Water Research 184 (2020) 116165

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Water Research
journal homepage: www.elsevier.com/locate/watres

Filtration of microplastic spheres by biochar: removal efficiency and

immobilisation mechanisms
Ziheng Wang a, Majid Sedighi b,∗, Amanda Lea-Langton c
a
PhD Student, Department of Mechanical, Aerospace and Civil Engineering, School of Engineering, The University of Manchester, Manchester, M13 9PL,
United Kingdom
b
Senior Lecturer, Department of Mechanical, Aerospace and Civil Engineering, School of Engineering, The University of Manchester, Manchester, M13 9PL,
United Kingdom
c
Lecturer, Department of Mechanical, Aerospace and Civil Engineering, School of Engineering, The University of Manchester, Manchester, M13 9PL, United
Kingdom

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

Article history: Extensive presence of microplastic pollution in the aquatic environment has recently been identified as a
Received 6 March 2020 critical global challenge. A large proportion of the microplastic in aquatic environments originates from
Revised 8 July 2020
the effluent discharges from wastewater treatment plants and urban runoff. We present an experimental
Accepted 9 July 2020
study on the removal of microplastic spheres using biochar as potential low-cost material for integra-
Available online 10 July 2020
tion in sand filter systems to improve their efficiency for removing microbeads in wastewater treatment
Keywords: plants. Based on the results of a series of filtration tests and microscopic characterisation, the major
Microplastic mechanisms of interactions between the microplastic spheres and biochar and immobilisation processes
Biochar are presented.
Morphology
Immobilisation The results of leaching column tests on three biochar samples produced at three different temperatures
Porous media from corn straw and a hardwood biochar are compared. The results show that the biochar filters provide
Wastewater significant capacity for the removal and immobilisation of 10 μm diameter microplastic spheres (above
95%) which is much larger than that of similar grain-sized sand filter studied. The extensive ESEM micro-
scopic examination on the samples retrieved after the leaching tests show that the microplastic spheres
were immobilised through three morphologically controlled mechanisms which are conceptualised to be
‘Stuck’, ‘Trapped’ and ‘Entangled’ whilst the microplastic spheres only ‘Stuck’ in sand filter. The presence of
abundant honeycomb structures and thin chips to the high removal and immobilisation capacity of corn
straw biochar produced at 500 °C and the hardwood biochar. In this study, we demonstrate that biochar
can offer extensive potential for immobilisation of microplastic spheres (microbeads). This capacity can
in principle be investigated and utilised to improve the efficiency of sand filters to remove microplastic
in wastewater treatment plants.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction impact of primary microplastic sourcing from industrial detergents

(Qi et al., 2020) is of particular concern with regards to their toxic
The alarming extent of microplastics presence in the aquatic potential (Jaikumar et al., 2019).
environment has recently attracted global attention to the po- The production and release of microplastic particles in numer-
tential health and environmental issues, as well as the research ous forms and from various anthropogenic activities to the aquatic
need for developing sustainable solutions to reduce its emission environment is significant and still growing (Miranda et al., 2019).
and release to the aquatic environment. Although the toxicologi- It is estimated that approximately 80% of the microplastic in ocean
cal impacts of microplastic pollution to the living organisms and originates from land-based sources which are mainly related to the
human health are yet to be explored (Barboza et al., 2018), the effluent discharges of sewage, wastewater treatment plants and ur-
World Health Organisation recognises the microplastic pollution in ban runoff (Ritchie and Roser, 2020). Sewage systems are a major
aquatic environment to be an urgent global problem. The potential pathway of microplastic transportation (Zhang and Chen, 2020);
despite the fact that WWTPs have shown to be able to retain
∗ the majority of microplastic particles. Although the importance of
Corresponding author.
E-mail address: [email protected] (M. Sedighi).

https://doi.org/10.1016/j.watres.2020.116165
0043-1354/© 2020 Elsevier Ltd. All rights reserved.
2 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

sewer overflow on microplastic transport has only limited study terial and widely utilised in agriculture to improve the soil prop-
(Siegfried et al., 2017), it has been found that the sewer over- erties with significant economic added value (Oni et al., 2020). It
flow can be an important pathway for the transport of microplastic has been shown that replacing activated carbon can fully or par-
during heavy precipitations (Mak et al., 2020). The overflow from tially by biochar (Kah et al., 2017) significantly reduce the process
WWTPs sewer and municipal drainage can facilitate the trans- cost (including regeneration cost) while maintaining a similar level
port of microplastics to the aquatic environment (Ó Briain et al., of removal efficiency in WWTPs. Due to the high adsorption ca-
2020). Recent studies provide evidence of enhanced microplastic pacity of biochar, the low cost of the pyrolysis process to manu-
release after rainy days into rivers due to municipal sewer over- facture biochar and the extensive potential for the local produc-
flow (Cheung et al., 2019; Chen et al., 2020). tion (using locally available feedstock), the application of biochar
Studies on microplastics in the influent and effluent of waste in water/wastewater treatment systems has received an increasing
water treatment plants (WWTPs) reveal that the efficiency of pri- attention (Inyang and Dickenson, 2015).
mary, secondary and tertiary treatment processes to remove/retain Despite the fact that a wealth of knowledge on adsorption of
microplastic particles is mostly above 90% (Ziajahromi et al., 2017; various chemicals on biochar has been developed (Dai et al., 2019),
Conley et al., 2019; Talvitie et al., 2017a) and majority of mi- research on potential use of biochar in removing microplastic is
croplastic particles in the effluent remains in the sludge (Ngo et al., only at the very early stages of development. The microstructure
2019). Despite the high efficiency of the treatment systems in of biochar contains pores at varying scales ranging from 50 μm
WWTP to remove the majority of microplastic prior to the dis- to less than 1 nm. The complex and multiscale structure provides
charge to aquatic environment, the quantity microplastic parti- an ideal porous structure for the removal of turbidity from water
cle released is still of great concern due to the significant vol- (Marcus et al., 2014). In this paper we look at whether such ca-
ume of wastewater treated on a daily base (Enfrin et al., 2019; pacity can be utilised for the removal of microplastics. We present
Long et al., 2019). Improving the effectiveness of microplastic re- a fundamental investigation into mechanisms of interactions be-
moval is therefore of high importance to minimise the release of tween biochar and microplastic spheres.
microplastics. With regards to the size, microplastic is categorised as parti-
Case studies reported highlight the importance and effective- cles down to 0.1μm (Sobhani et al., 2020) (smaller sizes are cat-
ness of the tertiary treatment processes in removing microplas- egorised as nanoplastics). Studies on microplastic in WWTPs are
tic (Talvitie et al., 2017b). Rapid sand filters (as part of the last mostly refer to the particles larger than 10 μm (Rajala et al.,
stage of the tertiary treatment) present a high efficiency and po- 2020). It is recognised that smaller size microplastic is more likely
tential for removing microplastic particles at a reasonable scale. In to break through the WWTPs (Mintenig et al., 2017). The trans-
an examination of a number of WWTPs in Finland, the efficiency port of plastic particles ranging between 0.02 μm and 2 μm in
of rapid sand filter to remove the microplastic from the effluent sand and biochar has recently been reported (Tong et al., 2020).
of secondary treatment stage was found to be 97% (Talvitie et al., This range of microplastic sizes (0.02 μm-2 μm) is close to col-
2017a). A similar study on different tertiary treatment systems of loid sizes (0.001 μm-1 μm) (Jonasz and Fournier, 2007) for which
WWTPs (coagulation plus either of the final stage treatments in- the magnitude and polarity of surface charge can play critical role
cluding ozone, membrane disc-filter and rapid sand filtration) in in governing the interactions between the particles and surfaces
South Korea, has shown that the removal efficiencies for all treat- whilst the pore system effects become less prominent and visi-
ment systems are larger than 98.9%, although the rapid sand filter ble (Bhattacharjee, 2016). However, understanding of potential re-
demonstrated the lowest removal efficiency compared to the other tardation and immobilisation of microplastic particles by biochar
two methods (Hidayaturrahman and Lee, 2019). through its complex microstructure and pore system is largely un-
In this paper, we present an investigation on filtration char- known. We present an experimental investigation that aims to
acteristics of biochar for removing sphere-shape microplastic par- develop a fundamental understanding of the underlying mecha-
ticles. The aim of this research was to develop a fundamen- nisms of immobilisation of microplastic spheres in biochar for po-
tal understanding required for assessing the capacity and poten- tential applications as a low cost, low maintenance porous fil-
tial of biochar for integration within the conventional sand fil- ter for microplastic. The inclusion of biochar in rapid sand fil-
ter technology. Microbeads (spherical shape microplastic particles) ter has the potential to increase the removal efficiency of the
mostly originate from personal care and cosmetics products at tertiary treatment system. This is important for upgrading exist-
sizes varying (in diameter) from <63 μm to 20 0 0 μm in the in- ing WWTPs to minimise the discharge of microplastic as alter-
fluent and effluent of WWTPs (Estahbanati and Fahrenfeld, 2016). native methods (e.g. membrane) can be expensive, energy de-
Hidayaturrahman and Lee (2019) have shown that the microbeads manding and difficult to be implemented; especially in Global
comprise the highest percentage of the composition of microplastic South.
particles (with regards to the shape) present in the effluents from Microplastic spheres with 10 μm diameter were selected to
the different tertiary treatments system. Due to the smooth surface study in this research to develop an understanding of the ef-
of microbeads, lower adsorption capacity of microbeads in sand fil- fects of morphology of pore system and the extent the porous
ter is expected compared with that of irregular shape particles of system can play to immobilise the microplastic spheres. This
microplastic (e.g. fibres, fragments, films and sheets) (Ding et al., size was of microplastic particles (10 μm) was chosen to elim-
2020). inate the potential impact of surface charges on removal to be
Rapid sand filters are a feasible treatment technology with able to focus on morphology and pore system effects. Filtra-
favourable characteristics including minimum maintenance and en- tion characteristics of uniform microplastic spheres in four dif-
ergy usage (Mutemi et al., 2020) in comparison with alternative ferent types of biochars (three biochars from pyrolysis of corn
solutions such as membrane-based filtration, which consumes a straw and 1 biochar from hardwood feedstock) are presented.
significant amount of energy (half of the total energy consump- Hemocytometer analysis (also known as ‘counting chamber’ in
tion in water treatment process) (Wang et al., 2020). Rapid sand medical science) was adopted in this research to measure the
filters integrated with activated carbon have been shown to of- concentrations of microplastics and determine the removal effi-
fer an enhanced adsorption capacity; improving the competitive- ciency. We present the results of an extensive microscopic char-
ness of sand filter in comparison with other methods (e.g. mem- acterisations based on Environmental Scanning Electron Micro-
branes), which offer a higher removal efficiency of various con- scope (ESEM) which allows the filters to be imaged without
taminants (Kalmykova et al., 2014). Biochar is a carbonaceous ma- pre-treatment.
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 3

Table 1
Physical properties of biochar samples

Biochar SSA by EGME m2 /g Particle Density Mg/m3 Bulk density Mg/m3

C300 808.3±81.9 1.318 0.059

C400 609.0±83.5 1.226 0.083
C500 177.5±16.3 1.208 0.121
Hardwood 292.8±69.3 1.312 0.413

Table 2
Elemental contents of biochar and sand (w/w %).

Elements C300 C400 C500 Hardwood Sand

C 70.0 81.3 68.7 84.7 6.01

O 18.7 11.7 19.1 14.1 46.69
N 3.1 3.7 2.2 0.3 -
K 2.6 0.3 1.8 0.2 0.08
Ca 2.4 0.8 2.0 0.5 0.09
Mg 1.3 0.3 0.6 0.1 -
P 1.2 0.2 1.5 - -
Cl 0.2 - 0.1 - -
S 0.2 0.3 0.2 - -
Si 0.2 1.1 3.4 - 31.41
F 0.1 - - - -
Na - 0.1 - - -
Al - - 0.1 - 0.4
Fe - - 0.1 - 3.13
Mn - - 0.1 - -

Fig. 1. Particle size distribution of biochar samples and sand used in this study.
the SSA in biochar in other studies (Günal et al., 2018; Laird et al.,
2010; Arthur et al., 2015).
A summary of physical and chemical properties of the biochars
2. Materials and methods
used in this study is presented in Table 1.
A leaching column system was designed and developed to mea-
sure the removal efficiency of microplastic sphere by biochar and 2.2. Microscopic characterisation
sand filters. The immobilisation mechanisms were analysed from
the perspective of morphology through microscopic examination. The Scanning Electron Microscope (SEM) examination were car-
ried out by FEI Quanta 650 FEGSEM. The elemental data was gener-
ated by Oxford Instrument Energy Dispersive X-ray detector (EDX)
2.1. Biochar and silica sand and analysed by AZtec®. The X-ray powder diffractometer (XRD)
measurement was carried by the PANalytical’s X’Pert Pro, Malvern
Two types of biochar have been selected and used in this study Instruments, and the crystalline phases were identified by High-
which are corn straw biochar and hardwood biochar. The corn score®. The crystalline phase candidates were selected based on
straw biochar was acquired from the Nanjing Zhironglian Technol- previously reported phases in biochar (Singh et al., 2017). The sur-
ogy Company (based in China). The biochar samples were manu- face roughness was measured by Keyence X200K 3D Laser Mi-
factured through slow-pyrolysis process of biomass at three differ- croscope. The Zeta potential was measured by Zetasizer Nano ZS,
ent temperatures. The biochar samples from the corn straw used Malvern Instruments. All microscopic characterisation tests have
are manufactured at 30 0°C, 40 0°C and 50 0°C (labelled as C300, been carried out by the facilities at the University of Manchester.
C400 and C500 in this work which represent the pyrolysis temper- The main content of the four biochar species was found to be
ature 300°C, 400°C and 500°C, respectively). The hardwood biochar amorphous carbon from the XRD results (Table 2) (Singh et al.,
was purchased from the Oxford Charcoal Company (based in the 2017) and high elemental content of carbon (Table 2). As shown
UK). The biochar had been produced through a traditional open fire in the elemental map (from Figure S1 to Figure S4 in Appendix A),
stove method as a by-product of charcoal rather than a fixed tem- the structure of biochars used consist of carbon and oxygen, while
perature method. The silica sand used in this study was acquired silicon was also detected at minor scale, due to the presence of
from Garside Sands from the resourced based at Leighton Buzzard soil particle in the corn straw and wood (Table 3). The full results
in Bedfordshire (UK). of characterisation by EDX and XRD are presented in the supple-
The particle size distribution tests were carried out based on mentary information.
BS-1377-2 (RDB, 1990). The biochar samples were mildly ground The ESEM results for different biochar samples used in this
and mixed into the same particle size distribution to obtain d50 study are presented in Fig. 2 which shows the morphology of pore
around 0.6-0.7 mm which is similar to that of sand. Fig. 1 presents system. The microstructures of biochar can be categorised as ‘rind’,
the particle size distribution of sand and biochar samples. ‘chip’, ‘loofah’ and ‘honeycomb’ for the samples studied. Biochar
The density was measured by small pycnometer method ac- possess a complex heterogeneous porous system at microscopic
cording to BS-1377-2 (RDB, 1990). The specific surface area of length scale.
the samples was measured using Ethylene Glycol Monobutyl Ether The main reasons for the difference in morphology are the
(EGME) method to obtain the total specific surface area (SSA). This difference in the biomass feedstock and the pyrolysis tempera-
method has been reported to be successfully used for measuring ture. The organic matter of the wood cells is normally removed
4 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Table 3
Crystalline phases of the biochar and sand materials used.

C300 SiO2 , Na(AlSi3 O8 ), KCl

C400 SiO2 , Na(AlSi3 O8 ), KCl
C500 SiO2 , Na(AlSi3 O8 ), KCl
Hardwood SiO2 , Ca(C2 O4 )(H2 O), K2 SO4 , CaCl2 , Na2 Mg(SO4 )2 (H2 O)4 , Na2 CO3 , KNO3 , CaCO3
Silica sand∗ SiO2 , Al2 O2 , Fe2 O3 , CaO, K2 O, Na2 O, MgO, P2 O5 , Cr2 O3
∗
Information provided by the supplier.

Fig. 2. Microstructure and morphology of the pore system of biochar samples: ‘Rind’ in C300 (a, b), ‘Chip’ in C400 (c, d), ‘Loofah’ in C500 (e, f) and ‘Honeycomb’ in Hardwood.
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 5

Table 4
Surface roughness of biochar and sand.

Sa ∗ Sz † Spc ‡ Sdr §
Biochar
Avg∗∗ SD†† Avg SD Avg SD Avg SD

C300 12.0 3.2 159.3 45.6 17554 11124 25.3 22.1

C400 7.4 2.3 106.3 22.3 18486 9857 17.1 12.0
C500 4.1 2.5 59.7 35.4 7483 1808 4.5 5.1
Hardwood 4.1 2.2 48.9 21.3 14639 5786 5.8 4.8
Sand 2.8 1.3 31.2 15.5 8955 1618 4.2 2.4
∗
Arithmetical Mean Height (μm);
†
Maximum Height (μm);
‡
Arithmetic Mean Peak Curvature (1/mm); Developed Interfacial Area Ratio;
∗∗
Average (n=12);
††
Standard deviation.

by the gasification process (Hagemann et al., 2018) and the hard 2.4. Leaching column tests
cytoderm remained, forming a honeycomb structure as shown in
Fig. 2g. However, the corn straw do not have secondary growth by To investigate the removal efficiency of microplastic spheres by
the production of concentric annual rings so the majority of ar- different biochar filters, a series of leaching column experiments
eas at the cross section was occupied by pith (Fosket, 1994) which were carried out. The breakthrough curves of each biochar filter
cannot survive the pyrolysis process. Therefore, the corn straw were first measured. The experiments were followed by flushing
biochar exhibited layered shape consisting of epidermis cytoderm the system by distilled water to assess the stability of microplastic
and vascular bundle. particles trapped or adsorbed in the system. The filter was initially
With regards to the effects of pyrolysis temperature, from 300 dry and flushed with the solution after the emplacement in the
°C to 400°C (Fig. 2a–c), the microstructure surface and the thick- system. The biochar samples with 70 mm length where packed in
ness of layers become smoother and the layers become thinner. 100 mm length and 30 mm dimeter cylindrical columns. The sam-
It is observed that from 400°C to 500°C (Fig. 2c–e), the rela- ple was sandwiched between two layers of silica sand each at 15
tively weaker components were removed which resulted in high mm length as shown in Fig. 3. The packing process was carefully
pore system. As shown in Table 1, the specific surface area (SSA) conducted to ensure minimum mixing between sand and biochar
decreases with the increase of pyrolysis temperature. This phe- can happen during the process.
nomenon can be explained by the results of surface roughness in The inflow solution was injected from the bottom of the cell by
Table 4 where the Developed Interfacial Area Ratio (Sdr ) values a peristaltic pump at constant flow rate 180 ml/h. A manometer
have the same trend as the SSA. was placed between the inlet of column and the outlet of pump
to monitor the water pressure/head. The hydraulic conductivity of
filter system was then calculated using the pressure gradient and
flow rate in Eq. (1). For the case of sand filter, the 70 mm biochar
2.3. Microplastic solution/suspension filter bed was replaced by silica sand (the same sand used as sup-
porting material in biochar filter). The operation conditions are
In this study 10 μm polystyrene microsphere (from Thermo summarised in Table 5.
ScientificTM ) was selected and used. The concentration of mi-
croplastics in sewage varies site to site and from less than 1 to
Q = kiA (1)
several 10,0 0 0s of particles per litre (Sun et al., 2019). For example, where, Q is the flow rate (L3 /T),
k is the hydraulic conductivity
the presence of a wide range of both light and heavy density mi- (L/T), i is the hydraulic gradient (L/L) and A is the cross-section
croplastic particles in sewage sludge (approximately from 20 0 0 to area.
51,0 0 0 particles per kg of sewage) has been reported in an investi- The ingress of microplastic suspension consisted of 3 pore vol-
gation in Spain (van den Berg et al., 2020). In the study reported by ume injections. This was then followed by flooding the system by
van den Berg et al. (2020), the smallest particles accounted were distilled water for up to 10 pore volume. The tests were carried
found to be larger than 50 μm; noting the fact that the smaller out at ambient temperature (25±1 °C).
particles present at higher concentrations (Marcus et al., 2014). We At the end of the leaching tests, the biochar/sand filters were
have focused on microbeads as they represent the highest possibil- removed from the column and samples were taken for the SEM
ities of escape from sand filters due to absence of surface interac- imaging under the ESEM mode of imaging. The samples were col-
tions (Ding et al., 2020). We have selected a high concentration of lected from near the inlet and transferred to the ESEM holder
a uniform micro-spheres suspension at 1.6 × 108 (±0.2) particles without any treatment prior to imaging. Inside the chamber, the
per litre of solvent to be able to readily detect how the system stage temperature was set at 5°C and chamber pressure was 5.0-
retain the particles. It is recognised that this concentration does 6.2 Torr (0.67-0.83kPa). All images were taken at 6.2 Torr. The pore
not necessarily represent a specific field concentration. The solvent water in the biochar and sand was gently removed by vapouring at
used is distilled water and the pH of the solution used is 7.56. 5.0 Torr until the microplastic particles and filter surface showed
The concentration of the suspension was measured by Neubauer up.
improved counting chamber (haemocytometer) (Randolph, 1944;
Wen et al., 2021). The concentration of particles in each sample 3. Results and discussions
was measured 6 times and the average values are reported. The
microplastic spheres have similar sizes with the cells (the object 3.1. Column tests: microplastic spheres retentions and stability
that counting chamber is designed for). The microplastic spheres
were distinguishable from biochar particles due to their distinctive Fig. 4a and b show the concentration of microplastic measured
regular and shapes. in the effluent for biochar and sand. The average of 6 measure-
6 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Table 5
Operating conditions of the leaching column tests.

Filter system Weight (g) Height (cm) Diameter (cm) Pore volume (ml) Flow rate (ml/h) Initial concentration (N/l) Hydraulic conductivity (m/s)

C300 2.9 7.0 3.0 47.28 180.0 1.6 5.41 × 10−5

C400 4.1 46.14 (±0.2) × 108 7.13 × 10−5
C500 6.0 44.49 7.84 × 10−5
Hardwood 21.0 34.89 3.72 × 10−5
Silica sand 110.0 10.0 31.40 1.34 × 10−3

Fig. 3. Schematic of the leaching column setup designed and used in this study.

ments is reported (n = 6). The results show that apart from the ble S1, Appendix B) which is as the result of the negative surface
silica sand filter, the concentration of microplastic has significantly charges. Therefore, the hydrogen ions in the distilled water are ad-
dropped after filtering with the biochar. Biochar C500 demon- sorbed on the surface of particles, so that the concentration of hy-
strates the highest removal capacity where almost no microplas- droxide ions is higher than that of hydrogen ions, and the solution
tic was detected during the tests whereas C300 provides the low- becomes alkaline. The effluents from biochar filters were found to
est removal capacity among the 4 types of biochars tested in this be more alkaline than those of sand filter because small biochar
research. Data are presented in a semi-log coordinate in Fig. 4b particles eroded from filter.
to demonstrate that less than 1% of initial concentration of mi- In order to obtain a better understanding of the immobilisa-
croplastic was found in both C400 and Hardwood filters’ effluent tion process in the filters studied, the results from the sand fil-
which is below the detection limit of the experimental method ter and the biochar filters are further analysed with the Herzig-
adopted. Leclerc-LeGoff model (HLL) which is a class filter model for collide
The removal efficiencies of the 5 filters tested are shown in transport (Logan, 2001). This model describes the transported of
Fig. 5. In the first 3 pore volumes where 1.6 × 108 particles/l mi- particles which are sieved by the solid porous fabric and as the
croplastic suspension was injected, the removal efficiency was cal- result porosity can decrease and possible clogging of the porous
culated by dividing concentration difference (retained by filter) by medium may occur (deep bed model assumptions) (Logan, 2001).
initial concentration. For the following pore volumes that distilled A simplified form of this model is used which assumes a steady
water was supplied, the release rate was calculated by dividing state flow (the case applicable to the leaching experiments here);
the residual concentration in effluent by 1.6 × 108 particles/l to and an equilibrium state of filtration where capacity of filter is
demonstrate leakage potential in the same figure. not reached (nor the flow is clogged). In addition, it is assumed
Both C400 and C500 showed no leakage from 3 to 10 pore vol- that the dispersion of particles plays a negligible effect of the
umes. However, 6.85%, 0.23% and 0.1% of total retained microplastic overall transport process (i.e. advection is the dominant trans-
in first 3 pore volumes escaped during 3-10 pore volumes for Silica port mechanism). Accordingly; the variation of particle concentra-
sand, Hardwood and C300 respectively. The results are compatible tions can be describe by the analytical solution to the HLL model
with those by Tong et al. (2020) where sand filter released more (Logan, 2001):
micro- and nano-plastic particles than the biochar filter. The efflu-
ent concentration decreased with the pore volume and eventually C (x, t ) = C0 e−λx (2)
decreased at a level which was under the detection limit at 10th
pore volume. This indicates that the leakage rate of decreased and where C(x, t) is the concentration (particles/L); x is the distance
particles inside the filters remained in place. Biochar filters showed from inlet boundary (cm), t is time (min), C0 is the inlet concen-
better removal efficiencies than that of sand filters and C500 filter tration which is 1.6 × 108 (particles/L) for the experiments in this
was the best showed 100% removal and 0% releasing. study. λ represents the filter coefficient (cm−1 ).
As shown in Fig. 6, all samples were found to be alkaline. Sand, The concentration of immobilised particles; σ (x, t), per unit
biochar and microplastic have negative Zeta potential value (Ta- volume of the filter medium (particles/L) can be described by
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 7

Fig. 4. Concentrations of microplastic particles measured in the effluent.

(Logan, 2001): ues for λ removal of PVC particles (1.3 μm) in sand filters is
  0.06-0.14 cm−1 (Herzig et al., 1970). It is noted that our experi-
xθ mental data indicate that removal efficiencies of Hardwood, C400
σ (x, t ) = λvC0 e−λx t − (3)
and C500 biochar approaches 100%. Therefore, the filtration curve
v
(green dashed lines in Fig. 7) plunged below the detection limit in
where v is the discharge flow rate (cm/min) which is calculated by the middle of the filter. Although, C300 represents the lowest re-
Darcy’s law and is constant for the case of leaching experiments. moval efficiency among all biochars, the filter coefficient for C300
θ is porosity and for the cases of experiments presented in this is 4.5 times larger than that of sand filter.
work; total volume of immobilised microplastic particles is less Fig. 8 presents the variations of immobilised particles for the
than 0.025% of total pore volume. Therefore, the change of porosity sand and C300 biochar filter for different pore volumes calculated
is negligible. based on Eq. (3). The porosity of sand and biochar used in the cal-
Fig. 7 presents the variations of microplastic concentration in culation are given in
the domain calculated using Eq. (4) for the case sand filter and Table 5. At a given distance from the inlet boundary (2 cm; ar-
C300 biochar filter. The average concentration of the outlets from bitrary chosen), the variations of the concentration of immobilised
experimental results were used to obtain the value of filter coef- particles varies linearly with time; providing a constant rate of
ficient (λ). The values of filter coefficient (λ) for C300 and sand 3.68 × 108 particle/L per min for the C300 biochar and 1.56 × 108
filter are 0.59 cm−1 and 0.13 cm−1 , respectively. A range of val- particle/L per min for sand filter. The removal rate of biochar filter
8 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Fig. 5. The removal efficiency of microplastic spheres at different pore volumes.

tion which provide insight into the governing mechanisms of re-

tardation of microplastic in the pore system.

3.2. Microscopic examination of microplastic spheres in biochar and

sand

The Biochar and sand filter samples were analysed by the use
of ESEM after the leaching column experiments were completed.
The aim was to develop an understanding of retention mechanisms
of microplastics in biochar and sand. In general, the surface mor-
phology of biochar is more complex and fluctuant than that of
sand. This can be observed from Figs. 9 to 13 as shown by the
Sa and Sz values in Table 4. For the case of sand filter, microplastic
particles were mainly found adhered onto clean surfaces (Fig. 13),
whereas in biochar filters, the microplastic particles were entan-
gled by small biochar chips and grains as shown in Figs. 9b and
c and 12c. From the images obtained, the microplastic particles in
the sand filter were likely to be more mobile than those in the
biochar filter due to the clean surface of sand.
By adjusting the beam energy at the ESEM process, the mi-
croplastic particles which are not immediately visible and locate
underneath the biochar particles were identified. Examples are
Fig. 6. Variations of pH in the effluent with pore volume.
presented in Figs. 9 and 10d which reflect the behaviour on the
hollow structure fabric of biochar. In addition, some microplastic
particles were found in the pores which are slightly larger than
for microplastics is 2.36 times that of sand filter with similar size, that of microplastic particles, as shown in Figs. 11a and b and 12c
and if converted to unit mass of filter, it is more than 10 times. and d.
A large difference between the values of filter coefficient for
C300 biochar and sand was obtained which indicate that for ob- 3.3. Immobilisation mechanisms of microplastic particles in biochar
taining an equal removal efficiency of 7cm C300 biochar filter, the
length of sand filter should be extended from 7 cm to 34 cm. Previous studies have shown that microplastic particles (with
It is noted that the particle sizes distributions for the sand and 1μm diameter) can be trapped in pine chip biochar by the large
biochars used in this study are very similar. It is therefore antic- internal space of biochar (Abit et al. (2014). In this study, the mi-
ipated that certain macroscopic porous characteristics of the ma- croplastic particles used are larger in size (10 μm) than previous
terials are similar (e.g. porosity, tortuosity). Both sand and biochar studies (Abit et al., 2014; Tong et al., 2020). The reason was to
are negatively charged; hence the polarity of the filter medium is eliminate the effects associated with surface interaction with col-
similar. The structure difference is reflected in surface roughness, loid size such as ionic strength, Zeta potential, van der Waals forces
as stated in Table 4, and SEM/ESEM images (Fig. 2). It is therefore to be able to observe the pore system effects. As described ear-
concluded that the main reason for the considerably higher reten- lier, the surface effects have small effects for interaction between
tions is the existence of additional retardation mechanisms than the 10-μm microplastic particles and porous system of biochar. As
surface interactions; governed by microscopic and pore structure. shown in Fig. 14, three categories of particles retained in the sys-
We provide in the next section, a series of microscopic examina- tem by different mechanisms/modes of microplastic immobilisa-
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 9

Fig. 7. Variations of concentration of microplastic inside the filters calculated by the HLL model and calibrated based on the outflow concentrations.

Fig. 8. Theoretical variations of σ in the domain at different pore volumes.

tion were observed from ESEM images which are classified and efficiency of sand filter for microplastic particles depends on the
introduced as ‘Stuck’, ‘Trapped’ and ‘Entangled”. It can be observed size of sand particles and the size of plastic particles.
that the microplastic particles were only Stuck in the sand filter The particles can also be ‘trapped’ in the pore system which is
while all three modes of interactions were found to exist in rela- by a mechanism that only exists in the filter with porous structure
tion to microplastic spheres retained in biochar samples. such as the activated carbon and biochar. Plastic particles may en-
The first type of particles retained in the porous system is Stuck ter the pores with slightly larger size and lose their mobility when
in the pore system which describe a mechanism by which the mi- the water flow happens at slow rate in the pores smaller than 30
croplastic particles are retailed in the gaps between the filter par- μm (Downie, 2011). This phenomenon is observed mostly in Hard-
ticles which are smaller than the particle size. In other words, the wood biochar and C500 biochar because of the ‘honeycomb’ and
porous system acts as a sieve. This explains why smaller microplas- ‘loofah’ structures.
tic dominated in effluent of water treatment plants while large The entrapped particles exist at much larger number in biochar
particles were stuck (Talvitie et al., 2017a). Therefore, the removal system than sand (Abit et al., 2014). Although there are micro-
10 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Fig. 9. ESEM images of C300 biochar filter; the area under higher beam energy is shown in green box (larger visible depth); blue arrow shows the spotted microplastic
particles.

scopic holes on sand surface in Fig. 13b), there is rarely a hole ade- c and 12b Since both biochar and polystyrene particles’ surfaces
quately deep to provide restriction for microplastic spheres against are negatively charged (El-Gholabzouri et al., 2006; Hong et al.,
water flow. This mechanism could also explain the reason why 2019; Yang et al., 2017), the force between the two would be Van
C300 filter showed relatively low removal efficiency. C300 is the der Waals force. Entangled microplastic particles would be immo-
closest biochar to the original corn straw in terms of microstruc- bilised due to increase of size, or microplastic particles would be
ture and the honeycomb structure is not the primary structure for wrapped and attached on filter bed. Furthermore, based on interac-
the cases of C300. tion volume theory (Kanaya, 1972; Goldstein, 2018), the thickness
Biochar contains many flaky shaped particles which can rela- of entangled flaky biochar can be estimated by changing the beam
tively easily detach themselves from the main particles or those energy of SEM as shown in Fig. 15.
may exist originally among the particles. Such flaky shapes par- The visible depth under SE detector is similar with that of
ticles exist especially in C300 and C400 as shown in Fig. 2a– BSE detector because secondary electron class 2 (SE2) and sec-
d. Although relatively large biochar particles and plastic particles ondary electron class 3 (SE3), which are generated by BSE, account
do not exhibit the properties of colloidal particles, flaky parti- for the majority of total SE (Peters, 1982). Furthermore, depth
cles do. It was observed that microplastic particles were likely where 90% of BSE occurs which is 0.285 Kanaya-Okayama range
entangled by small particles or chips as shown in Figs. 9b and (RK-O ) (Goldstein, 2018) can be taken as visible depth. RK-O can be
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 11

Fig. 10. ESEM images of C400 biochar filter (red square – local zoom in; blue arrow – spotted microplastic particles).

calculated by: tardation efficiencies of biochars can be summarised and ranked

  as: C50 0>C40 0>Hardwood>C30 0>Silica sand. From analysing the
A
RK−O = 27.6 E0 1.67 (4) immobilisation mechanisms, C300 has less ‘honeycomb’ structure
Z 0.89 ρ
while the biochar chips are relatively thick (>2 μm) indicating less
where, A is the atomic weight (g/mol), Z stand for the atomic num- effect by the van der Waals forces which have resulted in less im-
ber, ρ is the density (g/cm3 ) and E0 is the incident beam energy mobilisation by the ‘Trapped’ and ‘Entangled’ mechanisms, respec-
(keV). tively. As for Hardwood, it has the most abundant ‘honeycomb’
Therefore, the thickness of biochar chips attached on microplas- structure. However, thin chips were rarely found. C500 could be
tic particles can be estimated by adjusting beam energy until the the best balance so all three immobilisation mechanisms were re-
chips become transparent. alised during the column transport tests resulted in the best per-
The results showed that the thickness mostly ranged from 2 μm formance.
to 0.5 μm or even thinner. From the results of the leaching col- Sphere-shaped microplastic particles are only one type of mi-
umn tests and in terms of immobilisation of microplastic, the re- croplastic; but represent a category of sizes which are likely
12 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Fig. 11. ESEM images of C500 biochar filter (red square – local zoom in; blue arrow – spotted microplastic particles.
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 13

Fig. 12. ESEM images of Hardwood biochar filter; red square – local zoom in; green square – area under higher beam energy (larger visible depth); blue arrow – spotted
microplastic particles.
14 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Fig. 13. Sand surface before the leaching test (a, c) and after the test with microplastic particles attached to the surfaces (b, d).

to be more easily escape from tertiary treatment (including Biochar manufacturing is a mature and well-known process.
from rapid sand filter). While it is recognised that the shape Biochar is affordable and widely used in agriculture activities. The
and surface properties of microplastic in aquatic environment price of biochar in comparison with activated carbon is very low.
(e.g. rivers or industrial effluents) may differ from the mi- For example, in this study, the corn straw biochar is produced at
croplastic spheres used in this study, the study presented pro- a rate of 350 kg/h in each production line (based on communica-
vides critical knowledge on potential use of biochar as a mi- tions with the supplier based in Nanjing, China). The price of the
croplastic filter and mechanisms of interactions. It is, how- high-quality corn biochar used in this study is 564 USD per ton
ever, recognised that further research on real-world microplas- while the price of activated carbon (in the same geographical lo-
tic systems effluents of primary and secondary WWTS would cation) is 2524 USD per ton. The straw feedstock is in principle
be required to provide further confidence on the efficiency of an agriculture waste with no added value for the farmers and re-
technology. duce the carbon emission associated with burning the straw waste
Absence of wide spread use of high standard and advanced (Chalco Vera et al., 2017). Utilisation of agriculture waste in the
WWTPs (due to the cost) in global South has been reported which form of biochar and for various applications (including in wastew-
provide the base for integration of low cost/low maintenance tech- ater treatment) can create local economic values.
nologies. (Nansubuga et al., 2016). In this paper, we demonstrated The costly process of regeneration of activated carbon in in-
that biochar is a promising porous material for the removal of mi- tegrated sand filters can considerably add to the overall mainte-
crobeads, and we envisage that the potential integration in rapid nance cost of the system. With regards to regeneration, the tra-
sand filters can provide techno-economically feasible solution to ditional biochar regeneration methods would be applicable for
enhance the capacity of WWTPs; especially as a solution for the the case of applications in microplastic treatment (i.e. adsor-
global south. bate decomposition and adsorbate desorption). The decomposi-
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 15

Fig. 14. Three mechanisms for microplastic immobilisation – ‘Stuck’ (a); ‘Trapped’ (b); ‘Entangled’ (c), corresponding ESEM images – sand filter (d, g); biochar filter (e, f, g)
and optical microscope image (i).

tion through thermal regeneration has been recommended and cultural wastes and regeneration may not represent the most
widely used in industry which represents a cost-effective pro- feasible options. The results of the research presented outline
cess (Román et al., 2013). Alternative potential approach for re- the potential use of biochar in microplastic removal. It is recog-
generation is desorption such as dispersing and collecting by mag- nised that further research on various aspects of such appli-
net (Tong et al., 2020). It is noted that the gross cost of feed- cation is required to demonstrate the technical and economic
stock can be close to shipping cost where the feedstock is agri- feasibility.
16 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165

Fig. 15. Illustration of the interaction volume theory utilised for detecting microplastic and calculating biochar chip thickness (a); same area under SEM at beam energy of
10 KeV (b) and 20 KeV (c).

4. Conclusions biochar is at least 4.5 times larger than that of sand by application
of Herzig-Leclerc-LeGoff model (HLL) model under steady state
We presented the first experimental study on filtration char- flow.
acteristics and performance of biochar for immobilisation of uni- -Using a detailed ESEM microscopic examination, microplastic
formly graded microplastic spheres based on a series of leach- particles were found to be retained on the surfaces, pores and
ing tests and microscopic examination of four types of biochars underneath of the biochar chips for all biochar filters which are
and sand. The main conclusions drawn from this work are as associated with three mechanisms of ‘Stuck’, ‘Trapped’ and ‘Entan-
follows: gled’ are identified, controlling the fate of microplastic spheres in
-For all biochars analysed, the removal efficiency of the fil- biochar. The ‘Trapped’ and ‘Entangled’ immobilisation mechanisms
ter to microplastic spheres is higher than 95% and substantially provide the biochar a high removal efficiency than that of similar-
larger than that of sand (60-80%). Only less than 0.5% of the sized sand filter.
retained microplastic particles in biochars were found to be re- -This study highlights a strong capacity and potential for
leased when the samples were flushed back with distilled wa- biochar to be used for improving the performance of rapid sand
ter. The retention behaviour was found to be significantly higher filter to remove microplastic and in particular microbeads in ter-
than that measured for sand (6.85%). The filter coefficient for tiary treatment systems of WWTPs. Such capacity can in principal
 Z. Wang, M. Sedighi and A. Lea-Langton / Water Research 184 (2020) 116165 17

offer low cost/low maintenance solutions to improve the efficiency Conley, K., Clum, A., Deepe, J., Lane, H., Beckingham, B., 2019. Wastewater treatment
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and co-analysed the results, co-drafted the original manuscript
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Fosket, D.E., 1994. 1 - Introduction. In: Fosket, D.E. (Ed.), Plant Growth and Devel-
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The authors declare that they have no known competing finan- Goldstein, J.I., 2018. Scanning Electron Microscopy and X-Ray Microanalysis, 4th ed.
cial interests or personal relationships that could have appeared to Springer New York, New York, NY 2018. edn.
influence the work reported in this paper. Günal, E., Erdem, H., Çelik, İ, 2018. Effects of three different biochars amendment on
water retention of silty loam and loamy soils. Agric. Water Manag. 208, 232–
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Acknowledgement Hagemann, N., Spokas, K., Schmidt, H.-P., Kägi, R., Böhler, M., Bucheli, T., 2018. Ac-
tivated carbon, biochar and charcoal: linkages and synergies across pyrogenic
carbon’s ABCs. Water 10 (2). doi:10.3390/w10020182.
The authors gratefully acknowledge the financial support pro- Herzig, J.P., Leclerc, D.M., Goff, P.L., 1970. Flow of suspensions through porous
vided for the project Lotus by the University of Manchester’s Re- media—application to deep filtration. Ind. Eng. Chem. 62 (5), 8–35. doi:10.1021/
search England GCRF QR Allocation. M Sedighi acknowledges the ie50725a003.
Hidayaturrahman, H., Lee, T.G., 2019. A study on characteristics of microplastic in
financial support by The British Academy/Newton Fund through
wastewater of South Korea: identification, quantification, and fate of microplas-
the project Socio-technical solutions to water security challenges in tics during treatment process. Mar. Pollut. Bull. 146, 696–702. doi:10.1016/j.
urban areas and post-disaster scenarios. Z Wang acknowledges the marpolbul.2019.06.071.
Hong, M., Zhang, L., Tan, Z., Huang, Q., 2019. Effect mechanism of biochar’s zeta
financial support by the Department of Mechanical, Aerospace and
potential on farmland soil’s cadmium immobilization. Environ. Sci. Pollut. Res.
Civil Engineering at the University of Manchester in the form of 26 (19), 19738–19748. doi:10.1007/s11356- 019- 05298- 5.
a PhD Scholarship. The authors thank the technical support from Inyang, M., Dickenson, E., 2015. The potential role of biochar in the removal of
the Electron Microscopy Centre of The University of Manchester organic and microbial contaminants from potable and reuse water: a review.
Chemosphere 134, 232–240. doi:10.1016/j.chemosphere.2015.03.072.
through the training provided to Z Wang by Dr P Hill and Dr M Jaikumar, G., Brun, N.R., Vijver, M.G., Bosker, T., 2019. Reproductive toxicity of pri-
Nikiel for the ESEM imaging and analysis reported here. The au- mary and secondary microplastics to three cladocerans during chronic exposure.
thors also thank the staff in the Department of Materials at the Environ. Pollut. 249, 638–646. doi:10.1016/j.envpol.2019.03.085.
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University of Manchester for the access provided to the XRD Facil- Jonasz, M., Fournier, G.R. (Eds.), Light Scattering by Particles in Water. Academic
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Kah, M., Sigmund, G., Xiao, F., Hofmann, T., 2017. Sorption of ionizable and ionic
organic compounds to biochar, activated carbon and other carbonaceous mate-
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Supplementary material associated with this article can be dation of petroleum hydrocarbons, polycyclic aromatic hydrocarbons, alkylphe-
nols, bisphenol a and phthalates in landfill leachate using sand, activated
found, in the online version, at doi:10.1016/j.watres.2020.116165.
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