 100-70 0.04-2 weit et
ASE 14 eOH 0.1g biochar, feedst
pine har 0; 1h 0.9 i al.,
(1:1) 100 °C and ock
shavi 2012)
1000 psi resour
ngs
ce and
pyroly
sis
tempe
rature
56%
Red
of the
woo
PAHs
d,
lower
rice 0.1-5.7
DCM than
straw for
300 °C 5.0 g biochar, limit
, biocha
; 12 h 100 °C, 10.3 of (Fredd
maiz r and
Bioc and Mpa. 60 ml detect o et
ASE c e, 9 8.7 for
har exractant, 5 ion al.,
saw gasific
600 °C min static, 1 88% 2012)
mill ation
;5h static cycle of
soft biocha
PAHs
woo DCM/Me2 r
lower
d and CO (1:1)
than
bam
limit
boo
of

52
 detect
ion
81%
of
PAHs
lower
Me2CO/he
than
xane (1:1)
limit
of
detect
ion
1.0 g biochar,
100 °C and perfor
2000 psi, mance
preheating 5 of
DCM/Me2
min, 5 min ASE
CO
static, flush inferi
(1:1)
volume 60%, or
Woo
purge time to
d,
with N2 1 Soxhl
grass 600-75 (Hilbe
c Bioc MPa for 60 s et , 9.1-35
ASE or 0 4 r et al.,
har Toluene ASE 5.2
their n.a. 2012)
not
resid
capabl
ues
2000 psi, e of
Toluene/M other extrac
eOH conditions as ting
(1:6) above PAHs
heavie
r than
CHR.
5.0 g biochar,
100 °C and
(Mach
1500 psi, 5
Corn esky
Bioc 450-75 Me2CO/he min static, 26.2-1
ASE c stove 9 n.a. and
har 0; n.a. xane (1:1) flush volume 02%
r Holm,
60% for100
2011)
s, 3 static
cycles.
Micro Rice (Quilli
Hexane/M 20 ml
wave husk, Bioc 450; 9.6-64. am et
2 e2CO/Me3 exractant, 5 g n.a.
accele woo har 48h 7 al.,
N (10:9:1) biochar
rated d 2013)
a
Compounds for determination of recovery were perdeuterated phenanthrene and perdeuterated
53
pyrene; b compounds for determination of recovery were acenaphthene-d10, phenenthrene-d10,

chrysene-d12; c compounds for determination of recovery were 16 EPA PAHs; d compounds for

determination of recovery were13 EPA PAHs, with naphthalene, acenapthylene and acenaphthene

excluded; tested samples included traffic soot, oil soot, wood soot, coal soot, coal and charcoal; e

compounds used for determination of recovery were phenenthrene-d10, pyrene-d10,

benz[a]anthracene-d12, benzo[a]pyrene-d12 and benzo[g,h,i]perylene-d12; f compound for

determination of recovery was indeno[1, 2, 3-cd]fluoranthene; g solvents were mixed in volume

ratio. Some solvent names (abbreviation): dichloromethane (DCM), methanol (MeOH),

acetonitrile (MeCN), acetone (Me2CO), ethanol (EtOH), triethylamine (Me3N); h sum of 12 US

EPA PAHs (phenanthrene to benzo[ghi]perylene) + triphenylene + benzo[e]pyrene; i sum of 10 US

EPA PAHs (without naphthalene, acenaphthene, acenaphthylene, fluorene, benzo[k]fluoranthene,

dibenz[a,h]anthracene).

54
 Highlights

•Review of research progress on PAHs in biochar. •Temperature the key factor for

PAH formation and yield. •Slow pyrolysis and longer residence time result in

lower PAHs vs. fast pyrolysis. •Soxhlet and accelerated solvent extraction major

methods to extract PAHs from biochar. •Gaps and future research needs

highlighted

55
 Low temperature
Formation mechanism
High temperature
Soxhlet extraction
Accelerated solvent extraction

Analysing method for total PAHs Ultrasonication extraction

Thermal extraction
Measures to reduce
Microwave-assisted extraction
PAHs in biochar PAHs in biochar
Feedstock resources
and future research
Pyrolysis temperature
Impact factors Pyrolysis process (heating rate, residence time)
Treatment during and after pyrolysis

Moisture, oxygen, mineral content, etc.

Bioavailable PAHs in biochar

56