Journal of Environmental Management 377 (2025) 124660

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Journal of Environmental Management

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Research article

Enhanced simulated sunlight photolysis of antibiotics on soil surfaces by

biochar: Effects and mechanisms
Yuying Wu a , Dengmiao Cheng a,* , Jisen Xiong a , Shaoyu Tang a ,
Jonathan Woon Chung Wong a , Zhaojun Li b,**
a
Research Center for Eco-Environmental Engineering, Dongguan University of Technology, Dongguan, 523808, China
b
Shandong Key Laboratory of Animal Disease Control and Breeding, Institute of Animal Science and Veterinary Medicine, Shandong Academy of Agricultural Sciences,
Jinan, 250100, China

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

Keywords: The photocatalysis performance of biochar (BC) was often underestimate when it was employed to remediate
Antibiotics antibiotic-contaminated soil. In our study, we adopted sawdust, rice husk, and tobacco straw to prepare biochar
Biochar at three carbonization temperature (300 ◦ C, 500 ◦ C, and 700 ◦ C) and explored the effect of biochar amendment
Soil
on the sunlight photolysis of typical antibiotics tetracycline (TC), sulfamerazine (SM1), and enrofloxacin (ENR)
Photodegradation
Reactive oxygen species
on soil surfaces. The photolysis of three examined antibiotics in the surface layer of soil-biochar followed a quasi-
first-order reaction kinetics model (R2 > 0.9), and the photocatalytic activity of R500 (rice husk carbonized at
500 ◦ C) was the most prominent, which reduces the half-life t1/2 of TC, SM1 and ENR in red soil by 47.0%, 8.83%
and 17.1%, respectively. The results of quenching experiments demonstrated that reactive oxygen species (ROS)
1
O2 played a crucial role in promoting the degradation of TC and ENR while the 3DOM* greatly contributed to
the photodegradation of SM1. A maximal degradation rates of TC and ENR could be observed at a neutral pH but
the photolysis rate of SM1 peaked at a pH of 9. Both photolysis and indirect photolysis with the participation of
ROS led to the degradation of three antibiotics in soil as suggested by analyzing of degradation pathways. The
results of this study highlight the performance of biochar in photocatalysis by generating ROS, contributing to
further research on biochar that could achieve in-situ remediation of antibiotic-contaminated soils.

1. Introduction indirectly impacts the soil biota community and crop growth (Chung
et al., 2017; Liu et al., 2012; Mu et al., 2022), posing a potential threat to
The appropriate utilization of antibiotics in animal husbandry not human health (Liang et al., 2017).
only serves to treat bacterial infections, but also facilitates the growth of Solar light is a highly representative and potent natural source of
livestock and poultry (Yu et al., 2016). Antibiotics cannot be completely illumination. The annual influx of solar energy reaching the Earth’s
metabolized when entering organisms, most of which are excreted in the surface amounts to nearly 4 × 1024 J which induces irreversible
form of maternal or metabolic products (Carvalho and Santos, 2016), photochemical transformation of organic pollutants, serving as a crucial
and eventually enter the soil environment through channels such as mechanism for the photodegradation of antibiotics in surface soil (Xu
manure and irrigation of wastewater containing antibiotics (Lin et al., et al., 2019; Kabir et al., 2018). The photochemical degradation of soil
2016; Massé et al., 2014). Although the half-life of antibiotic pollutants antibiotics primarily occurs in the surface soil, predominantly attributed
in the environment varies from hours to months (Gavalchin and Katz, to the direct photolysis induced by the absorption of light radiation
1994), their continuous production, utilization, and release into the ranging from 290 nm to 800 nm by the chromophore groups within
environment contribute to their persistent presence. This directly and antibiotics. Additionally, reactive oxygen species (ROS) generated by

Abbreviations: BC, Biochar; OFG, Oxygen-containing functional groups; BCM, Biochar carbon matrix; PFRs, Presence of persistent free radicals; DOM, Dissolved
organic matter; 1O2, Singlet oxygen; SM1, Sulfamerazine; ENR, Enrofloxacin; TC, Tetracycline; IPA, Isopropanol; SA, Sorbic acid; SO, Sodium oxalate; DOC, Dissolved
organic carbon; TOC, Organic carbon; CEC, Cation exchange capacity; h+, Hole; 3DOM*, Excited triplet dissolved organic matter.
* Corresponding author.
** Corresponding author. Institute of Animal Science and Veterinary Medicine, Shandong Academy of Agricultural Sciences, Jinan, 250100, China.
E-mail addresses: [email protected] (D. Cheng), [email protected] (Z. Li).

https://doi.org/10.1016/j.jenvman.2025.124660
Received 28 October 2024; Received in revised form 12 February 2025; Accepted 18 February 2025
Available online 21 February 2025
0301-4797/© 2025 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

photosensitizers promote indirect photolysis (Jia et al., 2023). The (TCs) and quinolones (QNs) are the dominant antibiotics observed in soil
photodegradation process in natural soil environments is influenced by and sulfonamides (SAs) is capital antibiotic observed in surface water
multiple factors, including antibiotic properties (Lyu et al., 2022; (Lyu et al., 2020). Therefore, in this paper, biochars (BCs) from three
Mathon et al., 2021), as well as environmental variables such as light typical feedstocks (sawdust, rice husks and tobacco stalks) were pre­
intensity, initial concentration, soil moisture content, pH, photosensi­ pared and characterized. The impact of biochar amendment was eval­
tizers, background electrolytes and metal ions (Chen et al., 2011; Li uated by photodegradation of sulfamerazine (SAs), enrofloxacin (QNs),
et al., 2016; Song et al., 2020). and tetracycline (TCs) in surface red soil under simulated sunlight was
Biochar is a carbon-rich solid material that is obtained through the investigated. Additionally, the influence of different biochar types and
pyrolysis of biomass under limited oxygen conditions (Cernansky, dosages, as well as soil pH, on the photolysis of experimental antibiotics
2015). Due to its unique characteristics, such as a diverse adsorption on the soil surface was examined. A comprehensive analysis was con­
sites, abundant surface functional groups, high specific surface area, ducted to elucidate the potential photocatalytic mechanism and pro­
microporosity, and ion exchange ability, it exhibits a broad spectrum of posed degradation pathways. This study aims to reveal the photolysis
environmental applications (Oliveira et al., 2017). Suggested the bio­ mechanism of biochar amendment on typical antibiotics in soil, and
char addition significantly enhances microbial growth through provides insights for the further development of biochar materials for
increased adhesion area and nutrient availability, while also improving in-situ soil remediation.
bacterial activity and adaptability to antibiotics by altering fatty acid
composition and increasing gene expression levels (Yang et al., 2021a). 2. Materials and methods
Tang et al. (2024) reported an effective reduction in leaching of the two
sulfonamide antibiotics from soil amended with biochar (Tang et al., 2.1. Chemicals
2024); while biochar could accelerate the dissipation of tetracyclines
antibiotics and their intermediates in soil by altering soil properties (Yue Tetracycline (TC, >98%), sulfamerazine (SM1, >98%) and enro­
et al., 2019). However, few researches had focused on the photochem­ floxacin (ENR, >98%) were purchased from TCI Development Co., Ltd.,
ical performance of biochar (Guo et al., 2024). Shanghai. More information about the examined antibiotics could be
Biochar exhibits inherent photochemical properties, wherein the checked at Table 1S. Isopropanol (IPA, 99.5%), sorbic acid (SA, 99%),
presence of oxygen-containing functional groups (OFGs) facilitates their sodium oxalate (SO, 99.5%), and montmorillonite (MMT) were obtained
reactivity as sites for inducing the generation of reactive oxygen species from Macklin Biochemical Technology Co., Ltd. The high-performance
(ROS). The presence of quinone and anthracene functional groups on liquid chromatography (HPLC) grade acetonitrile (ACN), methanol,
biochar has been suggested by Xu et al. (2013) to contribute to its and formic acid were procured from Thermo Fischer Scientific Ltd.
photocatalytic functionality (Xu et al., 2013). The biochar carbon matrix China. The experiment was conducted using deionized water exclu­
(BCM) in biochar exhibits a structural resemblance to semiconductors sively. All other reagents employed in this study were of analytical
(Fang et al., 2017). This similarity enables the generation of photo­ grade.
generated electrons and holes that can react with dissolved oxygen,
leading to the formation of ROS. Moreover, the presence of persistent 2.2. Preparation and characterization of biochar
free radicals (PFRs) within biochar can effectively facilitate the gener­
ation of ROS (Fang et al., 2014; Huang et al., 2020). The dissolved The biomass raw materials contained a moisture of 7.54–10.50 wt%,
organic matter (DOM) produced during the biomass pyrolysis process 37.28–66.14 wt% of C and 33.09–46.68 wt% of O. The detailed infor­
can also generate excited organic matter under light irradiation, leading mation of biomass raw materials could be checked at SI (Figs. 1S and
to the production of singlet oxygen (1O2) or other ROS through energy 2S). Before placed in muffle furnace (Fig. 3S), the biomass raw materials
transfer (Yang et al., 2021b). As a conductor, the utilization of biochar were dried, crushed, and passed through a 20-mesh sieve, then put into
can enhance the facilitation of electron shuttling, thereby influencing porcelain crucibles and closed the lids. In order to decrease oxygen
the migration and transformation of pollutants in soil through mediating exposure, aluminum foil was used to wrap the porcelain crucibles
electron transfer reactions (Klüpfel et al., 2014). tightly. At an oxygen-limited condition (no sweeping gas flew into the
The conventional microbial degradation of most antibiotics in the pyrolysis reactor; during the pyrolysis process, no gas was introduced
soil environment is indeed limited due to their potent inhibition of into the pyrolysis plant, and the ventilation valve of the pyrolysis plant
environmental microorganisms (Kümmerer, 2009; Werner et al., 2009), was closed), the initial temperature was 25 ◦ C, the heating rate was
whereas hydrolysis also plays a limited role in the removal of antibiotics 10 ◦ C/min, with the carbonization temperatures were 300 ◦ C, 500 ◦ C,
in soil (Tang et al., 2024). Actually, under solar radiation, organic pol­ and 700 ◦ C, respectively, and kept for 120 min. In this study, five types
lutants can undergo direct photolysis by absorbing sunlight or indirect of biochar were prepared and labeled as S300, S500, S700, R500, and
photolysis facilitated by photosensitizers (photocatalysts) (Zhou et al., T500 respectively. The labels S, R, and T represent the raw materials
2024). Therefore, the transformation of antibiotic in the soil surface is used: sawdust, rice husk, and tobacco straw. Additionally, the numbers
mainly controlled by the photolysis process. However, the photolytic 300, 500, and 700 indicate the corresponding carbonization tempera­
behavior of antibiotics in soil is often underestimated (Tang et al., tures in degrees Celsius.
2024). Currently, the focus in biochar soil remediation is on the The specific surface area and pore size distribution of the biochar
adsorption of antibiotics and the modification of soil properties by particles was assayed by N2 adsorption at − 196 ◦ C using automatic
biochar to enhance the microbial degradation of antibiotics (Patel et al., surface area porosity analyzer (ASAP, ASAP2460, Micromeritics, USA).
2022; Zheng et al., 2022). Limited research has been conducted on the The functional groups of biochar particles were determined by Fourier
photodegradation effect of antibiotics adsorbed by biochar on solid transform infrared spectroscopy (FTIR, LUMOS, Bruker Optics, Ger­
surfaces (Bhattacharjee and Ahmaruzzaman, 2024; Wu et al., 2018). many). Elemental analyzer (EA, Vario Micro Cube, Elementar Company,
Furthermore, there is a scarcity of studies investigating the photo­ Germany) was used to analyzed the content of each element in biochar.
catalytic properties of biochar itself in soil environments and its asso­ The dissolved organic carbon (DOC) of biochar was measured on a TOC
ciated influencing factors, such as the impact of pH value on antibiotic analyser (varioTOC, Elementar, Germany). The pH and electrical con­
photolysis within the biochar-soil system and the influence of active ductivity (EC) of biochar is obtained by measuring the mixture of bio­
species on soil antibiotic photodegradation. char and deionized water (1:10, W/V) with a pH meter (FE28, Mettler
It is widely known that sawdust and tobacco stalks are typical agri­ Toledo, Switzerland) and conductivity meter (LE703, Mettler Toledo,
culture waste, and rice husk is an inevitable by-product of rice-farming Switzerland). Environmental persistent free radical signals were detec­
countries (Gan et al., 2022). Meanwhile, it is reported that tetracyclines ted by electron paramagnetic resonance spectroscopy (EPR, A200,

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Bruker, USA). Scanning electron microscope/energy dispersive spec­ either 0.1 mol/L HCl or 0.1 mol/L NaOH with an error margin of ±0.2.
troscopy (SEM/EDA, Merlin, Zeiss, Germany/AZtceOne, OXFORD, The moisture content was set at 60% to investigate the impact of varying
Britain) was used to observe the morphology of biochar and analyze its soil pH levels on the photochemical degradation of antibiotics in soil
element types and contents; Thermogravimetric analyze (TGA) was treated with 2% R500. In order to analyze the photodegradation
employed to evaluate carbonization state. In order to assess the risk of mechanism of examined antibiotics in soil amended with biochar, the
biochar amendment on the soil environment, the polycyclic aromatic degradation intermediates of TC, SM1 and ENR were identified by
hydrocarbons (PAHs) content (Table 2S) in biochar, the pH, EC and conducting photolysis kinetic experiment with a sampling interval of 0,
heavy metal content of the soil-biochar system were analyzed. A 6, 12, 24, and 48 h.
detailed description of biochar characterization and analysis methods
was provided in the Supplementary Information (SI). 2.4. Analysis of antibiotics and photoproducts of the irradiated soil
samples
2.3. Photolysis experiment
The extraction of antibiotics from soil samples was appropriately
The surface soils (0–20 cm depth) were collected from the Qiyang modified based on the method developed by Zhao et al. (2010) (Zhao
Red Soil Experimental Station of the Chinese Academy of Agricultural et al., 2010). A 500 mg solid-phase sample (dw) was accurately weighed
Sciences, representing a typical soil profile in southern China. The soil into a 10 mL centrifuge tube and vigorously mixed for 1 min with 2.0 mL
exhibited a pH of 5.44, a cation exchange capacity (CEC) of 5.74 cmol/ EDTA-McIlvaine buffer, followed by addition of 2.0 mL
kg, an organic matter content of 13.18 g/kg, a total organic carbon methanol-acetonitrile mixture (1:3, V/V). Subsequently, ultrasonic
(TOC) concentration of 0.57%, alkali hydrolyzed N of 65.45 mg/kg, extraction was performed for 10 min, followed by centrifugation at
available P of 27.45 mg/kg, available K of 75.07 mg/kg, Cu of 32.5 mg/ 5000 rpm for 5 min to collect the supernatant. The extraction process
kg, Zn of 75.7 mg/kg, Cd of 0.29 mg/kg, Cr of 74.9 mg/kg and Pb of was repeated twice. The supernatant was thoroughly mixed in prepa­
37.5 mg/kg. Details of the methods and instrumentation for the analysis ration for subsequent analysis of targeted antibiotics.
of soil samples have been supplemented in the SI. After air drying, the The samples were subjected to analysis using the ACQUITY UPLC H-
soil was sieved through a 1 mm nylon sieve and subsequently sterilized Class System in conjunction with the Xevo TQD Tandem Mass Spec­
in an autoclave at 121 ◦ C for 24 h. It was then stored in a low- trometer (Waters, USA). The sample separation was performed on a
temperature freezer for future use. UPLC HSS T3 column (2.1 × 100 mm, 18 μm, Waters), with the column
The photochemical reactions were conducted in a solid medium temperature maintained at 30 ◦ C during the detection process. The
surface photochemical reaction chamber, equipped with two 500 W mobile phase consists of acetonitrile (A) and a 0.1% aqueous solution of
xenon lamps (Fig. 4S) to simulate solar irradiation (λ > 290 nm) using a formic acid (B), with a flow rate of 0.2 mL/min, using the gradient
pyrex-well cooled and filtered system (Fig. 5S). The average light in­ elution method (Table 3S) and a sample volume of 3 μL. The ionization
tensity reaching the soil surface was measured to be 27.5 ± 0.15 mw/ source used was electrospray ionization (ESI) in positive ion detection
cm2 using an optical power meter (PM100D + S425C, Thorlabs). mode. The detailed settings for the mass spectrum are presented in
Additionally, it featured a rotating sample reaction tray and a water- Table 4S. The samples were detected by external standard method.
cooled air-cooled control system. The rotatable sample reaction tray However, in order to further eliminate the matrix effect, the standard
ensures uniform illumination of soil photolysis reaction samples, while solution was prepared by diluting the standard antibiotic reserve solu­
the water-cooled and air-cooled control system guarantees precise tion with the extraction solution of blank soil sample. The average re­
control of the photolysis temperature in this reaction system at 30 ± covery of SM1, TC and ENR was 82.4%, 83.4% and 69.1%, respectively.
2 ◦ C. The samples were flattened in 35 mm glass culture ware, each The detection limits of SM1, ENR and TC were 1.92, 2.33 and 1.86 μg/L,
containing 490 mg red soil and 10 mg biochar (2% dry weight). Sub­ respectively.
sequently, a mixed antibiotic solution was added to achieve final con­ The degradation intermediates of TC, SM1 and ENR were identified
centrations of TC, SM1 and ENR at 250 mg/kg each. The adsorption using a Q-Exactive Plus hybrid quadrupole-Orbitrap mass spectrometer
equilibrium and uniform distribution of antibiotics in biochar-soil can (Thermo Scientific) coupled with a Dionex Ultimate 3000 UHPLC sys­
be achieved following thorough shaking (100 rpm) and subsequent 24-h tem. The scanning range m/z was 50–500, and the detailed settings for
standing period (Srinivasan et al., 2014). The thin layer of soil has a this mass spectrum are presented in Table 5S. Compound Discoverer 3.1
thickness of approximately 0.2 mm. The soil moisture was maintained at software was utilized for facilitating product analysis.
approximately 60% throughout the duration of the experiment. The
weight of each glass culture ware containing soil sample was recorded 3. Results and discussion
before placed into the photochemical reaction device and a phenome­
non that the humidity of the soil sample would decrease to about 20% in 3.1. Biochar characterization
2 h could be observed. Therefore, an appropriate amount of deionized
water was added to the soil samples to maintain a humidity of 60% every It was reported that the SAs possess a high mobility in soils, while the
2 h. Sampling was conducted at intervals of 0, 6, 12, 24, and 48 h. Dark photodegradation of antibiotics in soil mainly occur at surface soil (Jia
controls were conducted under identical experimental conditions. Each et al., 2023). Hence, adsorption tests were conducted to evaluate the
experiment was replicated thrice. adsorption capacity of biochars, and the result suggested a limited
The quenching tests were conducted using sorbic acid (SA), iso­ adsorption capacity to SM1 (removal rate <15%) of soil amended with
propanol (IPA), sodium oxalate (SO), and sodium azide (NaN3). Spe­ R300, R500, T300 and T700 respectively, indicating SM1 had the risk of
cifically, IPA was employed to quench hydroxyl radical (•OH), SA was migrating deep into the soil and not being able to absorb optical radi­
utilized to quench excited triplet dissolved organic matter (3DOM*), ation. From the perspective of practical application, if the biochars were
NaN3 captured singlet oxygen (1O2), and SO captured hole (h+) (Cheng not capable to fix the examined antibiotics in the superficial layer of the
et al., 2018; Rao et al., 2022). soil, it would be of limited use to study the effect of biochar addition on
To assess the impact of varying concentrations of biochars on the the photodegradation of antibiotics. Therefore, in this study, the prop­
photodegradation of three antibiotics, R500 biochar was incorporated erties and performance of R300, R500, T300 and T700 would not be
into soil at ratios of 0.5%, 1%, 2%, and 4% dry weight. The experiment further investigated.
maintained a soil moisture level of approximately 60% throughout, with Due to variations in biomass raw materials, significant disparities
sampling conducted at time intervals of 0, 6, 12, 24, and 48 h. were observed in the physicochemical properties of the biochar
The pH of the red soil was adjusted to 3, 5, 7, 9 using a solution of (Table 1). With the elevation in carbonization temperature, the pH and

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Table 1
Physicochemical properties of biochar used in this study.
Biochar pH ECa (μs/cm) Elemental composition (%) Atomic ratio DOCb (%) SSAc (m2/g) PVd (cm3/g)

C H N O C/N C/O C/H

S700 11.03 943.90 89.60 1.39 0.62 7.97 144.52 11.24 64.40 0.15 511.75 0.28
S500 10.50 634.87 79.99 2.32 0.47 15.00 170.19 5.33 34.48 0.29 406.34 0.18
S300 8.03 354.30 64.84 2.80 0.23 31.76 281.91 2.04 23.16 1.02 1.79 0.0062
T500 10.32 5213.00 70.67 5.19 1.74 10.40 40.61 6.80 13.62 1.10 2.85 0.0082
R500 10.32 877.67 49.10 5.35 0.45 28.80 109.11 1.70 9.18 0.26 120.28 0.072
a
Electrical conductivity.
b
Dissolved organic carbon.
c
Specific surface area.
d
Pore volume.

EC of the biochar derived from sawdust demonstrated an increasing carbonization at a temperature of 700 ◦ C. For sawdust biochar, an
trend. Compared to R500 and T500, S500 exhibited a higher carbon (C) increasing carbonization temperature resulted in a progressive
content and a lower hydrogen (H) content, contributing to the highest enhancement of both specific surface area (SSA) from 1.79 m2/g to
C/H ratio (34.48) among biochars prepared at same temperature 511.75 m2/g and total pore volume (PV) from 0.0062 cm3/g to 0.28
(500 ◦ C). The C/H and C/O ratios of sawdust biochar exhibited an in­ cm3/g (Table 1). This result was in accordance with the SSA and PV of
crease with rising carbonization temperatures, ranging from 23.16 at sawdust biochar as reported in a previous study (Xu et al., 2021). The
300 ◦ C to 64.40 at 700 ◦ C and 2.04 at 300 ◦ C to 11.24 at 700 ◦ C, generation of SSA during the carbonization process mainly results from
respectively. Furthermore, the elevation of carbonization temperature the volatilization mechanisms and subsequent liberation of organic
can induce the degradation of organic matter, leading to a gradual substances, leading to the formation of voids within the biochar matrix
reduction in oxygen content in sawdust biochar. These findings suggest (Xu et al., 2021; Oliveira et al., 2017). Conversely, the decomposition of
that biochar’s aromaticity increases with higher carbonization temper­ cellulose initiates at approximately 300 ◦ C, leading to the gradual pro­
atures, while its polarity decreases and stability improves (Spokas, duction of bio-oil and a mixture of gases (Patel et al., 2022). Therefore,
2010). the lower the temperature, the smaller the SSA and pore volume. Several
The FTIR spectra for all five types of biochars are presented in factors, including the pyrolysis temperature and biomass feedstock type,
Fig. 1a. The abundance of functional groups exhibited a decrease with can significantly influence the properties of biochar (Oliveira et al.,
the increasing pyrolytic temperature of the biochar. Xiao et al. (2020) 2017). The relatively low SSA and PV observed in T500 may be attrib­
also observed a decline in the abundance of functional groups within uted to the raw material tobacco straw. In the study conducted by (Feng
biochar as the pyrolysis temperature increased during the preparation et al., 2022), it was observed that the tobacco straw biochar exhibited a
process (Xiao et al., 2020). The absorption peak of the hydroxyl func­ specific surface area of only 3.53 m2/g and a pore volume of 0.0061
tional group (-OH) was observed at approximately 3450 cm− 1. Ab­ cm3/g. The carbon content of wood biochar is comparable to that
sorption peak around 2920 cm− 1 was generally considered to be examined by (Yue et al., 2019). As evidenced by the results obtained
generated attributed to the stretching vibrations of -CH3; The signal from EDS analysis, The content of mineral metals in tobacco straw
observed near 1735-1710 cm− 1 could be corresponded to aromatic biochar is significantly higher than that in other types of biochar.
carbonyl/carboxyl/quinone of C=O; The spectral range of 1610-1450 Consequently, T500 exhibits the highest conductivity among all tested
cm− 1 exhibited characteristic peaks corresponding to the benzene ring samples (Yue et al., 2019). Additionally, R500 exhibits an exceptionally
or aromatic group, indicating the presence of stretching vibrations high Si content of 7.29%, due to the substantial presence of phytolith in
associated with C=C and C=O bonds within the aromatic ring of biochar the rice husk (Gan et al., 2022).
(Fang et al., 2017; Xiao et al., 2020). The characteristic absorption peak
at 1381 cm− 1 corresponds to the carboxylate (COO group) or aliphatic 3.2. Photodegradation of antibiotics
(CH3 or CH2 groups). In the fingerprint region, the strong peak observed
near 1100 cm− 1 represents stretching vibration of C-O, and this signal A limited change of pH, EC and heavy metals content could be
also could be correlated to the bending vibrations of Si− O− Si (Guo observed after the addition of examined biochars (Fig. 6S). The result of
et al., 2024; Lu et al., 2024). Pearson’s rank correlation analysis (Table 6S) suggested no correlation
The EPR spectrum of the biochar is shown in Fig. 1b, exhibiting an between the photolysis of antibiotics and the presence of heavy metals in
initial strengthening followed by weakening with increasing carbon­ the soil-biochar system. The dark control test revealed no significant
ization temperature, and reaching its peak intensity at a carbonization degradation of antibiotics in the soil treated with darkness during the
temperature of 500 ◦ C. The weak EPR signal observed in biochar pre­ 48-h experimental period, indicating minimal impact from microbial
pared at a lower carbonization temperature of 300 ◦ C can be attributed degradation or hydrolysis throughout the experiment. However, when
to the incomplete reaction of biomass constituents. However, with an exposed to simulated sunlight (λ > 290 nm), all three antibiotics
increase in temperature to 700 ◦ C, there is a significant degradation of exhibited noticeable photolysis in the biochar-treated soil (Fig. 3). The
organic matter components leading to a pronounced attenuation of experimental results of photochemical degradation of antibiotics in soil
biochar EPR signal (Cui et al., 2017). The TGA result of biochar could be and biochar treated soil surface (Table 7S) can be well fitted (R2 > 0.95)
checked in Fig. 1c, indicating the carbonization status of biochar. For the by the pseudo-first-order reaction kinetics equation:
biochar prepared at relatively high temperatures (≥500 ◦ C), as most of
Ln(Ct / C0 ) = -Kobs × t (1)
component in the biomass had carbonized, attenuation of the mass was
not very significant with increasing temperature; On the contrary, for where t is the photoreaction time (h), Ct is the antibiotic concentration
S300, an obvious mass reduction could be observed at temperatures over when the photoreaction time reaches t (mg/kg), C0 is the antibiotic
300 ◦ C which could be attributed to the loss of volatile and decompo­ concentration at the initial time (mg/kg), Kobs denotes the apparent rate
sition of lignin, cellulose and hemicellulose (Oliveira et al., 2017). constant of pseudo-first-order.
As shown in Fig. 2, the SEM images demonstrate that the biochar The corresponding half-life (t1/2) can be calculated as:
maintains its original porous structure even after undergoing

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

rates of SM1 and ENR, with Kobs values of 8.09 × 10− 3 h− 1 and 8.19 ×
10− 3 h− 1 respectively.
Due to the low-temperature carbonization, the S300 biochar
exhibited a significantly elevated concentration of DOC (Table 1)
(Oliveira et al., 2017; Wu et al., 2020). It also means the heightened
DOM concentration can effectively quench the excited molecules of TC
and ENR, thereby impeding their photodegradation. Furthermore, the
DOM can also compete with TC and ENR molecules for photons in
simulated sunlight, thereby influencing the direct photolysis of TC
(Liang et al., 2015). However, sulfonamide compounds (SAs) exhibit
enhanced reactivity in the three-dimensional ordered mesoporous
structure (3DOM*), thereby facilitating the photodegradation of SM1
when a certain amount of S300 is added (Li et al., 2015).
The surface of biochar at a moderate carbonization temperature
(500 ◦ C) exhibited a substantial presence of OFGs, which underwent
photoexcitation to generate ROS (Chen et al., 2017; Xiao et al., 2020; Xu
et al., 2013). The BCM structure of biochar generates electron-hole pairs
upon light irradiation, thereby facilitating the production of other ROS
(Velo-Gala et al., 2017). Simultaneously, stable PFRs were observed on
the surfaces of S500, T500, and R500, further enhancing ROS generation
(Huang et al., 2020). Silicon had been proven to be photocatalytically
active, while rice husk was a silicon-rich biomass material that contains
SiO2 that could be converted to amorphous silicon at moderate
carbonization temperatures (Gan et al., 2022; Shen, 2017). And it was
reported that amorphous silicon could facilitated photooxidation of
sulfadiazine in water by increasing reactive oxygen species ROS con­
centration (Guo et al., 2024). The photochemical activity of R500 was
enhanced due to the existence of silicon (Fig. 2) and hence R500
exhibited a considerable photochemical performance. The exceptional
conductivity exhibited by T500 enables the effective segregation and
movement of photo-induced electrons and holes, consequently
enhancing charge carrier transportation (Li et al., 2018). Additionally,
Song et al. (2020) have demonstrated that tetracycline can form com­
posite compounds with enhanced photochemical effects upon Ca2+
binding, leading to augmented removal kinetics and efficacy (Song
et al., 2020). This finding further elucidates the exceptional photo­
chemical performance of T500, characterized by a substantial concen­
tration of metal ions.
The addition of S700 exhibits a modest inhibitory effect on the
photolysis of ENR and SM1, potentially attributed to its higher pore
volume compared to other biochar types. Consequently, SM1 and ENR
can penetrate the porous structure, thereby attenuating their direct
photolysis. The adsorption efficiency of quinolone antibiotics was found
to be significantly influenced by the surface area, porosity, and pore size
of the adsorbent in the study conducted by (Yu et al., 2016). Moreover,
the limited presence of oxygen-containing functional groups during
high-temperature treatment results in a diminished capacity for ROS
generation (Xiao et al., 2020).
Fig. 1. Fourier transform infrared (FTIR) spectrometers (a), electron para­
magnetic resonance (EPR) spectrometers (b) and thermogravimetric analysis 3.3. Determination of major reactive species
(TGA) curve (c) of five types of biochar, namely S300, S500, S700, R500, and
T500. The labels S, R, and T represent the raw materials used: sawdust, rice After the addition of 2% R500, the t1/2 values of TC, SM1, and ENR
husk, and tobacco straw respectively; the numbers 300, 500, and 700 indicate were observed to be 54.8 h, 85.7 h, and 84.6 h, respectively. In com­
the corresponding pyrolysis temperatures in degrees Celsius. parison with the control red soil, these values decreased by 47.0%,
8.83%, and 17.1% respectively. Therefore, due to its exceptional pho­
/
t1/2 = Ln 2 Kobs (2) tocatalytic performance, R500 was selected for subsequent
investigations.
The degradation of TC was enhanced by the addition of 2% biochar, Indeed, the presence of humic acid and metal ions in soil can induce
with the exception of S300. The Kobs value for TC photolysis in red soil the generation of ROS, thereby facilitating the degradation of pollutants.
without biochar (control check, CK) was determined to be 6.70 × 10− 3 Consequently, antibiotics undergo both direct and indirect photolysis in
h− 1. T500 and R500 exhibited the most pronounced impact on the shallow surface layer of soil (Xie et al., 2019). To further investigate
enhancing TC photolysis, with Kobs values of 12.90 × 10− 3 h− 1 and the types of indirect photolysis, the effects of four quenchers on the
12.70 × 10− 3 h− 1, respectively. Compared to the Kobs of SM1 in red soil photolysis of antibiotics in red soil were examined. After the addition of
(7.34 × 10− 3 h− 1), the addition of S300 significantly enhanced the quenching agents into the system, as depicted in Fig. 4, the photolysis of
photodegradation of SM1, resulting in an increased Kobs value of 8.80 × TC exhibited variable suppression, with SA and NaN3 demonstrating the
10− 3 h− 1. The presence of R500 significantly affected the degradation most pronounced inhibitory effect. The contribution of •OH and h + to

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Fig. 2. Scanning electron micrographs (SEMs) of S300 (a), S500 (b), S700 (c), T500 (d), and R500 (e) accompanied by their respective energy-dispersive X-ray
spectroscopy (EDS).

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Fig. 3. Photolysis kinetics of (a) TC, (b) SM1 and (c) ENR in red soils without biochar (CK) and red soil amended with 2% different biochar (S700, S500, S300, R500
and T500).

TC photolysis was relatively minor, with Kobs values of 6.33 × 10− 3 h− 1 addition of IPA. Additionally, Xiao et al. (2020) provided evidence
and 6.15 × 10− 3 h− 1 respectively. As mentioned earlier, the presence of highlighting the significant contribution of h + to the photolysis of ENR
DOM can potentially influence the self-sensitized photolysis of TC, (Xiao et al., 2020).
whereas SA not only acts as a quencher for 3DOM*, but also effectively
deactivates excited triplet molecules generated upon antibiotic photon
absorption. The presence of SA also partially hinders the direct photol­ 3.4. Effect of biochar concentration and pH on photodegradation of
ysis of TC (Cheng et al., 2018). The involvement of 1O2 as a crucial antibiotics
reactive species in the photodegradation of TC cannot be overlooked,
with the Kobs for TC decreasing to only 2.00 × 10− 3 h− 1 upon addition of The impact of biochar concentration on the photolysis efficiency of
NaN3. The study conducted by Chen et al. (2008) also revealed the three antibiotics is illustrated in Fig. 5a, wherein all observed photolysis
significant involvement of 1O2 in the photolysis process of TC in aqueous efficiencies surpassed those of the CK treatment. The photolysis
solutions under simulated sunlight (Chen et al., 2008). The addition of behavior of antibiotics on biochar-amended soil is influenced by two
SA significantly inhibited the photolysis of SM1, with an inhibition rate competing factors. On one hand, as previously mentioned, the presence
reaching 63.1%, thereby indicating the crucial role of 3DOM* as an of OFGs, PFRs, and DOMs attached to the surface of biochar can stim­
active species in promoting SM1 photolysis. The addition of IPA had ulate the generation of reactive species and thereby facilitate indirect
minimal impact on SM1, as evidenced by the Kobs value of only 6.91 × photolysis of antibiotics. Hence, it is undeniable that an increase in R500
10− 3 h− 1, suggesting that •OH exerted negligible influence on the concentration theoretically enhances antibiotic photolysis. On the other
photolysis of SM1. Li et al. (2015) also revealed that the presence of •OH hand, a high concentration of biochar covering the soil surface impedes
exhibited a limited impact on the photolysis process of sulfadiazine in xenon lamp radiation penetration, diminishing the extent to which
aqueous environments (Li et al., 2015). The photodegradation of SM1 in antibiotic molecules are exposed to radiation and consequently reducing
biochar-amended soil was mainly attributed to the contributions of both direct antibiotic photolysis (Luo et al., 2017; Serelis et al., 2021).
h+ and 1O2. Moreover, the concentration of DOM increases proportionally with the
The addition of four quenchers, as illustrated in Fig. 4c, inhibited the biochar concentration. This not only enables DOM to independently
photolysis of ENR. Notably, IPA, SO, and NaN3 consistently exhibited absorb photons but also facilitates the quenching of antibiotic molecules
significant inhibitory effects, suggesting the involvement of •OH, h+ and in their excited state (Liang et al., 2015; Serelis et al., 2021).
1
O2 in the photodegradation process of ENR. Wu et al. (2018) speculated The Kobs values of the three antibiotics exhibited a positive correla­
that •OH play a pivotal role in the photolysis of ciprofloxacin (Wu et al., tion with increasing biochar addition, reaching their maximum at 4%.
2018). In this study, the Kobs was determined to be 5.50 × 10− 3 h− 1 upon Specifically, the Kobs values for TC, SM1, and ENR were determined to be
19.30 × 10− 3 h− 1, 8.10 × 10− 3 h− 1, and 8.40 × 10− 3 h− 1 respectively.

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Fig. 4. Effects of different radical quenchers on the photolysis of (a) TC, (b) SM1 and (c) ENR in the shallow surface of soil. Reaction conditions: [SA] = 0.05 mmol/g,
[IPA] = 0.05 mmol/g, [SO] = 0.1 mmol/g and [NaN3] = 0.02 mmol/g.

Fig. 5. Effects of different concentrations (0%, 0.5%, 1%, 2% and 4%) of R500 on the photodegradation efficiencies of TC, SM1 and ENR (a), and effects of different
pH values (pH = 3, pH = 5, pH = 7 and pH = 9) on the photodegradation efficiencies of TC, SM1 and ENR in soil amended with 2% R500 (b).

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

However, the promotional effect of R500 on SM1 at a 4% ratio is not red soil was investigated and illustrated in Fig. 5b. At a pH of 3, the
statistically significant compared to TC and ENR, potentially due to the red soil exhibits a positive charge (Fig. 7S), and the three antibiotics
preferential infiltration of low molecular weight SM1 into the biochar’s exist in stable cationic forms. The contact between antibiotics and soil
pore structure, thereby attenuating direct photolysis. Serelis et al. was hindered by electrostatic repulsion, thereby impacting the transport
(2021) also observed a decrease in the degradation rate with increasing of light-generated ROS and other reactive species between soil and an­
biochar concentration during their investigation of the impact of biochar tibiotics, ultimately resulting in the lowest degradation rate among the
on the photodegradation of metrobuzin herbicide (Serelis et al., 2021). three antibiotics (Xing et al., 2023). With the increase in pH to
Considering the limited promoting effect of further increase biochar approximately 7, there is a gradual augmentation in the proportion of
concentration and the consumption for biochar production, the 2% zwitterionic forms, characterized by relatively weak stability and sus­
biochar concentration was selected for further research. ceptibility to photolysis (Araki et al., 2002). As the pH increases to 9,
The structures and ionization schemes of examined antibiotics was antibiotics undergo a transition in molecular structure, resulting in a
shown in Fig. 6. The pH value, as an ionic compound, plays a crucial role singular anionic state that promotes stabilization and induces electro­
in influencing the photolysis of antibiotics. Therefore, the impact of pH static repulsion with negatively charged soil-biochar carriers (Yue et al.,
on the photolysis behavior of three antibiotics in 2% biochar-modified 2019).

Fig. 6. Structures and ionization schemes of (a) TC, (b) SM1, and (c) ENR.

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Fig. 7. The possible reaction scheme for the transformations of TC parent compound to product T1~T7 (a), SM1 parent compound to product S1~S7 (b) and TC
parent compound to product E1~E12 (c).

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

Fig. 7. (continued).

Interestingly, the Kobs values of SM1 exhibit an increase from 7.02 × in Fig. 7.
10− 3 h− 1 to 9.59 × 10− 3 h− 1 with the elevation of pH from 3 to 9 Based on the results obtained from first-order mass spectrometry and
(Fig. 5b). The unique molecular structure of sulfonamide antibiotics Compound Discoverer 3.1 calculations, in conjunction with previous
(SMs) may account for this phenomenon (Lyu et al., 2022). The quantum studies (Liu et al., 2016; Niu et al., 2013; Tang et al., 2023), a putative
yield of SMs, such as sulfadiazine and sulfamethazine, has been reported photodegradation pathway of TC under xenon lamp irradiation was
to be higher in their anionic state compared to their amphoteric state proposed (Fig. 7a). The compound TC undergoes a hydrolysis reaction,
(Boreen et al., 2005). Moreover, in alkaline conditions, the presence of resulting in the removal of a hydroxyl group and the formation of
SMs facilitated the production of ROS (Álvarez-Esmorís et al., 2022). A product T2 (Liu et al., 2016). The dimethylamino moiety of the tetra­
similar trend was observed in the study of SMs in the photoconversion of cycline molecule has been reported to be susceptible to oxidation (Niu
water environments, whereas another study demonstrated that anionic et al., 2013), suggesting that this site may undergo demethylation and
sulfopyridine exhibited higher DOM reactivity compared to its neutral give rise to the product T4 upon attack by ROS. The C-N bond underwent
counterpart (Ge et al., 2019). direct photolysis and cleavage, resulting in the formation of product T5.
As the duration of illumination increases, the ring structure gradually
opens, leading to the detection of small molecule product T3. The
3.5. Possible pathways for the photodegradation of TC, SM1, and ENR presence of highly charged phenolic structures in TC molecules facili­
tates facile oxidation of phenolic hydroxyl groups into phenoxy groups
In order to further elucidate the mechanism underlying the impact of (Zhang et al., 2018). Considering the molecular structure’s stability, it is
biochar on photolysis of the three experimental antibiotics in soil, we plausible to infer that product T1 may be formed. The TC molecule
investigated the degradation products of TC, SM1, and ENR at five time undergoes double bond destruction and subsequent partial hydroxyl­
points (0, 6, 12, 24, 48 h) during the experimental cycle using a UHPLC- ation of amino methyl groups, resulting in the formation of product T6,
Q-Orbitrap HRMS method. According to the variation in product which further undergoes dealkylation to yield product T7.
composition, the potential degradation intermediate products of TC, The photodegradation pathway of SM1 was elucidated in Fig. 7b,
SM1 and ENR could be checked at Table 8S, Tables 9S and 10S encompassing three primary categories of photolysis reactions: direct
respectively, and transformation pathways are determined as illustrated

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Y. Wu et al. Journal of Environmental Management 377 (2025) 124660

photolysis, amino nitrogen oxidation, and amino carboxylation. During Acknowledgments

the direct photolysis process of SM1, the S-N bond undergoes cleavage,
resulting in the formation of product S1 (Yang et al., 2017). Addition­ This work was financially supported by the Basic and Applied Basic
ally, C-N bond scission leads to the generation of sulfaguanidine (S3). As Research Foundation of Guangdong Province (2022A1515010751) and
previously mentioned, the photolysis of SM1 involved h+ and 1O2, the National Natural Science Foundation of China (52370141,
leading to amino nitration on the benzene ring and resulting in the 31772395).
formation of product S2. The presence of •OH likely induces the hy­
droxylation of amino groups on the benzene ring, leading to the for­ Appendix A. Supplementary data
mation of product S4. Meanwhile, SM1 undergoes Smiles-type
rearrangement upon photolysis (Boreen et al., 2005), resulting in the Supplementary data to this article can be found online at https://doi.
formation of products S7 and SO2. The amino groups on the benzene ring org/10.1016/j.jenvman.2025.124660.
of S7 undergo hydroxylation (S5) and nitration (S6).
Referring to the photolysis pathway of ciprofloxacin adsorbed on Data availability
montmorillonite under xenon lamp, we hypothesize that the degrada­
tion of ENR under xenon lamp primarily manifests in the piperazine Data will be made available on request.
group (Fig. 7c), as commonly reported through various oxidation pro­
cesses (Wu et al., 2018; Xiao et al., 2020). Under the influence of ROS, a References
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