Sun et al.

Biochar (2022) 4:60

https://doi.org/10.1007/s42773-022-00184-9 Biochar

ORIGINAL RESEARCH Open Access

Development of a new hydrophobic

magnetic biochar for removing oil spills
on the water surface
Xiaojun Sun1,2, Hongrui Fu1,2, Mutai Bao1,2* , Wei Liu1,2, Chengyi Luo1,2, Yang Li3, Yiming Li1,2 and Jinren Lu2

Abstract
More technologies are urgently needed for combined use to effectively eliminate the effect of oil spills, an envi-
ronmental problem of widespread concern. Among these technologies, sorption methods are available to remove
residual oil and prevent the further spread on the water surface. In this study, biochars, prepared from different feed-
stock materials and pyrolysis temperatures, were screened and further modified to improve their application in the
water environment. Among cornstalk biochar (CSBC), corncob biochar (CCBC), Sophora sawdust biochar (SSBC), and
rice husk biochar (RHBC), the CSBC had excellent oil sorption capacity, especially prepared at 350℃ (CSBC350), which
has a complete and full pore structure. Furthermore, magnetic and silane agent modifications of CSBC350 (OMBC)
were performed to enhance the properties of the magnetic field controllability and hydrophobicity to increase oil
sorption. The OMBC exhibited satisfactory oil sorption capacities to crude oil, diesel oil, and engine oil in the water-oil
system of 8.77 g ­g−1, 4.01 g ­g−1, and 4.44 g ­g−1, respectively. The sorption process of CSBC350 and OMBC complied
with the pseudo-second-order kinetics ­(R2 > 0.97) and the Langmuir isotherm models ­(R2 > 0.80) based on the highest
regression coefficients. The sorption mechanisms are dominated by hydrophobic forces, pore intercepts, and hydro-
gen-bond interactions. The biochar adsorbent can availably cooperate with other physical methods to eliminate oil
contaminants, which can be an outstanding fuel source for producing heat.

Highlights

• Low temperature (350℃) pyrolyzed cornstalk biochar has the highest oil sorption ability among the various bio-
chars.
• Modified cornstalk biochar has excellent hydrophobicity and floatage with a higher oil adsorptivity.
• The oil sorption process of the modified biochar conforms to pseudo-first-order kinetics and the Langmuir iso-
therm models.

Keywords: Oil spill, Cornstalk biochar, Hydrophobic magnetic biochar, Oil sorption

*Correspondence: [email protected]
1
Frontiers Science Center for Deep Ocean Multispheres and Earth System,
and Key Laboratory of Marine Chemistry Theory and Technology, Ministry
of Education, Ocean University of China, Qingdao 266100, China
Full list of author information is available at the end of the article

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Sun et al. Biochar (2022) 4:60 Page 2 of 17

Graphical Abstract

1 Introduction marine oil spill response. Even though these techniques

Crude oil, as the dominant primary energy resource and are partly successful, there are a few environmental issues
raw material in modern industrial systems, is constantly and weaknesses that limit their application to thoroughly
exploited, processed, transported, and stored, which remove oil, for example, the ecotoxicity of chemical dis-
inevitably results in oil wastewater effluents as well as oil persants, the release of toxic matter by burning, and
spills (Emeka Ndimele et al. 2018). According to statistics incomplete results of oil collection (Bianco et al. 2021).
from 1970 to 2021, approximately 5.87 million tonnes Nevertheless, from an economic and ecological perspec-
of oil were lost as a result of tanker incidents globally tive, sorption methods, including natural organic/min-
(ITOPF 2022). Some well-known catastrophic accidents eral materials, synthetic organic, and inorganic materials,
have caused extensive concern for petroleum pollution, are the most suitable to remove and collect oil slicks,
such as the Deepwater Horizon spill that lost 779 million preventing spilled oil from further drift and diffusion.
liters of oil (Atlas et al. 2011), the Hebei Spirit spill that Ideal adsorbents should have the following features: inex-
led 10,900 tons of crude oil to escape into the sea (Yim pensive and easily available, porous, with high specific
et al. 2011), and the Sanchi spill that released almost 1 surface area, environmentally friendly, and easily recov-
million barrels of oil (Chen et al. 2020a, b). Oil spill is erable (Gurav et al. 2021a, b). Natural sorbents, especially
a serious marine environmental problem and a press- carbonaceous materials, are the most environmentally
ing social problem for the government. When spilled oil friendly and easily available, compared with other materi-
enters the marine environment, these petroleum hydro- als (Gupta et al. Gupta and Tai 2016).
carbons cause the mass mortality of sea birds, seals, sea Biochar (BC) is a carbon-rich solid material produced
otters, and other sea life within a few weeks (Barron through pyrolysis at specific temperatures (300–900℃) in
2012). In the long term, the oil will give rise to the decline an oxygen-limited environment (Liang et al. 2021). The
and eventual extinction of fish stocks, damage to the tis- precursor materials of biochar generally include agri-
sue of the digestive gland of krill, and chlorophyll-defi- cultural wastes, kitchen wastes, animal manure, crusta-
cient propagules in mangroves (Veldkornet et al. 2020). cean shells, and municipal solid wastes. Thermochemical
As a persistent organic pollutant, hydrocarbons may conversion of solid waste into biochar can bring multi-
cause extensive or permanent damage to marine ecosys- functional benefits to the circular economy in addition
tems (Chandra et al. 2013). to climate change mitigation and carbon sequestration.
For that reason, a sequence of classical physical, chemi- As a carbon–neutral tool for sustainable development,
cal, and bioremediation techniques including in situ biochar is widely used in soil amendment, delivery of
burning, dispersants, physical containment, skimmers agrochemicals and microbes, catalyst production, envi-
and adsorbents, and biodegradation have been applied ronmental remediation, building material manufacturing,
to clean the oil slicks (Liu et al. 2017; Tran et al. 2021). and feed formulation (Wang et al. 2021). In the aspect of
However, how to remove oil more effectively from sea- contamination remediation, biochar is an almost ideal
water is a critical problem, as it is of great importance to adsorbent. It has been used in the removal of organic
Sun et al. Biochar (2022) 4:60 Page 3 of 17

contaminants containing antibiotics (Liang et al. 2022), n-octadecyl trimethoxy silane (OTMS) was obtained
dyes (Wathukarage et al. 2019), persistent organic pol- from Rhawn (China). Ferrous sulfate heptahydrate
lutants (POPs) (Shi et al. 2016; Zhang et al. 2018), heavy ­(FeSO4·7H2O), ferric chloride hexahydrate ­(FeCl3·6H2O),
metals (Agrafioti et al. 2014), nitrogen and phosphorus sodium hydroxide, and ethanol were purchased from Sin-
(Dai et al. 2020), based on its porosity, high surface area, opharm Chemical Reagent Limited Corporation (Shang-
and abundant functional groups, etc. hai, China). Diesel and engine oil were provided by a local
In recent years, biochar has gradually attracted much petrol station (Qingdao, China). Crude oil was obtained
attention on adsorbing oil. In previous studies, various from an oilfield in the Bohai Sea (China).
biochars have been studied as adsorbents for the puri-
fication of oil pollution, such as rice husk BC (Angelova
et al. 2011), peat-derived BC (AlAmeri et al. 2019), and 2.2 Preparation of biochar
sawdust BC (Silvani et al. 2017). The oil sorption effi- The process of biochar preparation is shown in Addi-
ciency of pristine BC to a great extent relies on its hydro- tional file 1: Fig. S1. The feedstock material, with impu-
phobicity, which guarantees that biochar does not sink rities removed, was chopped into small chunks, washed
into the aqueous phase (Madhubashani et al. 2021). The with deionized water 3 times, and dried at 105℃ over-
enhancement of hydrophobicity by modifying the bio- night. A crucible was filled with feedstock material and
char surface can facilitate the sorption of the oil. Hence, was wrapped in aluminum foil. Then pyrolysis was per-
research focused on biochar modification had been con- formed at 350℃, 500℃, and 650℃ in a muffle furnace
ducted by researchers. Fir BC, red pine BC, and lettuce (Zhonghuan, SX-G07103) under oxygen-limited condi-
BC decorated with lauric acid, coconut oil, and polydi- tions achieved by nitrogen gas ­(N2) purging in advance.
methylsiloxane (PDMS) have been studied to improve The heating rate of the reactor was 10℃ ­min−1 and the
sorption (Chen et al. 2020a, b; Gurav et al. 2021a, b; target pyrolysis temperature was maintained for 4 h.
Navarathna et al. 2020). However, there are few research After the reactor was cooled to room temperature, the
concerns about the oil sorption variation resulting from biochars were removed and milled, passing through a
the difference in precursor materials and pyrolysis tem- 0.55 mm mesh screen for later use. According to the
perature. Accordingly, we investigated the characteris- pyrolysis temperature and feedstock, the prepared pris-
tics of the inherent properties and sorption capacity of tine biochars were referred to as CSBC350, CSBC500,
biochars produced from different representative feed- CSBC650, CCBC500, SSBC500, and RHBC500. Fur-
stock materials and pyrolysis temperatures. The water thermore, the specific biochars were screened into three
repellency of biochar has been unsatisfactory for a long different sizes, small (0.55–0.25 mm), medium (0.25–
time. n-Octadecyl trimethoxy silane (OTMS) is a hydro- 0.15 mm), and large (< 0.15 mm).
phobic modification reagent with excellent performance
and eco-friendliness. Hydrolysis and condensation reac- 2.3 Modification of biochar
tions easily occur to form a hydrophobic film layer on the The magnetic biochar was prepared as described by
material surface, which makes the material have better Mohan (2014). The main process is presented in Fig. 1a.
water resistance. Then, biochar modification was per- ­FeCl3·6H2O (1.80 g) and F ­ eSO4·7H2O (1.85 g) were dis-
formed by employing n-Fe3O4 and OTMS for control- solved in 150 mL distilled water for 5 min at 60℃ to
lability and hydrophobicity. The surface morphology, prepare the F­ e2+/Fe3+ solution. Then, 2.0 g of CSBC350
surface element distribution, BET surface area, functional was slowly added to the ­Fe2+/Fe3+ solution and stirred
groups, crystal structure, magnetic properties, thermal for 30 min, forming a mixed suspension. After that, 1 M
analysis, flotation, and wettability of the prepared adsor- NaOH was carefully added to the mixed suspension
bents were investigated. The performances of the sorp- until the pH reached ~ 11, and the suspension succes-
tion capacity, availability, sorption kinetics, and sorption sively became brown and black at ~ pH 6 and ~ pH 10,
isotherm were tested. The target adsorbent is expected to respectively. Subsequently, the suspension was heated
float on the water to adsorb spilled oil individually or as to 80℃ for 1 h and aged at room temperature for 2 h.
a complement to other techniques, which is beneficial to Then, a magnet was used to separate the magnetic bio-
the thoroughness of oil spill clean-up work. char (MBC), and the product was washed several times
with distilled water and ethanol. Finally, the prepared
2 Materials and methods MBC was filtered by a vacuum suction filter and dried
2.1 Feedstock and chemicals at 50℃ in a vacuum drying chamber. The fabrication of
Cornstalk (CS), corncob (CC), Sophora sawdust (SS), hydrophobic magnetic biochar was as follows: the mag-
and rice husk (RH) were collected from a local farm- netic biochar and OTMS were mixed and heated for 3 h
land and wood-working factory (Qingdao, China). The in 100 mL of 25% aqueous ethanol solution, centrifuged
Sun et al. Biochar (2022) 4:60 Page 4 of 17

Fig. 1 General scheme for the preparation of the hydrophobic magnetic biochar (a). The schematic diagram of the silylation reaction mechanism
for the magnetic biochar modification with OTMS (b)

for 10 min at 6000 rpm and washed several times with The sorption capacity of these adsorbents was calcu-
ethanol. The obtained biochar was named OMBC. lated as follows (Eq. 1):
mc −mb −ma
2.4 Sorption experiment Q= (1)
ma
The adsorptive performance of several pristine biochars
was determined in a pure oil system. The detailed steps where Q is the mass sorption capacity of the adsorbent (g
were performed according to the standard test method ­g−1), ma is the weight of the adsorbent (g), mb is the mass
for the sorption performance of sorbents as given by sorption capacity of the control grid (g), and mc is the
ASTM F726 (Bazargan et al. 2015). A certain quantity final weight of the grid and adsorbent after sorption (g).
of biochar was placed on a preweighed stainless steel The experiments to determine the effect of salinity, pH,
grid and immersed in the oil for 1 h to equilibrate at and temperature on the sorption of crude oil by OMBC
room temperature. Afterward, before being weighed, were carried out by changing a single condition based
the excess oil was drained from the grid for 30 min on the above description. After reaching adsorption
until no drops fell. The sorption capacity was obtained equilibrium, a magnet was used to collect the OMBC oil
by subtracting the sorption capacity of the grid. BC and mixture. Then, 20 mL of n-hexane was used to elute the
modified biochars (MBC, OMBC) were employed for adsorbed oil for three times, and the sorbent was washed
the removal of petroleum oil from the water surface. again with deionized water. Finally, the cleaned sorbent
Measurement of the adsorptive capacity in the oil- was dried and weighed.
water system was similar to that in the oil system. In
brief, 200 mL of freshwater was poured into a beaker
(250 mL) and 2.0 g of oil was added to simulate spilled 2.5 Sorption kinetics and isotherm models
oil. The stainless steel grid carrying 0.2 g of adsorbent The kinetics and isotherm models for oil sorption on bio-
was placed in the oil and was allowed to float on the char and modified biochar were studied in a water–oil
surface of water for 2 h at room temperature. Next, system at 25℃. The adsorbent kinetics were determined
the excess oil was allowed to drain off the grid for by adding 200 mL of distilled water and 2 g of oil to a
30 min, and the grid was dried in a drying oven at 60℃ 250 mL glass beaker and varying the contact time from
to remove adsorbed water. In the same way, the blank 0 to 240 min. For the isotherm study, adsorbent uptake
net was used as a control to measure the real sorption capacities were determined by changing the quantity
capacity. For the modified biochars (MBC, OMBC), a of each added oil from 0.30 to 7 g with 0.20 g of mate-
magnet was used to separate and collect the biochars rial while holding other factors constant. The detailed
after sorption equilibrium.
Sun et al. Biochar (2022) 4:60 Page 5 of 17

contents of the models are presented in the Supplemen- full holes became crevices, which is attributed to the
tary Information. formation of fine stomates that connect and destroy
the original structure (Xiong et al. 2021). The prop-
2.6 Characterization methods erties and structure of biochar rely on the type and
The surface morphology and elemental compositions of nature of the lignocellulosic feedstock used. Agricul-
the adsorbent material were observed through scanning tural residues, such as corn stalks, contain more cel-
electron microscopy (SEM, TESCAN, TESCAN MIRA4, lulose and hemicellulose and less lignin. During the
Czech Republic) equipped with an energy dispersive preparation process, the cellulose and hemicellulose,
spectrometer (EDS, Xplore). The ­N2 adsorption–desorp- which needed a low pyrolysis temperature (200–400℃)
tion experiments were conducted using a surface area first decomposed to form pores. Subsequently, lignin
analyzer (Micromeritics, APSP 2460, USA). The surface gradually decomposed with increasing pyrolysis temper-
area and pore size of the biochars were obtained via the ature (> 500℃), which left a portion of air holes (Yaashi-
Brunauer–Emmett–Teller (BET) and Barrett-Joyner- kaa et al. 2019). Under high temperature conditions,
Halenda (BJH) analysis. The composition of CSBC350, cellulose and hemicellulose were completely gasified, and
MBC, and OMBC was analyzed using X-ray diffractom- lignin began to change, which caused the catastrophic
etry (XRD, Rigaku, SmartLab-SE, Japan) from 5° to 90°. collapse of the porous structure.
The changes in the functional groups of the samples were The SEM images of MBC and OMBC are shown in
determined by Fourier transform infrared spectroscopy Fig. 3. As shown in Fig. 3a, abundant magnetic parti-
(FT-IR, MAGNA-560, Nicolet, USA) within the range cles and their aggregates were deposited on the surface
of 4000 to 400 ­cm−1 in transmittance mode. The hydro- of the biochar. Likewise, there was a depositional plane
phobicity of the CSBCs and modified BC was measured at the opening of the channel, as seen in Fig. 3b. Nota-
by a contact angle measuring device (CA, OCA 20, Data bly, there was no blocking phenomenon in the porous
Physics ES, Germany) at room temperature by releasing structure, and the original porous construction was
2 μL of water on the sample surface. The magnetic prop- maintained to a large extent. As seen in Fig. 3c, the
erties of the samples were recorded by vibrating sample magnetic nanoparticles had a lamellate structure, with
magnetometer (VSM, Lake Shore, 7404, USA) in a field a nano magnitude size of less than 100 nm (Karuna-
of 15,000 to 15,000 Oe. The thermal stability of adsor- nayake et al. 2019; Navarathna et al. 2019). After fur-
bent was characterized by thermogravimetric analysis ther modification using OTMS, the MBC appeared to
(TGA and DTG, METTLER TOLEDO, TGA2/DSC3, have a smoother surface that coated the rough magnetic
Switzerland) under nitrogen conditions from 30 to 800℃. layer (Fig. 3d). At the same time, the macropores left by
The iron content of the water sample was measured by pyrolysis had well-defined borders as before, as shown in
inductively coupled plasma-mass spectrometry (ICP‒ Fig. 3d and e. The surface element compositions of the
MS, Agilent, 7700, USA). OMBC were analyzed by EDS spectroscopy. The distri-
bution of elemental C, O, Fe, and Si was observed from
3 Results and discussion the corresponding SEM‒EDS mapping images (Fig. 3 g),
3.1 Characterization of the adsorbents with their peaks appearing at approximately 0.267, 0.521,
3.1.1 Surface morphology and surface area analysis 0.710, and 1.74 keV, respectively (Additional file 1: Fig.
The surface appearances of the CSBCs produced at S2). Elemental C and O were the main component ele-
three pyrolysis temperatures (350℃, 500℃, and 650℃) ments, mainly from the biochar substrate. Elemental Fe
were observed by SEM, as shown in Fig. 2. The images and Si were found in trace amounts in the biochar and
show that all CSBCs had an obvious three-dimensional were mainly a result of the magnetic nano iron oxide and
macropore structure, regardless of the preparation the OTMS coating, respectively. In summary, according
temperature. However, there were still some evident to their elemental mapping images (Fig. 3g), iron oxide
structural distinctions that can be found among them. nanoparticles were evenly distributed on the surface of
Figure 2 shows that with the increase in pyrolysis tem- the biochar, and homogeneously covered by the OTMS.
perature from 350℃ to 650℃, the porous structure of The modification reaction process is presented in Fig. 1b.
CSBCs appeared to gradually shrink, and even collapse. The -SiOCH3 functional group of the OTMS hydrolysis
Specifically, CSBC350 had a tidy, full, and sharply mar- became -SiOH. Then, the dehydration reaction occurred
ginated cellular pore structure (Fig. 2a and b). CSBC500 between the -SiOH and the hydrophilic -OH functional
appeared as a disordered, fragmented surface under groups on the surface of the MBC.
continuous pyrolysis (Fig. 2c and d). Furthermore, the The specific surface area and pore size of the biochars
situation of CSBC650 was more prominent (Fig. 2e were obtained via the Brunauer–Emmett–Teller (BET)
and f ): numerous pores existed on the surface, and
Sun et al. Biochar (2022) 4:60 Page 6 of 17

Fig. 2 The SEM images of the CSBC350 (a, b), CSBC500 (c, d), and CSBC650 (e, f)
Sun et al. Biochar (2022) 4:60 Page 7 of 17

Fig. 3 SEM micrographs of MBC (a–c) and OMBC (d–f). A selected area on the OMBC for EDS measurement (f). Elemental mapping images of
OMBC for C, O, Fe, and Si (g)

Table 1 BET surface area and pore size of biochars and Barrett-Joyner-Halenda (BJH) analyses. The detailed
data are shown in Table 1.
Biochars BET surface Pore Average pore BJH pore
area ­(m2 volume diameter (nm) diameter The biochar obtained at low pyrolysis temperature-
­g−1) ­(cm3 ­g−1) (nm) shas more macropores, relatively few mesopores and
micropores, and a smaller BET surface area. With the
CSBC350 3.1982 0.005847 5.7095 12.3097
increase of the pyrolysis temperature, the hemicellulose
CSBC500 7.8631 0.012912 5.6284 14.7617
and lignin in the cornstalk gradually volatilized, which
CSBC650 208.3195 0.096402 1.8256 3.2387
resulted in the shrinkage or fragmentation of macropores
MBC 48.2159 0.209931 14.9065 17.1995
and the increase in the ratio of mesopore and micropore,
OMBC 1.8881 0.002258 4.2508 5.9620
thus BET surface area and pore volume increased. This
Sun et al. Biochar (2022) 4:60 Page 8 of 17

is the reason why the CSBC650 had a higher BET sur- compound-rich carbon material with lower polarity (Kei-
face area and pore volume, reaching 208.3194 ­m2 ­g−1 and luweit et al. 2010; Sun et al. 2011). For the MBC spectra,
0.096402 ­cm3 ­g−1, respectively. However, at higher pyrol- the most noteworthy was the Fe–O characteristic peak
ysis temperatures, the macropores and mesopores were (575 ­cm−1), which indicates the success of magnetic
reduced, and the micropores became the main pores. loading on CSBC350 (Tapia et al. 2019). In the OMBC
Hence, the average pore diameter and mesopore diame- spectrum, the peaks at approximately 2917 and 2846,
ter were smaller for CSBC650, 1.8256 nm and 3.2387 nm, 1466 ­cm−1 were attributed to aliphatic CH and ­ C H2
respectively. The above results were also verified in Fig. 2 stretching vibrations. Furthermore, the peaks at 1027,
SEM images. 790 ­cm−1, and 880 ­cm−1 were associated with Si–O–Si
In addition, the BET surface area, pore volume, and (Villegas et al. 1988) and Si–C (Zhou et al. 2018) stretch-
BJH pore diameter of MBC were increased to 48.2159 ing vibrations, respectively. Simultaneously, the peak at
­m2 ­g−1, 0.209931 nm, and 17.1995 nm, due to the depo- around 575 ­cm−1 was also from the Fe–O band. The pri-
sition of magnetic nanoparticles on the surface and the mary peaks in the OMBC spectrographic curve strongly
macropore’s inner wall of CSBC350 (Fig. 3a–c). How- suggested that the magnetic nanoparticles and the long-
ever, the modification of OTMS caused the rough sur- chain hydrophobic alkyl groups of OTMS had been
face of MBC to become smooth, destroying the existing grafted onto the surface of biochar as expected.
mesoporous and microporous structures. Therefore, XRD analysis was used to determine the crystalline
the BET surface area, pore volume, and pore diameter structures of the samples. As shown in Fig. 4b, the peak
of OMBC were decreased compared with before the at around 22.7° in the XRD pattern of CSBC350 was the
modification. diffraction from the transformation of the lignocellu-
losic crystal structure to a more carbonaceous structure
3.1.2 FT‑IR and XRD analysis after pyrolysis (Regmi et al. 2012). This broad peak dis-
Figure 4a demonstrates the FT-IR spectra of CSBC350, appeared after magnetite precipitated due to magnetite’s
CSBC500, CSBC650, MBC and OMBC. From the spec- highly intense crystalline peaks (Navarathna et al. 2020).
trogram of the CSBCs, it can be easily concluded that It can be seen from the spectra of CSBCs that the peaks
the organic functional groups either faded away or were at 28.41°, 40.51°, 50.25°, and 58.66°, etc. indicate the pres-
eliminated, and the curves became smooth as the pyrol- ence of potassium chloride, especially in CSBC500. This
ysis temperature increased. These organic and inor- is due to the release of potassium from biomass in the
ganic functional groups were predominated by –OH form of potassium chloride during the pyrolysis process
(3406 ­cm−1), aliphatic CH stretching (2927 ­cm−1), ester (Fatehi et al. 2015). It is more pronounced at 500℃ and
C=O (1698 and 1562 ­cm−1), aromatic C=C (1580 ­cm−1), alleviated due to volatilization at higher pyrolysis tem-
and C–O (1200 to 1060 ­cm−1) (Qian et al. 2016; Xie peratures (650℃) (Jensen et al. 2000). For both modified
et al. 2021). The biochar produced at lower tempera- adsorbents, it was completely obvious that there were
tures had lower aromaticity, compared with the biochar multiple typical iron oxide diffraction peaks. The peak
prepared at higher temperatures, which was an aromatic shapes of MBC and OMBC indicates that a precipitated

Fig. 4 The FT-IR characterization of the CSBCs and OMBC (a). The XRD spectra of CSBCs, MBC, and OMBC (b)
Sun et al. Biochar (2022) 4:60 Page 9 of 17

layer of magnetite particles had formed. The major peak separation and the saturation magnetization was 14.19
at 35.62° was attributed to the crystalline plane of ­Fe3O4 emu ­g−1, indicating outstanding magnetic properties (Yin
(Karunanayake et al. 2017). The other peaks at 30.16° et al. 2021). Furthermore, the OMBC iron loading rate
(220), 43.24° (400), 53.79° (422), 57.15° (511), 62.83° was 16.86%, which is slightly lower than the theoretical
(440), and 74.26° (620) were also observed. Remarkably, value (18.26%).
the peak at 21.5° (002) in OMBC was attributed to S ­ iO2 The thermal gravimetric analyses (TGA) results of
(Alchouron et al. 2020). CSBC, MBC, and OMBC at 30–800℃ are shown in
The crystallite sizes of the F
­ e3O4 deposited on MBC Fig. 5b. In the initial stage, CSBC, MBC, and OMBC had
and OMBC were analyzed through the Scherrer equation a small amount of weight loss below 150℃ to varying
(Eq. 2) (Navarathna et al. 2020). The magnetite crystallite degrees, which was caused by the evaporation of physi-
sizes were deduced from the peak of D311 for MBC, and cally adsorbed water. During this period, it is noticeable
OMBC, which were 8.65 nm and 8.85 nm, respectively. that the OMBC lost relatively little weight, which may be
a result of its hydrophobic nature. A weight loss occurred
k
Dhkl = (2) in the temperature range of 170–260℃ was mainly due
βcosθhkl to the dihydroxylation and the loss of unreacted oxygen-
where k is the shape factor, with k = 0.89 for cubic crys- containing species on the OMBC (Yang et al. 2021). In
tals,  is the XRD analysis wavelength (nm), β is the full the temperature range of 350–550℃, there was great
width at half-maximum value (rad) for XRD lines, and θ weight loss for CSBC (15.85%) and MBC (9.87%), which
is half the diffraction angle 2 θ. was attributed to the pyrolysis of the biochar produced at
350℃. Over the same temperature range, the OMBC dra-
3.1.3 Magnetic moment and thermal analysis
matically lost almost 31% of its weight, which was mainly
The magnetic properties of OMBC were investigated by attributed to the thermal decomposition of the OTMS
vibrating sample magnetometry (VSM). The loading of chain grafted on the MBC surface (Liu et al. 2015). This
magnetic nanoparticles offered OMBC paramagnetic phenomenon exactly indicates that the alkyl chains (–
behavior with no hysteresis while removing the magnetic CH2(CH2)16CH3) of OTMS were efficaciously grown
field (Fig. 5a). The magnetic moment illustrates that the on the surface of the magnetic biochar. The weight loss
saturation magnetization of OMBC was 24.21 emu ­g−1, at temperatures above 550℃ resulted from the thermal
which was less than value of iron oxide (66.75 emu g­ −1). decomposition of the biochar substrate, whereby almost
The reason for this phenomenon is the coating effect of 74%, 69%, and 54% of the weight was lost for MBC,
OTMS on ­Fe3O4 and the low proportion of magnetic CSBC, and OMBC, respectively, at temperatures up to
particles. However, the saturation magnetization of 800℃.
OMBC was sufficiently high to be separated by a magnet. As seen in the CSBC curve, three stages typically
Similarly, Raj et al. had prepared a magnetic adsorbent existed in the process. In the first stage (below 200℃), the
nanocomposite material, in which the magnetization decrease in mass was owning to the evaporation of mois-
was 15.00 emu g­ −1 (Raj et al. 2015). Yin et al. had pro- ture and light volatiles (Cárdenas-Aguiar et al. 2017). The
duced carbonized ­Fe3O4@cotton for use in the oil-water next stage was from approximately 200 to 500℃, during

Fig. 5 Magnetic hysteresis loop of magnetic ­Fe3O4 and OMBC (a). Thermogravimetric analysis curves (10℃ ­min−1 heating rate under ­N2
atmosphere) of CSBC (350℃), MBC, and OMBC (b)
Sun et al. Biochar (2022) 4:60 Page 10 of 17

which CSBC had a significant mass loss. As the primary the hydrophobic characteristic that allows the material
process, polymerized organic compounds, such as hemi- to float on the surface of the water. Additional file 1: Fig.
cellulose and cellulose, were volatilized and decomposed S3b shows the situations of CSBC350, MBC, and OMBC
at a fast rate. In the third stage above 500℃, the slow in water after stirring to test the floatability. CSBC350
weight loss was caused by the decomposition of lignin and MBC were mixed into the water phase, and OMBC
and other organic matter with stronger chemical bonds, was still floating on the surface yet. The silane reagent’s
and residual organic matter was further transferred into hydrocarbon chains on the surface of OMBC prevent
biochar gradually (Yuan et al. 2019). Overall, although water from adhering to the surface and entering the pore
the weight loss can be caused by the modifying agent, the network, whereas the OMBC remains buoyant and does
TG curve for the OMBC corresponded to the change in not sink. The excellent hydrophobicity and floatabil-
the weight of the biochar during the pyrolysis process. ity help to guarantee efficient oil sorption on the water
surface. In addition, even when entering the water, since
3.1.4 Wettability measurement hydrocarbons are entrapped inside the pore network,
As depicted in Additional file 1: Fig. S3a, the wettabil- biochar particles also provide a favorable environment
ity of the CSBCs and OMBC was studied by water con- for the colonization of oil-degrading microorganisms
tact angle (WCA). Hydrophilicity is defined as a water (Nguyen et al. 2013).
contact angle less than 90° and vice versa. The WCA
of CSBC350 was 86.23° (< 90°), appearing hydrophilic. 3.2 Oil sorption capability
However, it was significant that the WCA of the CSBCs The oil sorption ability of different biochar was
gradually increased with increasing pyrolysis tempera- researched. We selected three representative oils with
ture (Additional file 1: Fig. S3a). The hydrophilicity and different densities and viscosities to study the adsorption
hydrophobicity of biochar are determined by the organic properties of biochar on typical oils. Figure 6a shows that
groups on the surface (Yuan et al. 2019). However, a there were obvious differences in the oil sorption abil-
higher pyrolysis temperature leads to a decline in polar ity among the biochars produced from different biomass
functional groups on the biochar surface, which enhances materials. At the same pyrolysis temperature (500℃), the
the hydrophobicity of the biochar (Ahmad et al. 2014). In CSBC had the maximum oil sorption ability for crude
detail, the biochar produced at low temperatures had an oil (8.45 g ­g−1), being almost 2 times that of CCBC and
abundance of hydrophilic groups, such as oxhydryl and SSBC, while RHBC was the most inefficient. Based on
carboxyl groups. In contrast, the biochar produced at the results, the CSBCs produced at different tempera-
higher temperatures was aromatic compound rich with tures were employed to adsorb the crude oil in the pure
high hydrophobicity. In Additional file 1: Fig. S3a, the oil system. CSBC350 had the strongest ability to adsorb
water contact angle of OMBC decorated with OTMS oil, as seen in Fig. 6a. The main reason for this result was
reached 138.00°, which indicates a stronger hydrophobic- that the CSBC350 had a more complete macropore struc-
ity compared with the substrate material (CSBC350). A ture to hold the oil, as mentioned before. The oil sorption
large number of long alkyl chains have been grafted on ability of biochar is closely associated with the pyrolysis
the surface of OMBC and in the crevices, which result in temperature and feedstock material (Lian et al. 2017).

Fig. 6 The oil capacity of biochar and modified biochar. The crude oil sorption capacity of biochar that pyrolyzed from various feedstock materials
prepared at 500℃ and the corn stock biochar that was pyrolyzed at different temperatures (a). The sorption capacity of different sizes of CSBC350
for three oils. (Small: 0.55–0.25 mm, Medium: 0.25–0.15 mm, and Large: < 0.15 mm) (b). The sorption capacities of CSBC (350℃), MBC, and OMBC for
three types of oil in the oil–water system (c)
Sun et al. Biochar (2022) 4:60 Page 11 of 17

Generally, feedstock materials, such as agricultural stalks oil molecules on the surface of the material. In this case,
that are composed of cellulose and hemicelluloses, only the sorption effect is greater than the absorption effect.
need low preparation temperatures to form a fully porous Therefore, increasing the viscosity of the oil can increase
structure. Conversely, wood-like materials, contain- the oil absorption of the biochar (Ceylan et al. 2009; Zhu
ing a high proportion of lignin and celluloses, are often et al. 2011). The viscosity of crude oil is relatively high,
pyrolyzed at high temperatures to achieve volatilization and it easily attaches and accumulates inside the biochar.
and form pores (Yaashikaa et al. 2019). In addition, the Engine oil and diesel oil have lower densities and viscosi-
biochar particle size is a significant and neglected factor ties and, of course, lower storage ability in biochar.
in the sorption of organic pollutants, so the correlation
between removal efficiency and biochar particle size has 3.3 Sorption kinetics and sorption isotherm experiments
aroused controversy (Jin et al. 2022). The CSBC350 was As seen in Fig. 7, the sorption of crude oil by CSBC and
sieved into three different sizes: large (0.55–0.25 mm), OMBC reached equilibrium at 60 min, while the sorp-
medium (0.25–0.15 mm), and small (< 0.15 mm). Dif- tion equilibrium of diesel oil and engine oil was com-
ferent types of oil were used to measure the oil sorption pleted within 10 min. During the sorption of crude oil,
ability of the three biochar sizes in the pure oil environ- the sorption was rapid at the beginning, and after 30 min
ment. As shown in Fig. 6b, the oil sorption ability of bio- the sorption was sluggish. The reason for this process is
char in all sizes was the greatest for crude oil, with the that initially the surface of biochar contained many blank
results all being greater than over 10 g ­g−1. The medium- active sites, which contribute to the fast progress of sorp-
sized biochar has the best sorption to crude oil and diesel tion. With continuous sorption, the sites were occupied
oil. The small-sized biochar had a higher ability to adsorb by crude oil, and the crude oil had a high viscosity, hence,
engine oil. Overall, the medium-sized biochar had a bet- the sorption gradually slowed down. The increased sorp-
ter sorption effect on the three kinds of oil. The differ- tion after 30 min was probably attributed to the breakage
ences in the sorption of the three oils by different sizes of crude oil droplets, which reduces the diameter of the
were mainly due to the pore size. The undersized biochar crude oil droplets causing more interfacial pore area for
broke the initial macroporous structure, which made it the sorption to occur (Stang et al. 1994). However, in the
inefficient for oil sorption (Jin et al. 2022). presence of low viscosity oils, such as diesel and engine
The experimental results of CSBC350, MBC, and oil, the sorption was relatively fast. The pseudo-first-order
OMBC oil sorption in the oil-water system are shown in and pseudo-second-order models were used to simulate
Fig. 6c. It was obvious that the oil sorption ability of MBC oil sorption onto CSBC and OMBC, as shown in Fig. 7,
presented an obvious downward trend, due to the hydro- and the results and detailed parameters are summarized
philicity of the nano iron oxide and magnetite deposition in Additional file 1: Table S1. From the fitting results, the
enhancing the adsorbent weight. The MBC decorated by sorption kinetics of the CSBC and OMBC both coincided
OTMS had an oil sorption ability that was almost equal with the pseudo-second-order model, and the correlation
to that of CSBC350, reaching 8.54 g crude oil g­ −1, 5.03 g coefficients ­(R2) were high (> 0.99). When comparing the
engine oil ­g−1, and 4.30 g diesel oil ­g−1. Although the oil theoretical equilibrium sorption capacity produced from
sorption capacity of CSBC350 was slightly greater than the two kinetic models, the theoretical capacities fitted
that of OMBC, the capacity sharply declined when the from the pseudo-second-order model were closer to the
CSBC faced the turbulence of the water wave, which can experimental values. These fitting results illustrate that
provide a greater probability of contact with water. How- the sorption process was a chemical sorption process,
ever, OMBC can selectively adsorb oil on the water sur- not just simple physical sorption.
face in a floating posture due to its hydrophobic surface. The sorption isotherms of CSBC and OMBC are
Regarding oil types, crude oil always has the highest level shown in Fig. 8. The sorption isotherms are significant
of sorption capacity followed by engine oil and diesel oil, for describing the interaction between adsorbate and
regardless of the size of the original biochar or modifi- adsorbent (Sidik et al. 2012). Nonlinear Langmuir and
cation. In general, the difference in oil sorption capac- Freundlich isotherm models were employed to analyze
ity is related to the density and viscosity of the oil. The the experimental isotherm data. The detailed contents
greater the density of the oil is, the greater the quality of are listed in Additional file 1: Table S2. The Langmuir
the oil stored in the material space and the greater the isotherm model was most suitable for the sorption of
calculated oil sorption capacity. The viscosity is another three oils, with regression coefficient values (­R2) that
important influencing factor. Although a higher viscos- were both greater than 0.95 for CSBC and greater than
ity of oil hinders the sorption of oil molecules into the 0.80 for OMBC, which indicates that the sorption of oils
internal structure of the material, for macroporous mate- was monolayer coverage onto the homogenous distribu-
rials, a higher viscosity is conducive to the sorption of tion of active sites on the CSBC or OMBC surface, where
Sun et al. Biochar (2022) 4:60 Page 12 of 17

Fig. 7 The pseudo-first-order kinetics model of oils sorption on CSBC (350℃) (a) and OMBC (c). The pseudo-second-order kinetics model of oil
sorption on CSBC (350℃) (b) and OMBC (d)

all active sites are energetically equivalent (Gurav et al. easily adsorbed. In addition, the influences of pH and
2021a, b). OMBC’s maximum oil sorption capacity (qm, temperature on crude oil sorption were surveyed. As
9.25 g crude oil ­g−1, 4.05 g diesel oil ­g−1, 4.41 g engine Fig. 9c shows, the sorption ability of OMBC in the low
oil ­g−1) calculated from the Langmuir model was close to pH range was greater than that in the high pH range,
the experimental value (qe, Exp, 8.77 crude oil g ­g−1, 4.01 and this result may be related to the charge change.
diesel oil g g­ −1, 4.44 engine oil g ­g−1). Certainly, the qm When the temperature was gradually increased, the vis-
values of CSBC were also nearly the same as the experi- cosity of crude oil decreased, and the sorption capacity
mental values. increased slightly (Fig. 9d).
The recovery rate of the sorbent is an important
3.4 Availability of sorbent parameter for magnetic oil sorbents. Hence, the recov-
The oil sorption capacity of OMBC in the seawater- ery rate of OMBC after oil sorption was tested, and the
oil system was measured, as shown in Fig. 9a. The results show that the recovery rate was almost stable
sorption ability of OMBC for the three oils showed a at approximately 75% regardless of the oil type (Addi-
slight decrease compared with the performance in the tional file 1: Fig. S4a). Furthermore, considering that
deionized water-oil environment (Fig. 6c). A similar the adsorbent will be used in the water environment,
result was also reported by other researchers (Navar- there may leach supported metals. Hence, after the
athna et al. 2020). Furthermore, the effect of salinity sorption of crude oil by OMBC, the iron contents of
on OMBC sorption of crude oil was investigated. Fig- deionized water and seawater were measured by ICP‒
ure 9b shows that the effect of salinity change on the MS (Additional file 1: Fig. S4b). Compared with the
sorption capacity of crude oil was small, but gener- blank water sample, it can be seen that iron was leached
ally showed a trend of decreasing and then increasing out neither in deionized water or seawater environment
in the range of 30–120‰. The reason for this may be after OMBC adsorbed crude oil.
that the hydrophobicity of the oil is enhanced under the Table 2 summarizes the capacities of oil sorbents
action of static electricity, which makes the oil more reported in the literature. It can be observed that our
Sun et al. Biochar (2022) 4:60 Page 13 of 17

Fig. 8 The Langmuir isotherm model of oil sorption on CSBC (350℃) (a), OMBC (c). The Freundlich isotherm model of oil sorption on CSBC (350℃)
(b), OMBC (d)

sorbent exhibited a great sorption performance, in on the surface and prevent the attachment and entry of
comparison with previous sorbent capacities. water. Moreover, the three-dimensional multiporous
structure of the biochar is one of the essential points
3.5 Sorption mechanism that dominates the oil removal efficacy. Specifically, this
Biochar is an ideal sorption material due to its high poros- three-dimensional structure increases the pore volume
ity, high specific surface area, abundant surface organic and provides more effective sites for oil sorption (Ha
functional groups, and outstanding cation exchange et al. 2016). For instance, higher pyrolysis temperatures
capacity and has extensive application in the remediation can lead to the destruction of the partial pore structure
of soil pollution, water treatment, and carbon sequestra- of rice husk biochar, which results in a further decrease
tion. The differences in the biochar characteristics were in removal (Zhao et al. 2013), similar to CSBC. The SEM
important reasons for the different sorption mechanisms. figure of OMBC shows that the porous structure was
As shown in Fig. 10, the oil sorption mechanisms of bio- unbroken, even though modification occurred. With the
char were mainly dominated by hydrophobic forces, pore sorption of the surface hydrophobic layer, the intact pore
intercepts, π–π electron attraction, hydrogen bonds, and structure associated with the presence of macropores can
electrostatic attraction. As another critical factor affect- hold more oil. Moreover, hydrogen bonds are formed
ing oil sorption capability, the hydrophobicity of the between polar components of the oil (especially resins
adsorbent is determined by the heterogeneity of the mor- and asphaltenes) and the biochar’s oxygen-containing
phology and surface chemistry and can be represented functional groups, including –COOH and –OH (Jiang
by water contact angle (Doshi et al. 2018). Through the et al. 2016). The graphene content of biochar is electron
aforementioned results of WCA analysis, the OMBC rich and interacts with electron-deficient components of
was identified as a hydrophobic material and can specifi- the oil, enhancing the π–π electron effect (Ahmad et al.
cally adsorb oil due to the fatty acid functional groups 2014). In addition, electrostatic interactions may have
Sun et al. Biochar (2022) 4:60 Page 14 of 17

Crude oil (a)

Engine oil

Diesel oil

120 (b)
Salinity (‰)

90
60
30

11 (c)
8
pH
5
2
Temperature (℃)

55 (d)
40
25
10

0 2 4 6 8 10 12
Capacity (g g-1)
Fig. 9 Sorption of oils by OMBC in the seawater-oil system (a). Sorption of OMBC on crude oil under different conditions, salinity (b), pH (c), and
temperature (d)

Table 2 Comparison with the oil sorption capacity of biochar in literatures

Biochars Type of oil Water medium Temperature Adsorption References
(℃) capacity (g ­g−1)

Coconut oil-modified wood biochar Crude oil Freshwater 25 5.32 Gurav et al. (2021a, b)
Coconut shell biochar-iron oxide composite Used motor oil Deionized water 25 7.65 Raj et al. (2015)
Lauric acid-coated magnetic biochar Crude oil Deionized water 25 6.30 Navarathna et al. (2020)
Rice husks biochar Crude oil Seawater 25 6.00 Angelova et al. (2011)
Rice husk biochar Crude oil Deionized water 25 3.23 Kandanelli et al. (2018)
Wood chip biochar Toluene Deionized water 25 0.18 Silvani et al. (2017)
Synthetic seawater 0.09
Spent coffee grounds biochar Diesel oil Deionized water 25 1.50 Lee et al. (2022)
OMBC Diesel oil Deionized water 25 4.30 This study
Engine oil 25 5.03
Crude oil 25 8.54
Sun et al. Biochar (2022) 4:60 Page 15 of 17

Fig. 10 The schematic diagram for sorption mechanisms of oil by OMBC

been created between the positively charged components Supplementary Information

of the oil and the negatively charged adsorbent sites (Xu The online version contains supplementary material available at https://​doi.​
et al. 2011). org/​10.​1007/​s42773-​022-​00184-9.

Additional file 1. Supplementary material.

4 Conclusion
Biochars prepared from different feedstock materials at
the same pyrolysis temperature (500℃) were used to deter- Acknowledgements
Not applicable.
mine the adsorbing capacity of crude oil (3.01–8.47 g ­g−1).
The results showed that CSBC had a relatively higher sorp- Author’s contributions
tion ability. Further research showed that CSBC350 had a XS: Conceptualization, data curation, investigation, writing—original draft. HF:
Conceptualization, formal analysis, data curation, writing—review and editing.
fully porous structure and was an excellent adsorbent to MB, YaL, YiL, JL: Investigation, supervision. WL: Formal analysis, visualization. CL:
oils, especially medium-size biochar. The OMBC modified Software, writing—review and editing. All authors read and approved the final
by the magnetic particles and OTMS presented outstand- manuscript.

ing hydrophobicity and satisfactory controllability. Addi- Funding

tionally, OMBC demonstrated a high oil sorption capacity This study is MCTL Contribution No. 307, and it is supported by the Major
to crude oil of 8.54 g ­g−1 in the oil-deionized water system. Scientific and Technological Innovation Project (MSTIP) of Shandong
(2021CXGC010705).
The kinetics model and isotherm model were conducted
to study the sorption process. The pseudo-second-order Data availability
kinetics and the Langmuir isotherm models were fitted All data generated or analysed during this study are included in this article.

compatibly to the sorption process. And OMBC main-

tained stable sorption capacity in different environmental Declarations
conditions and had good environmental applicability and Competing interests
availability. For that reason, when facing a complex hydro- The authors declare that they have no known competing financial interests
dynamic environment, OMBC could be an excellent oil or personal relationships that could have appeared to influence the work
reported in this paper.
adsorbent and could be employed as an effective measure
to combine with other physical methods to eliminate oil Author details
1
contaminants in the emergency handling of oil spills. After Frontiers Science Center for Deep Ocean Multispheres and Earth System,
and Key Laboratory of Marine Chemistry Theory and Technology, Ministry
adsorbing oils, in contrast to other adsorbents, material of Education, Ocean University of China, Qingdao 266100, China. 2 Col-
based on biochar was a high-performance and economi- lege of Chemistry and Chemical Engineering, Ocean University of China,
cal fuel, which realizes resource reuse and is in accord with Qingdao 266100, China. 3 China Petrochemical Corporation (Sinopec Group),
Beijing 100728, China.
the goal of carbon neutrality.
Received: 7 June 2022 Accepted: 26 September 2022
Sun et al. Biochar (2022) 4:60 Page 16 of 17

References fatty acids. Sci Total Environ 781:146636. https://​doi.​org/​10.​1016/j.​scito​

Agrafioti E, Kalderis D, Diamadopoulos E (2014) Ca and Fe modified biochars tenv.​2021.​146636
as adsorbents of arsenic and chromium in aqueous solutions. J Environ Gurav R, Bhatia SK, Choi T, Choi Y, Kim HJ, Song H, Lee SM, Lee Park S, Lee HS,
Manage 146:444–450. https://​doi.​org/​10.​1016/j.​jenvm​an.​2014.​07.​029 Koh J, Jeon J, Yoon J, Yang Y (2021b) Application of macroalgal biomass
Ahmad M, Rajapaksha AU, Lim JE, Zhang M, Bolan N, Mohan D, Vithanage M, derived biochar and bioelectrochemical system with Shewanella for the
Lee SS, Ok YS (2014) Biochar as a sorbent for contaminant management adsorptive removal and biodegradation of toxic azo dye. Chemosphere
in soil and water: a review. Chemosphere 99:19–33. https://​doi.​org/​10.​ 264:128539. https://​doi.​org/​10.​1016/j.​chemo​sphere.​2020.​128539
1016/j.​chemo​sphere.​2013.​10.​071 Ha NT, Van Cat Le, Anh PV, Lien TTT (2016) Research on oil adsorption capacity
Alameri K, Giwa A, Yousef L, Alraeesi A, Taher H (2019) Sorption and removal of of carbonized material derived from agricultural by-product (Corn Cob,
crude oil spills from seawater using peat-derived biochar: An optimiza- Corn Stalk, Rice Husk) using in oily wastewater treatment. Nat Sci Technol
tion study. J Environ Manage 250:109465. https://​doi.​org/​10.​1016/j.​jenvm​ 32(3):105–111
an.​2019.​109465 Itopf (2022) Oil tanker spill statistics 2021. ITOPF Ltd. Available via ITOPF Ltd.
Alchouron J, Navarathna C, Chludil HD, Dewage NB, Perez F, Hassan EB, Pitt- https://​www.​itopf.​org/​filea​dmin/​uploa​ds/​itopf/​data/​Docum​ents/​Compa​
man CU Jr, Vega AS, Mlsna TE (2020) Assessing South American Guadua ny_​Lit/​Oil_​Spill_​Stats_​2021.​pdf. Accessed 25 Apr 2022.
chacoensis bamboo biochar and F­ e3O4 nanoparticle dispersed analogues Jensen PA, Frandsen FJ, Dam-Johansen K, Sander B (2000) Experimental inves-
for aqueous arsenic(V) remediation. Sci Total Environ 706:135943. https://​ tigation of the transformation and release to gas phase of potassium and
doi.​org/​10.​1016/j.​scito​tenv.​2019.​135943 chlorine during straw pyrolysis. Energ Fuel 14(6):1280–1285. https://​doi.​
Angelova D, Uzunov I, Uzunova S, Gigova A, Minchev L (2011) Kinetics of org/​10.​1021/​ef000​104v
oil and oil products adsorption by carbonized rice husks. Chem Eng J Jiang YF, Sun H, Yves UJ, Li H, Hu XF (2016) Impact of biochar produced from
172(1):306–311. https://​doi.​org/​10.​1016/j.​cej.​2011.​05.​114 post-harvest residue on the adsorption behavior of diesel oil on loess
Atlas RM, Hazen TC (2011) Oil biodegradation and bioremediation: a tale of soil. Environ Geochem Hlth 38(1):243–253. https://​doi.​org/​10.​1007/​
the two worst spills in U.S. history. Environ Sci Technol 45(16):6709–6715. s10653-​015-​9712-1
https://​doi.​org/​10.​1021/​es201​3227 Jin Z, Xiao S, Dong H, Xiao J, Tian R, Chen J, Li Y, Li L (2022) Adsorption and
Barron MG (2012) Ecological impacts of the Deepwater Horizon oil spill: impli- catalytic degradation of organic contaminants by biochar: Overlooked
cations for immunotoxicity. Toxicol Pathol 40(2):315–320. https://​doi.​org/​ role of biochar’s particle size. J Hazard Mater 422:126928. https://​doi.​org/​
10.​1177/​01926​23311​428474 10.​1016/j.​jhazm​at.​2021.​126928
Bazargan A, Tan J, Mckay G (2015) Standardization of oil sorbent performance Kandanelli R, Meesala L, Kumar J, Raju CSK, Peddy VCR, Gandham S, Kumar P
testing. J Test Eval 43(6):20140227. https://​doi.​org/​10.​1520/​JTE20​140227 (2018) Cost effective and practically viable oil spillage mitigation: com-
Bianco F, Race M, Papirio S, Oleszczuk P, Esposito G (2021) The addition of bio- prehensive study with biochar. Mar Pollut Bull 128:32–40. https://​doi.​org/​
char as a sustainable strategy for the remediation of PAH-contaminated 10.​1016/j.​marpo​lbul.​2018.​01.​010
sediments. Chemosphere 263:128274. https://​doi.​org/​10.​1016/j.​chemo​ Karunanayake AG, Todd OA, Crowley ML, Ricchetti LB, Pittman CU, Anderson
sphere.​2020.​128274 R, Mlsna TE (2017) Rapid removal of salicylic acid, 4-nitroaniline, benzoic
Cárdenas-Aguiar E, Gascó G, Paz-Ferreiro J, Méndez A (2017) The effect of acid and phthalic acid from wastewater using magnetized fast pyrolysis
biochar and compost from urban organic waste on plant biomass and biochar from waste Douglas fir. Chem Eng J 319:75–88. https://​doi.​org/​
properties of an artificially copper polluted soil. Int Biodeter Biodegr 10.​1016/j.​cej.​2017.​02.​116
124:223–232. https://​doi.​org/​10.​1016/j.​ibiod.​2017.​05.​014 Karunanayake AG, Navarathna CM, Gunatilake SR, Crowley M, Anderson
Ceylan D, Dogu S, Karacik B, Yakan SD, Okay OS, Okay O (2009) Evaluation of R, Mohan D, Perez F, Pittman CU, Mlsna T (2019) ­Fe3O4 nanoparticles
butyl rubber as sorbent material for the removal of oil and polycyclic dispersed on Douglas Fir biochar for phosphate sorption. ACS Appl Nano
aromatic hydrocarbons from seawater. Environ Sci Technol 43(10):3846– Mater 2(6):3467–3479. https://​doi.​org/​10.​1021/​acsanm.​9b004​30
3852. https://​doi.​org/​10.​1021/​es900​166v Keiluweit M, Nico PS, Johnson MG, Kleber M (2010) Dynamic molecular struc-
Chandra S, Sharma R, Singh K, Sharma A (2013) Application of bioremedia- ture of plant biomass-derived black carbon (Biochar). Environ Sci Technol
tion technology in the environment contaminated with petroleum 44(4):1247–1253. https://​doi.​org/​10.​1021/​es903​1419
hydrocarbon. Ann Microbiol 63(2):417–431. https://​doi.​org/​10.​1007/​ Lee K, Cheng C, Lee D, Chen W, Vo DN, Ding L, Lam SS (2022) Spent coffee
s13213-​012-​0543-3 grounds biochar from torrefaction as a potential adsorbent for spilled
Chen J, Di Z, Shi J, Shu Y, Wan Z, Song L, Zhang W (2020a) Marine oil spill diesel oil recovery and as an alternative fuel. Energy 239:122467. https://​
pollution causes and governance: a case study of Sanchi tanker collision doi.​org/​10.​1016/j.​energy.​2021.​122467
and explosion. J Clean Prod 273:122978. https://​doi.​org/​10.​1016/j.​jclep​ro.​ Lian F, Xing B (2017) Black carbon (Biochar) in water/soil environments:
2040.​122978 molecular structure, sorption, stability, and potential risk. Environ Sci
Chen J, Yu Y, Shang Q, Han J, Liu C (2020b) Enhanced oil adsorption and nano- Technol 51(23):13517–13532. https://​doi.​org/​10.​1021/​acs.​est.​7b025​28
emulsion separation of nanofibrous aerogels by coordination of Pomelo Liang L, Xi F, Tan W, Meng X, Hu B, Wang X (2021) Review of organic and
peel-derived biochar. Ind Eng Chem Res 59(18):8825–8835. https://​doi.​ inorganic pollutants removal by biochar and biochar-based composites.
org/​10.​1021/​acs.​iecr.​0c005​12 Biochar 3(3):255–281. https://​doi.​org/​10.​1007/​s42773-​021-​00101-6
Dai Y, Wang W, Lu L, Yan L, Yu D (2020) Utilization of biochar for the removal of Liang H, Zhu C, Ji S, Kannan P, Chen F (2022) Magnetic ­Fe2O3/biochar com-
nitrogen and phosphorus. J Clean Prod 257:120573. https://​doi.​org/​10.​ posite prepared in a molten salt medium for antibiotic removal in water.
1016/j.​jclep​ro.​2020.​120573 Biochar. https://​doi.​org/​10.​1007/​s42773-​021-​00130-1
Doshi B, Sillanpää M, Kalliola S (2018) A review of bio-based materials for oil Liu L, Chen Y, Huang P (2015) Preparation and tribological properties of organi-
spill treatment. Water Res 135:262–277. https://​doi.​org/​10.​1016/j.​watres.​ cally modified graphite oxide in liquid paraffin at ultra-low concentra-
2018.​02.​034 tions. Rsc Adv 5(11):9525–9953. https://​doi.​org/​10.​1039/​c5ra2​0065b
EmekaNdimele P, Saba AO, Ojo DO, Ndimele CC, Anetekhai MA, Erondu ES Liu Q, Tang J, Gao K, Gurav R, Giesy JP (2017) Aerobic degradation of crude oil
(2018) Remediation of crude oil spillage. In: The political ecology of oil by microorganisms in soils from four geographic regions of China. Sci
and gas activities in the Nigerian aquatic ecosystem, Elsevier, pp 369–384. Rep. https://​doi.​org/​10.​1038/​s41598-​017-​14032-5
Fatehi H, He Y, Wang Z, Li ZS, Bai XS, Aldén M, Cen KF (2015) LIBS measure- Madhubashani AMP, Giannakoudakis DA, Amarasinghe BMWP, Rajapaksha AU,
ments and numerical studies of potassium release during biomass Pradeep Kumara PBT, Triantafyllidis KS, Vithanage M (2021) Propensity and
gasification. P Combust Inst 35(2):2389–2396. https://​doi.​org/​10.​1016/j.​ appraisal of biochar performance in removal of oil spills: a comprehen-
proci.​2014.​06.​115 sive review. Environ Pollut 288:117676. https://​doi.​org/​10.​1016/j.​envpol.​
Gupta S, Tai N (2016) Carbon materials as oil sorbents: a review on the synthe- 2021.​117676
sis and performance. J Mater Chem 4(5):155–1565. https://​doi.​org/​10.​ Mohan D, Kumar H, Sarswat A, Alexandre-Franco M, Pittman CU (2014) Cad-
1039/​c5ta0​8321d mium and lead remediation using magnetic oak wood and oak bark fast
Gurav R, Bhatia SK, Choi T, Choi Y, Kim HJ, Song H, Park SL, Lee HS, Lee SM, Choi pyrolysis bio-chars. Chem Eng J 236:513–528. https://​doi.​org/​10.​1016/j.​
K, Yang Y (2021a) Adsorptive removal of crude petroleum oil from water cej.​2013.​09.​057
using floating pinewood biochar decorated with coconut oil-derived
Sun et al. Biochar (2022) 4:60 Page 17 of 17

Navarathna CM, Karunanayake AG, Gunatilake SR, Pittman CU, Perez F, Mohan Xiong Z, Huanhuan Z, Jing W, Wei C, Yingquan C, Gao X, Haiping Y, Hanping
D, Mlsna T (2019) Removal of Arsenic (III) from water using magnetite pre- C (2021) Physicochemical and adsorption properties of biochar from
cipitated onto Douglas fir biochar. J Environ Manage 250:109429. https://​ biomass-based pyrolytic polygeneration: effects of biomass spe-
doi.​org/​10.​1016/j.​jenvm​an.​2019.​109429 cies and temperature. Biochar 3(4):657–670. https://​doi.​org/​10.​1007/​
Navarathna CM, Bombuwala Dewage N, Keeton C, Pennisson J, Henderson s42773-​021-​00102-5
R, Lashley B, Zhang X, Hassan EB, Perez F, Mohan D, Pittman CU, Mlsna Xu R, Xiao S, Yuan J, Zhao A (2011) Adsorption of methyl violet from aqueous
T (2020) Biochar adsorbents with enhanced hydrophobicity for oil spill solutions by the biochars derived from crop residues. Bioresource Tech-
removal. Acs Appl Mater Inter 12(8):9248–9260. https://​doi.​org/​10.​1021/​ nol 102(22):10293–10298. https://​doi.​org/​10.​1016/j.​biort​ech.​2011.​08.​089
acsami.​9b209​24 Yaashikaa PR, Senthil Kumar P, Varjani SJ, Saravanan A (2019) Advances in
Nguyen HN, Pignatello JJ (2013) Laboratory tests of biochars as absorbents for production and application of biochar from lignocellulosic feedstocks
use in recovery or containment of marine crude oil spills. Environ Eng Sci for remediation of environmental pollutants. Bioresource Technol
30(7):374–380. https://​doi.​org/​10.​1089/​ees.​2012.​0411 292:122030. https://​doi.​org/​10.​1016/j.​biort​ech.​2019.​122030
Qian L, Zhang W, Yan J, Han L, Gao W, Liu R, Chen M (2016) Effective removal of Yang Y, Chen X, Li Y, Yin Z, Bao M (2021) Construction of a superhydrophobic
heavy metal by biochar colloids under different pyrolysis temperatures. sodium alginate aerogel for efficient oil absorption and emulsion separa-
Bioresource Technol 206:217–224. https://​doi.​org/​10.​1016/j.​biort​ech.​ tion. Langmuir 37(2):882–893. https://​doi.​org/​10.​1021/​acs.​langm​uir.​0c032​
2016.​01.​065 29
Raj KG, Joy PA (2015) Coconut shell based activated carbon–iron oxide mag- Yim UH, Ha SY, An JG, Won JH, Han GM, Hong SH, Kim M, Jung J, Shim WJ
netic nanocomposite for fast and efficient removal of oil spills. J Environ (2011) Fingerprint and weathering characteristics of stranded oils after
Chem Eng 3(3):2068–2075. https://​doi.​org/​10.​1016/j.​jece.​2015.​04.​028 the Hebei Spirit oil spill. J Hazard Mater 197:60–69. https://​doi.​org/​10.​
Regmi P, Garcia Moscoso JL, Kumar S, Cao X, Mao J, Schafran G (2012) Removal 1016/j.​jhazm​at.​2011.​09.​055
of copper and cadmium from aqueous solution using switchgrass Yin Z, Pan Y, Bao M, Li Y (2021) Superhydrophobic magnetic cotton fabricated
biochar produced via hydrothermal carbonization process. J Environ under low carbonization temperature for effective oil/water separation.
Manage 109:61–69. https://​doi.​org/​10.​1016/j.​jenvm​an.​2012.​04.​047 Sep Purif Technol 266:118535. https://​doi.​org/​10.​1016/j.​seppur.​2021.​
Shi K, Qiu Y, Li B, Stenstromb MK (2016) Effectiveness and potential of straw- 118535
and wood-based biochars for adsorption of imidazolium-type ionic Yuan P, Wang J, Pan Y, Shen B, Wu C (2019) Review of biochar for the manage-
liquids. Ecotox Environ Safe 130:155–162. https://​doi.​org/​10.​1016/j.​ ment of contaminated soil: preparation, application and prospect. Sci
ecoenv.​2016.​04.​017 Total Environ 659:473–490. https://​doi.​org/​10.​1016/j.​scito​tenv.​2018.​12.​
Sidik SM, Jalil AA, Triwahyono S, Adam SH, Satar MAH, Hameed BH (2012) 400
Modified oil palm leaves adsorbent with enhanced hydrophobicity for Zhang P, Sun H, Min L, Ren C (2018) Biochars change the sorption and
crude oil removal. Chem Eng J 203:9–18. https://​doi.​org/​10.​1016/j.​cej.​ degradation of thiacloprid in soil: insights into chemical and biologi-
2012.​06.​132 cal mechanisms. Environ Pollut 236:158–167. https://​doi.​org/​10.​1016/j.​
Silvani L, Vrchotova B, Kastanek P, Demnerova K, Pettiti I, Papini MP (2017) Char- envpol.​2018.​01.​030
acterizing biochar as alternative sorbent for oil spill remediation. Sci Rep. Zhao MY, Cui YB, Li X, Liu YH, Li HX (2013) Study on purification of oil-polluted
https://​doi.​org/​10.​1038/​srep4​3912 sea water by rice hull adsorbent. Appl Mech Mater 295–298:1245–1248.
Stang M, Karbstein H, Schubert H (1994) Adsorption kinetics of emulsifiers at https://​doi.​org/​10.​4028/​www.​scien​tific.​net/​AMM.​295-​298.​1245
oil-water interfaces and their effect on mechanical emulsification. Chem Zhou S, You T, Zhang X, Xu F (2018) Superhydrophobic cellulose nanofiber-
Eng Process 33:307–311. https://​doi.​org/​10.​1016/​0255-​2701(94)​02000-0 assembled aerogels for highly efficient water-in-oil emulsions separation.
Sun K, Ro K, Guo M, Novak J, Mashayekhi H, Xing B (2011) Sorption of bisphe- ACS Appl Nano Mater 1(5):2095–2103. https://​doi.​org/​10.​1021/​acsanm.​
nol A, 17α-ethinyl estradiol and phenanthrene on thermally and hydro- 8b000​79
thermally produced biochars. Bioresource Technol 102(10):5757–5763. Zhu H, Qiu S, Jiang W, Wu D, Zhang C (2011) Evaluation of Electrospun Polyvi-
https://​doi.​org/​10.​1016/j.​biort​ech.​2011.​03.​038 nyl Chloride/Polystyrene Fibers As Sorbent Materials for Oil Spill Cleanup.
Tapia JI, Alvarado-Gómez E, Encinas A (2019) Non-expensive hydrophobic Environ Sci Technol 45(10):4527–4531. https://​doi.​org/​10.​1021/​es200​2343
and magnetic melamine sponges for the removal of hydrocarbons and
oils from water. Sep Purif Technol 222:221–229. https://​doi.​org/​10.​1016/j.​
seppur.​2019.​04.​008
Tran H, Lin C, Bui X, Ngo H, Cheruiyot NK, Hoang H, Vu C (2021) Aerobic
composting remediation of petroleum hydrocarbon-contaminated soil.
Current and future perspectives. Sci Total Environ 753:142250. https://​doi.​
org/​10.​1016/j.​scito​tenv.​2020.​142250
Veldkornet D, Rajkaran A, Paul S, Naidoo G (2020) Oil induces chlorophyll
deficient propagules in mangroves. Mar Pollut Bull 150:110667. https://​
doi.​org/​10.​1016/j.​marpo​lbul.​2019.​110667
Villegas MA, Navarro JMF (1988) Characterization of ­B2O3-SiO2 glasses pre-
pared via sol-gel. J Mater Sci 23:2464–2478
Wang F, Harindintwali JD, Yuan Z, Wang M, Wang F, Li S, Yin Z, Huang L, Fu Y,
Li L, Chang SX, Zhang L, Rinklebe J, Yuan Z, Zhu Q, Xiang L, Tsang D, Xu
L, Jiang X, Liu J, Wei N, Kastner M, Zou Y, Ok YS, Shen J, Peng D, Zhang
W, Barcelo D, Zhou Y, Bai Z, Li B, Zhang B, Wei K, Cao H, Tan Z, Zhao LB,
He X, Zheng J, Bolan N, Liu X, Huang C, Dietmann S, Luo M, Sun N, Gong
J, Gong Y, Brahushi F, Zhang T, Xiao C, Li X, Chen W, Jiao N, Lehmann J,
Zhu YG, Jin H, Schaffer A, Tiedje JM, Chen JM (2021) Technologies and
perspectives for achieving carbon neutrality. Innovation (n Y) 2(4):100180.
https://​doi.​org/​10.​1016/j.​xinn.​2021.​100180
Wathukarage A, Herath I, Iqbal MCM, Vithanage M (2019) Mechanistic under-
standing of crystal violet dye sorption by woody biochar: implications for
wastewater treatment. Environ Geochem Hlth 41(4):1647–1661. https://​
doi.​org/​10.​1007/​s10653-​017-​0013-8
Xie J, Lin R, Liang Z, Zhao Z, Yang C, Cui F (2021) Effect of cations on the
enhanced adsorption of cationic dye in Fe3O4-loaded biochar and
mechanism. J Environ Chem Eng 9(4):105744. https://​doi.​org/​10.​1016/j.​
jece.​2021.​105744