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Biochar industry to circular economy

Qiang Hu, Janelle Jung, Dexiang Chen, Ken Leong, Shuang Song,
Fanghua Li, Babu Mohan, Zhiyi Yao, Arun Kumar Prabhakar,
Xuan Hao Lin, Ee Yang Lim, Le Zhang, Gupta Souradeep, Yong
Sik Ok, Harn Wei Kua, Sam F.Y. Li, Hugh T.W. Tan, Yanjun Dai,
Yen Wah Tong, Yinghong Peng, Stephen Joseph, Chi-Hwa Wang

PII: S0048-9697(20)37351-4
DOI: https://doi.org/10.1016/j.scitotenv.2020.143820
Reference: STOTEN 143820

To appear in: Science of the Total Environment

Received date: 13 September 2020


Revised date: 29 October 2020
Accepted date: 30 October 2020

Please cite this article as: Q. Hu, J. Jung, D. Chen, et al., Biochar industry to circular
economy, Science of the Total Environment (2020), https://doi.org/10.1016/
j.scitotenv.2020.143820

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© 2020 Published by Elsevier.


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Biochar Industry to Circular Economy

Qiang Hua, Janelle Jungb, Dexiang Chenb, Ken Leongc, Shuang Songd, Fanghua Lia, Babu
Mohane, Zhiyi Yaoe, Arun Kumar Prabhakara, Xuan Hao Linf, Ee Yang Lime, Le Zhanga,
Gupta Souradeepg , Yong Sik Okh, Harn Wei Kuai, Sam F. Y. Lif, Hugh T. W. Tand, Yanjun
Daij, Yen Wah Tonge, Yinghong Pengk, Stephen Josephl, Chi-Hwa Wange*
a
NUS Environmental Research Institute, National University of Singapore, 1 Create Way,
Create Tower #15-02, Singapore 138602, Singapore.
b
Research & Horticulture Department, Gardens by the Bay, 18 Marina Gardens Drive,

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Singapore 018953, Singapore.
c
Mursun PTE. LTD, 14 Robinson Road, Singapore 048545, Singapore.

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d
Department of Biological Sciences, National University of Singapore, 16 Science Drive 4,
Singapore 117558, Singapore.
e
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Department of Chemical and Biomolecular Engineering, National University of Singapore,
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4 Engineering Drive 4, Singapore 117585, Singapore.
f
Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore
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117543, Singapore.
g
School of Civil and Environmental Engineering, The University of New South Wales,
Kingsford NSW 2032, Australia.
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h
Korea Biochar Research Center & APRU Sustainable Waste Management Program &
Division of Environmental Science and Ecological Engineering, Korea University, Seoul
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02841, South Korea.


i
Department of Building, School of Design and Environment, National University of
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Singapore, 4 Architecture Drive, Singapore 117566, Singapore.


j
Institute of Refrigeration and Cryogenics, School of Mechanical Engineering, Shanghai Jiao
Tong University, 800 Dongchuan Road, Shanghai 200240, China.
k
Department of Mechanical Engineering, School of Mechanical Engineering, Shanghai
Jiao Tong University, 800 Dongchuan Road, Shanghai, P. R. China, 200240
l
School of Materials Science and Engineering, University of New South Wales, Kensington
NSW 2052, Australia.

*
Corresponding author:
Chi-Hwa Wang: chewch@nus.edu.sg, Professor, Department of Chemical and Biomolecular
Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117585,
Singapore.

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Abstract

Biochar, produced as a by-product of pyrolysis/gasification of waste biomass, shows

great potential to reduce the environment impact, address the climate change issue, and

establish a circular economy model. Despite the promising outlook, the research on the

benefits of biochar remains highly debated. This has been attributed to the heterogeneity

of biochar itself, with its inherent physical, chemical and biological properties highly

influenced by production variables such as feedstock types and treating conditions. Hence,

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to enable meaningful comparison of results, establishment of an agreed international

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standard to govern the production of biochar for specific uses is necessary. In this study,

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we analyzed four key uses of biochar: 1) in agriculture and horticulture, 2) as
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construction material, 3) as activated carbon, and 4) in anaerobic digestion. Then the

guidelines for the properties of biochar, especially for the concentrations of toxic heavy
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metals, for its environmental friendly application were proposed in the context of
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Singapore. The international status of the biochar industry code of practice, feedback

from Singapore local industry and government agencies, as well as future perspectives
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for the biochar industry were explained.


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Keywords: Biochar; Agriculture and horticulture; Construction material; Activated

carbon; Anaerobic digestion

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1. Introduction

The environment and sustainability of the world is being threatened by climate

change (Wang et al., 2020b). To pursue efforts towards the 2015 Paris Agreement, the

Singapore government has pledged to reduce the greenhouse gas emissions intensity by

36 percent from 2005 levels by 2030, and to stabilize emissions with the aim of peaking

around 2030 (National Environment Agency, 2015). Although many CO2 removal and

capture technologies are under development, a blocking pathway for the natural carbon

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cycle which relies on converting biomass to biochar is suggested as a way to provide both

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environmental and health benefits (Oleszczuk et al., 2013; Roberts et al., 2010). This

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would achieve a net CO2 removal by the sequestration of atmospheric CO2 via
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photosynthesis into a long-term stable reservoir (Woolf et al., 2016). The many

strategies for using the end-product, biochar, facilitates zero-waste and the development
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of a circular economy (Matrapazi & Zabaniotou, 2020).


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Pyrolysis/gasification of biomass waste is mainly done to produce bio-oil/syngas

which can be burned to generate hot water, steam and/or turbine-generated electricity as
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well as waste reduction, with biochar as a useful by-product that has much potential in
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agricultural, construction, and industrial applications. In recent years, the production and

application of biochar has been extensively developed all over the world. The production

of biochar implies a complex chemical reaction process where biomass undergoes

decomposition, depolymerization and condensation in anoxic high temperature

conditions (Wang & Wang, 2019; Wang et al., 2017; Zhao et al., 2013). The feedstock

category, production technology, and process conditions mainly define the yield, quality

and toxicity of biochar, and therefore affect the following biochar application strategy

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(Wang et al., 2020a; Yang et al., 2019a). The physicochemical properties of biochar

reveals its broad application prospects, including soil conditioning, compost additive,

construction material, activated carbon and anaerobic digestion promotor, and the list of

potential uses is continuing to expand (Cha et al., 2016; Kah et al., 2017; Pan et al., 2019;

Wang et al., 2019a; Woolf et al., 2010). As the number of applications for biochar

increases, so too do the number of manufacturers. However, it is neither financially nor

energetically feasible to produce and apply biochar with no guidelines or regulations in

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place for biochar production and application.

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To address this gap, many countries and regions are in the process of developing

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their standards. In 2015, the International Biochar Initiative (IBI) published a version 2.1
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of the standardized product definition and product testing guidelines for biochar used in

soil, and the standard is widely recognized and regarded as an international standard.
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Discussions with local agencies on the adoption of IBI biochar standard for Singapore
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has revealed that the wholesale application of IBI biochar standard is not appropriate.

This is because the allowable upper limit for heavy metal levels in IBI biochar standard is
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much higher than the Singapore Compost Standard and some agencies felt that the
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application of biochar with such high heavy metals within water catchments for

horticultural and/or agricultural use is of concern, especially when 2/3 of Singapore is

water catchment. Hence, in view of the promise of biochar as a natural climate solution

and industry interest in it as a key component in a potential circular economy pathway on

one hand, and the lack of appropriate standards to govern biochar utilization in Singapore

on the other, a Singapore Standard is needed to develop a promising sustainability

industry ecosystem in Singapore.

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Here we reviewed the biochar production and application standard for Singapore to

provide all the relevant agencies, producers and consumers with the requirements for the

physical, chemical and biological properties of biochar inclusive of the categorization and

labelling. This standard may be used as a tool for assessing biochar quality and may also

be used in whole as a fundamental quality assurance tool for making informed purchasing

and utilization decisions, and furthermore providing guidelines for the sustainable

production of biochar and its end use applications.

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2. International status of biochar industry code of practice

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Currently, International Biochar Initiative (IBI) biochar standard (America) and
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European Biochar Certificate (EBC) are the most widely used standards throughout the

world. These two standards were developed to help to reduce the health and
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environmental risk associated with biochar production and usage, especially in


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agriculture. However, the two above-mentioned standards are both voluntary industry

standards. Because biochar has great potential as a sustainable material in different


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industries, these two standards are apparently insufficient to regulate the quality of
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biochar produced for different industries. With the increasing interest in biochar, many

countries have their own biochar regulations aligned with IBI and EBC biochar standards.

Other countries which currently have no biochar standard are regulating biochar usage

with fertilizer standard or compost standard.

The Australian New Zealand Biochar Initiative (ANZBI) has been developing a

biochar standard since 2018 at the request of the industry and government regulators. A

draft was presented before the annual conference in 2019 to approximately 300

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participants. The details of the draft were then discussed during the annual 2019 meeting.

Because a standard can potentially take up to 3 years to get the approval, the meeting

decided to develop a code of practice first. A final draft is nearly complete and will be

circulated before the Virtual annual meeting in July 2020 (Australia New Zealand

Biochar Conference 2020 & Study Tour ANZBC20, www.anzbc.org.au).

In South Korea, currently there is no integrated biochar standard available to guide

the application of biochar in different scenarios. Biochar used in agriculture or

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horticulture has been required to comply with the fertilizer standard which limits its

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heavy metal content. When biochar is used as the construction material, the composite

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standard should be applied. If biochar is used as activated carbon to adsorb the heavy
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metals, heavy metal contents from the leachate of used biochar should be limited to avoid

the pollution from further treating procedures.


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In Singapore, government agencies regulate the application of biochar according to


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the allowable input feedstock when used for horticultural purposes or other types of

applications. If the feedstock is biomass, horticultural or segregated food waste, the


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conversion is through a thermal process (for instance gasification), then the residue is
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termed a biochar and its use for horticultural or agricultural purposes is permitted.

Excessively stringent regulation on the feedstock can potentially hinder the development

of the waste-to-resource market and is a disadvantage to biochar utilization and

jeopardizes circular economy. Therefore, a standard to regulate production and

application of biochar would be necessary to facilitate the growth of the biochar industry.

The proposed biochar standard in this study can identify the most suitable applications

according to the properties of the particular biochar produced. If successfully

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implemented, the standard can be used to substantiate the limitations with specification

only input waste feedstock, therefore enhance the current practice of utilization of such

types of solid residues in industry, and finally realize the concept of circular economy.

3. Biochar used in agriculture and horticulture

3.1. Application of biochar in soils

The agricultural and horticultural application of biochar has been widely tested in

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the laboratory and field. It has been commonly applied as a component of chemical

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fertilizers (Glaser et al., 2002; Pandit et al., 2018), or as a soil amendment to improve

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crop productivity by enhancing nutrient availability (Glaser et al., 2002; Pandit et al.,
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2018), water-holding capacity (Mohamed et al., 2016) and soil microbial activity (Yang

et al., 2019b). Biochar has a liming effect and can increase the pH of highly acidic soils
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(Purakayastha et al., 2019; Ruzickova et al., 2020). It has also been reported to mitigate
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the release of heavy metals in soil (Qin et al., 2021; Rizwan et al., 2016; Rizwan et al.,

2018). Although biochar is also a type of soil conditioner, it differs from compost.
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Biochar is produced by the thermal decomposition of horticultural, food or municipal


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solid waste in an oxygen-limited environment whereas composting is the natural

biodegradation of organic substrates by the microbial community under aerobic

conditions. Organic matter in compost degrades quickly and becomes mineralized so its

beneficial effects are relatively short-lived unlike biochar which is able to persist in soil

for the long-term (Tratsch et al., 2019).

Biochar has great potential for large-scale agricultural application, but suitable

standards are lacking at the national level in most countries to regulate its use, thereby

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hindering its widespread adoption as a soil conditioner. Singapore, a tropical Asian city-

state, is a prime example. Biochar has been found to rehabilitate acidic soil commonly

found in Singapore (Yang et al., 2019b; Yang et al., 2016), improve crop yields (Shen et

al., 2020) as well as improve crop-nutrient profiles (Song et al., 2020). However,

Singapore biochar production is limited to waste processing so is highly regulated and

largely centralized in government-operated incineration plants.

Recognising the need for innovation in Singapore’s environmental services industry,

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the National Environment Agency (NEA), introduced the regulatory sandbox scheme in

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2019. The inaugural project approved under the new scheme in May 2019 was a waste

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upcycling project using an on-site compact waste gasifier located in Gardens by the Bay.
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Through the Micro Auto Gasification System, the project aims to 1) repurpose waste for

resources by utilizing thermal energy from the combustion of syngas to heat up a potable
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water tank for use by a food court at Gardens by the Bay, 2) reduce the volume of waste
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and hence residue that would be sent to the Semakau landfill, 3) sequester carbon in

biochar and 4) explore the application of biochar as a soil amendment and/or an


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alternative to horticultural peat as shown in Fig. 1. Horticultural waste collected within


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the Gardens by the Bay (woody tree branches from regular pruning on the grounds) is

first chipped, then dried using the cooling fans that exhaust the system heat. The dried

biomass is then fed into the gasification chamber with air introduced as the gasification

agent to achieve the autothermal gasification process. The gasification temperature is

controlled by adjusting the flow rate of air. The produced syngas from the gasifier is

combusted in the combustion chamber to produce heat with the temperature of up to

1100 °C. The thermal energy from the combusted hot gas is then extracted and

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transferred to the hot water tank through a series of heat exchangers. The feeding rate of

the gasifier used is approximately 30 to 40 kg h-1 depending on the waste characteristics.

The biochar is collected the next day before the system starts up for the next cycle of

gasification. The biochar produced has been used to grow leafy vegetables including pak

choi and lettuce to study whether biochar can be used as a growing medium and a

sustainable, partial replacement for peat moss (a non-sustainable growing medium

considered the gold-standard in the horticultural industry) (Fig. 1b).

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Fig. 1. Demonstration for a circular economy in Singapore via biochar production

and application in agriculture and horticulture. a) Biochar with soil for horticultural use. b)

Biochar used as a growing medium and a sustainable partial replacement for peat moss. c)

Biochar used as a soil amendment to remediate contaminated soil.

Although biochar has a similar purpose to compost in agriculture and horticulture, it

should not be considered a compost that follows the compost standard specifications.

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While the compost standard specifications can act as a guide for the categorization of

biochar based on its chemical and physical characteristics which include the nutrient

availability, texture, particle size, pH, carbon content, ash content and porosity. We

propose that, for use in Singapore, it is preferable to classify biochar according to its

carbon content. Biochar can thus be classified into three categories:

BHC: Biochar with high carbon content (>75%) is produced solely from

unprocessed feedstock (wood, bamboo, grass and other agricultural residue). Biochar

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with a lower ash content has a high porosity and greater carbon stability whereas biochar

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with a higher ash (nutrient) content has been shown to have a greater impact on biomass

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yields and soil improvement. These biochar types have been shown to be suitable as an
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animal feed supplement and for filtration and remediation of contaminated land.

BMC: Biochar with medium carbon content (>55% and <75%) is produced solely
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from unprocessed feedstock (wood, wood and mineral mixtures, bamboo, grass and other
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agricultural residue). These biochar types are generally suitable for livestock and any

other purpose.
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BLC: Biochar with low carbon content (30–55%) is produced solely from
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unprocessed feedstock (wood, bamboo, grass and other agricultural residues). These

biochar types are produced mainly from crop residue, food waste, manure, sludge and

wood and mineral mixtures. If heavy metals concentrations are within the regulation

limits, these biochar types can provide significant amounts of macro and micronutrients

to plants. The pH of BLC must be determined based on the target crop and the

characteristics of the growing medium to be enhanced. The pH of Singapore soils ranges

from 3–8 and may require liming with alkaline biochar or acidification with a low pH

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biochar (Sim et al., 1992; Ghosh et al., 2016). Biochar consisting of smaller particle sizes

ranging from 0.25–2 mm are best suited for plant growth.

Additionally, if biochar is used as a soil amendment for agriculture, the contaminant

levels should comply first and foremost with national regulations, if available. By

comparing several international standards for biochar used in agriculture and horticulture,

Table 1 serves as a guide on the suitability of a biochar for agricultural purposes in

Singapore. Given that the biochar performance is largely determined by its feedstock and

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the production conditions, a summary of the pyrolysis and gasification conditions (Table

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2) is provided as a guide for acceptable practices based on past studies. Although biochar

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may possess heavy metal and organic concentrations higher than the recommended or
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legislated limits, these contaminants may not be bioavailable. Therefore, it is

recommended that the producer undertake a Toxicity Characteristic Leaching Procedure


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(TCLP) test that is acceptable to the state regulator.


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Table 1. Suggested maximum concentrations of contaminants in biochar for agriculture

and horticulture application a.


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EBC b Korea Proposed


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IBI
Contaminant Units fertilizer Singapore
standard c
Basic Premium standard d standard

Lead mg kg–1 <150 <120 70–500 150 150


Cadmium mg kg–1 <1.5 <1 1.4–39 5 1
Mercury mg kg–1 <1 <1 1–17 2 1
Arsenic mg kg–1 <13 <13 12–100 50 15
Copper mg kg–1 <100 <100 63–1500 300 190
Nickel mg kg–1 <50 <30 47–600 50 70
Zinc mg kg–1 <400 <400 200–7000 – 720

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Chromium mg kg–1 <90 <80 64–1200 300 90


Selenium mg kg–1 <1 <1 2–36 – 1
Polycyclic
aromatic
mg kg–1 <12 <4 6–300 – 12
hydrocarbons
(PAHs)
a
The concentration of metals should be tested following the microwave acid digestion

with HF/HNO3 and determination of the metals with inductively coupled plasma method

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(DIN EN ISO 17294-2), and the concentration of polycyclic aromatic hydrocarbons

should be tested following the method of Soxhlet-extraction with toluene and

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determination with high-performance liquid chromatographic (DIN ISO 13877).
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EBC refers to the Europe Biochar Certificate. Basic grade follows Germany’s Federal
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Soil Protection Act and Premium grade follows Switzerland’s Chemical Risk Reduction
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Act (EBC, 2012).


c
IBI standard refers to the International Biochar Initiative standard (IBI Standard, 2015).
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d
Korea fertilizer standard refers to the Enforcement Decree of the Fertilizer Control
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Act for the hazardous standards for organic fertilizer and by-product fertilizer and heavy

metals among ordinary fertilizers ( Korea fertilizer standard, 2019).


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Table 2. Pyrolysis and gasification conditions for biochar production.

Production condition Pyrolysis Gasification


Temperature 350–800 °C 500–800 °C
Pressure No requirement No requirement

As specified by As specified by
Feedstock requirement
manufacturer manufacturer

End products

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Typical particle size 0.1–5mm 0.1–5mm


Typical ash content 5–70% <30%
Typical organic carbon 30–95% 70–95%

3.2. Biochar as a compost additive

Biochar has also been used as a compost additive to increase the composting rate. A

combination of 35% spent mushroom compost with 20% biochar has been shown to

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reduce the composting time to 24 days compared to the more typical 90–270 days (Zhang

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& Sun, 2014). The large porosity of biochar can also facilitate microbial growth in the

compost pile and therefore accelerate nutrient recycling (Sanchez-Monedero et. al, 2018).

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The addition of biochar in poultry manure for composting increased the maximum
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temperature reached and also shortened the thermophilic phase (Czekała et al., 2016). If
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biochar was used for co-composting it may be necessary to ensure that the end product

can meet the legislated Singapore compost standard (Table 3).


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Table 3. Physical, chemical and biological requirements of mature compost in Singapore.


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Measurement Class A Class B


6.0 – 7.0 5.0 – 8.0
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pH
Electrical conductivity (mS/cm) < 4.0 < 10.0
Organic matter (% dry weight) 30 – 60 30 – 60
C:N ratio > 18 and < 25 > 12 and < 35
99% passing through a < 85% passing through a < 10
Particle size (mm)
10 mm sieve mm sieve
Moisture content (%) > 25 and < 40 > 25 and < 55
Foreign matter or physical
contaminants (% dry matter < 0.5 <1
w/w)

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 Free from Salmonella enteriditis and Salmonella


Pathogens
typhimurium  Faecal coliforms < 1000 MPN g–1
Pests or invertebrates No live pupae or larvae of arthropods and snails
Chemical contaminants (heavy
Upper limit (mg kg–1)
metals)
Arsenic 15
Cadmium 1
Chromium 70
Copper 190

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Lead 100

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Mercury 0.5
Nickel
Selenium
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Zinc 720
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3.3. Biochar for organic farming


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With increasing awareness of food safety and the demand for organic food by the

public, there is an increasing number of Singapore farms interested in practicing organic


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farming. To promote the use of biochar, it would be ideal to include biochar as a


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permitted material for organic farming. However, the use of biochar is not explicitly

regulated under the Singapore Organic Farming Standard (SS 632:2017). Instead, this

standard permits the use of wood ash and wood charcoal, but requires the wood not being

chemically treated after felling, but it is unclear if biochar is a sub-category under wood

charcoal. Therefore, to regulate the use of biochar, the requirement for its use should be

explicitly listed in the standard, or more ideally, a general standard should be set for

biochar.

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3.4. In situ stabilization/immobilization of heavy metals in biochar soil amendment

To control the quality of biochar, it is vitally important to determine the organic and

inorganic impurities in biochar (Sormo et al., 2020). General organic and inorganic

contaminants affecting biochar quality include polycyclic aromatic hydrocarbons (PAHs),

polychlorinated biphenols (PCBs), dioxins, furans, and heavy metals (Weng et al., 2017).

Beyond the quality aspect related to the impurities, it is also essential to ensure that

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biochar bring more benefits to its applications, such as cation-exchange capacity,

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moisture retention, nutrient retention, plant growth promotion,

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stabilization/immobilization of heavy metals from soil or construction material etc. In the
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standardization of biochar, it would be reasonable to consider these benefits derived from

the application of biochar, especially on the stabilization/immobilization of heavy metals


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from soil. Some recent studies reported on the significant effect of biochar application on
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stabilization/immobilization of heavy metals from soil, which enhanced plant growth

(Kamran et al., 2020; Khan et al., 2020; Paul et al., 2020; Qian et al., 2019; Zeeshan et al.,
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2020). The efficacy of biochar stabilization/immobilization of heavy metals can be


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attributed to biochar’s high surface area, ability to increase the pH value, small particle

size etc. However, if biochar is directly used for its toxicity evaluation without soil, it is

commonly found to have a toxic effect on living organisms (Godlewska et al., 2021).

Such a negative effect is basically caused by its high pH value and possible contaminants.

But when biochar is mixed with soil in an appropriate percentage (for example 1% or

less), it usually does not have any apparent toxic effect. Instead it could increase plant

biomass and number of microorganisms in the soil, which are positive effects. Research

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reveals that the positive effects are attributable to the biochar raw material, pyrolysis

temperature, biochar percentage in soil, and the type of soil. The cleaner is the biochar

feedstock, the less toxic is the final biochar product. Plant-derived biochar generally has a

lower toxicity than those produced from sewage sludge or animal manure. Bioavailable

nutrients usually degrade with a higher pyrolysis temperature. Therefore, biochar from

low temperature pyrolysis or torrefaction contains a higher percentage of bioavailable

nutrients, which promote crop growth and microorganism reproduction. Soil quality in

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which biochar is added also affects the physiochemical properties of the biochar-

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enhanced soil. Key factors for soil quality could include particle-size distribution, bulk

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density, pH value, compaction, porosity, salinity, essential macronutrients (C, N, K, P,
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etc) and so on.

Biochar efficacy was reported for reducing heavy-metal uptake by cilantro


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(Coriandrum sativum) and spinach (Spinaccia oleracea) to minimize the human-health


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risk (Khan et al., 2020). They concluded that hardwood biochar application to Cr-Mn

mine contaminated soil effectively reduced available fractions of heavy metals and their
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subsequent bioaccumulation in leafy vegetables. Incorporation of hardwood biochar (3%


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w/w) into contaminated soil induced significant reduction in the phyto-available toxic

metal pool (Cr, Zn, Cu, Mn, Pb) and there was a decline in metal uptake by the leafy

vegetable. Zeeshan et al. (2020) investigated the efficacy of biochar of different particle

sizes on reducing the deleterious impacts of heavy-metal contamination on nutrient

availability and crop performance. The use of biochar (<3 mm particle size) significantly

increased the availability of N (by 28 and 75%), P (by 9 and 28%) and K (by 14 and

17%), and the saturation (by 9 and 10%) over biochar with 3–6 and 6–9 mm in size.

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Biochar (<3 mm) also significantly enhanced the plant growth rate (plant height by 12

and 22%, fresh weight by 13 and 17%, dry weight by 14 and 24%), produced higher

yields (flowers per plant by 6 and 15%, fruits per plant by 17 and 30% and fruit yield by

26 and 48%, respectively) over counterparts with biochar 3–6 and 6–9 mm in size. The

enhancement in the biochemical parameters (carotene, chlorophyll a, b and total

chlorophyll) was also observed with the use of the biochar of <3 mm particle size over its

larger counterparts. Kamran et al. (2020) revealed incorporation of woodchip-derived

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biochar along with domestic and industrial wastewater could reduce the heavy metal (Cr,

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Cd, Cu, Zn, Ni, Pb, Co, Mn and Fe) mobility in soil and their accumulation in rapeseed.

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Their results showed the positive role of biochar in improving rapeseed growth,
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physiological attributes and the antioxidant defence system through alleviating the

oxidative damage caused by wastewater containing heavy metals. For this application,
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incorporation of biochar at 2% was the most efficient application level for heavy metal
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immobilization in soil and ultimately lowered the uptake and phytotoxicity of these

metals in rapeseed shoots and roots. However, fine biochar particles were reported to
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have higher ecotoxicity on soil microbes. Particles < 0.5 mm of pine woodchip biochar
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can pose sub-lethal effects on soil biota (Prodana et al., 2019). Toxic contaminants in soil

could migrate to plants, microorganisms, invertebrates and arthropoda. However, with

large surface area, pore network and large numbers of functional groups, biochar has

strong adsorption properties to adsorb toxic contaminants in soil. Therefore, on one hand,

contaminants in biochar pose a risk to the surrounding environment, but on the other

hand, biochar’s affinity to these contaminants could reduce this risk. In addition,

biochar’s affinity to contaminants could also reduce the risks resulting from the toxic

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contaminants in soil. Hence, biochar not only reduces the mobility of its own toxic

contaminants but also reduces the mobility of the toxic contaminants in soil (Nejad et al.,

2018). This has been widely recognized in literature on pollution remediation techniques.

The beneficial application of biochar to stabilize/immobilize metal contaminants in

soil to reduce its deleterious impact on plant vegetable growth is illustrated in Fig. 1c.

The average sizes of germinated mini bok choy and radish plants were larger with the

addition of 10% (v/v) of biochar for those grown with heavily contaminated soil.

of
Although still not as good as the positive control (commercial KleenSoil Additive for

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stabilization/immobilization of heavy metals in soil) and blank control (no metal

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contaminants), the addition of biochar as a soil amendment did greatly improve the
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growth of vegetables and it may also have the potential to mitigate the other undesirable

impacts of metal contaminants on the environment.


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In Table 4, the proposed criteria for biochar to be used for in situ


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stabilization/immobilization of heavy metals in soil amendment are listed according to

the biochar adsorption capability of various heavy metals (Shakoor et al., 2020). The
ur

adsorption capacity of biochar can be tested for one or several relevant heavy metals, but
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not necessarily all listed in Table 4. Lead and cadmium contamination are the most

common and toxic heavy metals found in soil, so it would be reasonable to test the

biosorption capability for lead and/or cadmium. To simplify the test procedure, the

aqueous solution of heavy metals instead of contaminated soil could be used for the test

of biochar adsorption.

Table 4. Suggested ranges of biochar adsorption capacity for heavy metals in each

category of biochar.

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Soil Biochar Adsorption Capacity


Units
Contaminant High Medium Low
Lead mg g-1 > 80 30-80 <30
Cadmium mg g-1 > 15 5 - 15 <5
Copper mg g-1 > 30 5 - 30 <5
Nickle mg g-1 > 20 5 -20 <5
Zinc mg g-1 > 20 5 -20 <5
Chromium mg g-1 > 20 5 -20 <5

of
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4. Biochar used as construction material

4.1 Physical properties of biochar


-p
One of the emerging applications of biochar is as a constituent of cementitious
re
construction materials, especially as a sustainable alterative to cement, sand or other
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energy intensive admixtures used for concrete manufacturing (Akhtar & Sarmah, 2018;

Dixit et al., 2019; Gupta & Kua, 2019; Gupta & Kua, 2017). Recent studies (Akhtar &
na

Sarmah, 2018; Dixit et al., 2019; Gupta & Kua, 2018; Gupta & Kua, 2017; Gupta et al.,
ur

2018b) confirmed that biochar, prepared from different biomass feedstock under optimal
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pyrolysis conditions can lead to improvement in strength and ductility of biochar-mortar

by 15-20% compared to control mix. Filler effect of biochar particles can also contribute

to reduction in capillary water absorption and water penetration in biochar-mortar mix by

30-40%, thus suggesting reduction in water penetration and increased durability of the

composite (Gupta et al., 2018a).

The mechanical and durability performance of biochar-mortar or biochar-concrete

depends on a few key factors, namely biochar particle size, porosity, pore size

distribution, elemental contents, total surface area, pore volumes, and biochar dosage (as

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a percentage of the mass or weight of cement), which are in turn dependent on the

selected feedstock and preparation conditions.

Particle size determines the significance of the filler effect. For example, it was

observed that finer particles of biochar (maximum size less than 10 micron) with meso-

and micro-pores offered 10-15% higher compressive strength of cement-mortar

compared to macro-porous biochar prepared from the same feedstock (Gupta & Kua,

2019). The pores of biochar play significant role in distributing and retaining moisture

of
within the cementitious matrix (Gupta & Kua, 2019; Muthukrishnan et al., 2019).

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Muthukrishnan et al. (2019) found that combination of rice husk biochar (at 2-8 wt% of

-p
cement) and rice husk ash (12-18 % of cement replacement) prevented sealed shrinkage
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over the initial 42-day monitoring period after casting. Similar to Gupta and Kua (2020),

Muthukrishnan et al (2019) found that biochar made from rice husk has pozzolanic
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properties, which depends on the amorphousness of its silica content; this content can
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contribute to the late build-up of mechanical strength of mortar samples containing rice

husk biochar.
ur

Dosage of biochar in the mortar or concrete mixture affects the flowability of the
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mixture as well; it was found that dosage of biochar between 0.50 wt% to 2 wt% reduced

the flowability value (by 3 mm) compared to control (Muthukrishnan et al., 2019),

without having any detrimental effect on strength development at 1-, 7- and 28-day age

of biochar-mortar. Similarly, addition of 2 wt% biochar in concrete reduced the slump

value by up to 4 mm compared to control concrete without affecting strength

development; flowability of biochar-mortar and slump of biochar-concrete can be

determined according to ASTM C1437 and ASTM C143 respectively (ASTM, 2007).

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Addition of biochar in cement mortar and concrete to replace part of cement or sand

must offer satisfactory level of compressive strength and density to qualify as a structural

or non-structural construction material. The dosage of biochar can be adjusted to replace

2 - 10% by weight of cement or fine aggregate, provided that satisfactory workability,

strength and density are obtained. The flow and slump value of biochar added composites

must not be reduced by more than 5 mm, compared to control to ensure desired

workability level (ASTM, 2012). The hardened density of biochar-added mortar must not

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vary by more than ± 20 kg/m3 of the control mix. It is recommended that strength activity

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index (SAI) (Equation 1) of biochar-mortar or biochar-concrete must be at least 90% at 7-

-p
day and 28-day age for the biochar to qualify as a suitable supplementary material. This
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is similar to the standard specification of silica fume as mentioned in ASTM C1240
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(ASTM, C‐15, 2015).

𝜎𝐵𝐶,𝑀
𝑆𝐴𝐼 (%) = (1)
na

𝜎𝑐

where, 𝜎𝐵𝐶,𝑀 and 𝜎𝑐 are compressive strength of biochar added cementitious composites
ur

and control mix (with same aggregate, cement and water content) respectively.
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However, adding biochar that has high macro-porosity at higher than 2 wt%-10 wt%

is likely to lead to reduction in mechanical strength, because this increases the overall

porosity and permeability of the mortar or concrete. Also, the presence of C–H groups on

the surface of the biochar, due to the deposition of aliphatic and aromatic compounds,

may lead to weak biochar–cement matrix interfaces that leads to a reduction in strength

(Kua et al, 2021).

Although there is currently no specification for Oxygen-to-Carbon ratio of biochar

for use in cement-based materials, it is recommended that O:C ratio less than 0.30 shall

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be attained to ensure complete decomposition of hemicellulose and reactive groups on

biomass surface. O:C ratio < 0.30 is also associated with high stability of biochar under

soil environment (Spokas, 2010). Table 5 presents the recommendations of criteria of the

preparation and properties of biochar for application as cementitious admixtures based on

the review of latest publications on biochar concrete and mortar.

Table 5. Recommendations for preparation conditions and properties of biochar for

application as cementitious admixtures.

of
Recommended
Criteria Recommendations

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methods of evaluation
Selection of Ordinary Portland cement (ASTM Type 1)
cement and is generally compatible with biochar.
sand for
compatibility -p
Natural sand (ASTM C33) or manufactured
sand can be used as fine aggregates. Granite
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coarse aggregates can be used to
manufacture biochar-concrete.
Selection of Feedstocks must be chemically analyzed for X-ray fluorescence and
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feedstock any potential contaminants including heavy elemental analysis using


metals, phosphorus and the content of other Inductively Coupled
inorganic compounds, for example Plasma Mass
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potassium carbonate and calcium carbonate Spectrometry (ICP)


to prevent high ash content.
Biomass with detectable heavy metal
ur

content are not recommended for production


of biochar for use in concrete.
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Preparation Pyrolysis at temperature ranging from 400- X-ray diffraction shall


conditions 700 ˚C is recommended. Slow heating rate, be carried out to ensure
and 5-20˚C/min is recommended to obtain decomposition of
processing higher yield and well developed micro- cellulosic materials in
porosity in biochar. prepared biochar
Carbon Carbon content > 50% and O:C < 0.30 CHNS analysis using
content and ICP
Oxygen :
Carbon (O:C)
ratio
Particle size Depending on application, size range of 0.1- Laser diffraction
100 µm is recommended. Median particle analysis shall be used.
size shall be lower than cement used and Biochar can be dispersed
different from sand particles in water for particle size
measurement

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Surface area >5 m2/g. N2-BET method shall be


used to determine
specific surface area.
Biochar must be
degassed for 8 hours at
100˚C prior to analysis
Micro-pore >0.010 cm3/g Dubinin-Rudushkevich
volume equation can be
employed using N2
adsorption
pH >12, when mixed with cement filtrate or Cement filtrate shall be
pore solution prepared by mixing
cement and water in the

of
ratio of 1:10 and
filtering the fluid after

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24 hours. Biochar mixed
with cement filtrate must
be allowed to rest for at
-p least 24 hours before
measuring pH.
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Dosage 2-10 % by weight to partially replace
cement or sand
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4.2 Heavy metal and hydrocarbon contents of biochar

Heavy metal leaching is an issue observed with products from thermal treatment of
na

waste, including ash and biochar, with the heavy metal content being dependent on the
ur

sources (Kim et al., 2020). Heavy metal contained in the biochar may run off as leachate
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when the buildings are exposed to rain and other weathering agents (Lee & Bang, 2000).

Some commonly used leaching test methods are EN-12457-1, -2, -3 and -4 (single and

dual-stage batch leaching tests), percolation tests (such as CEN/TS 14405) for granular

materials, and CEN/TS 15853 (for monolithic materials). Specifically, EN-12457-4 is a

one-stage batch test using a liquid-to-solid ratio of 10 liters/kg for materials with particle

size below 10 mm (without or with size reduction), whereas CEN/TS 14405 is used for

testing the leaching of inorganic and non-volatile organic matters.

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The heavy metal limits for construction purposes of six countries, namely, Denmark,

Italy, Finland, Netherlands, Sweden and France, have been reviewed. A summary of their

respective limits is presented in Table 6.

Table 6. Heavy metal limits for leachate from additives in construction materials a.

Recommended
Denmark Italy Finland Netherlands Sweden France limits for
Singapore
Content or BS EN CEN/TS CEN/TS CEN/TS EN -
leaching EN12457- 12457- 14405 14405 14405 12457-
method used 1:2002 2 (for coal (based on (based 2

of
(for fly ash release to on
category used in soil and effects

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3 uses) paved water) on
structures) surface
water

Unit (mg/kg) -p bodies)


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Antimony - - 1.50 0.16 - 0.40 1.50
Arsenic 0.45 0.50 1.50 0.90 0.34 0.80 0.90
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Barium 24.00 1.00 60.00 22.00 - 56.00 24.00


Beryllium - 0.10 - - - 0.10
Lead 0.45 0.05 6.00 2.30 1.10 0.80 1.10
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Cadmium 0.13 0.005 0.04 0.04 0.02 0.32 0.13


Chromium 2.80 0.50 3.00 0.63 1.11 4.00 4.00
Cobalt - 2.50 - 0.54 - - 2.50
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Copper 9.00 0.05 6.00 0.90 0.81 50.00 9.00


Molybdenum - - 6.00 1.00 - 5.60 6.50
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Nickel 0.30 0.01 1.20 0.44 2.171 1.60 1.60


Mercury 0.0083 0.01 0.01 0.02 0.011 0.08 0.08
Selenium 0.11 0.10 0.50 0.15 - 0.50 0.50
Zinc 6.60 30.00 12.00 4.50 5.72 50.00 30.00
Chlorine 8,800 100 2400 616 2890 10,000 8,800
Fluorine - 1.50 50 - 2,230 60 60
Tin - - - 0.40 - - -
Vanadium - 2.50 3.00 1.80 - - 2.50
a
The values shown have already been normalized so that values obtained from the two

different tests can be directly compared with one another. The concentration of metals

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should be tested following the deionized water leaching and determination of the metals

with inductively coupled plasma method.

It is worth mentioning that under CEN/TS 14405, the emission limits are calculated

based on the release constant (specific for each element) and the critical compartment of

release (soil or groundwater) and the level of the compliance values in soil or

groundwater – whichever compartment is the most vulnerable within the next 100 years.

It is important to note that the leaching criteria for Denmark (Zomeren et al., 2014),

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which classifies the waste as Categories 1, 2 or 3. Permits are not required in order for

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Category 1 waste to be used for a range of uses, including construction of roads, paths,

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parking lots, noise reduction walls, ramps, dikes, dams, railway embankments, pipe/cable
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trenches, landscaping, marine constructions, refilling floors and foundations. Materials

under Category 2 (Kirkelund et al., 2012), require permits before they can be used and
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have site-specific requirements, before they can be used for roads, paths, cable graves,
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floors and foundations, noise banks, and ramps. Category 3 requires thorough

examinations before permits can be obtained for using them for roads, paths, cable graves,
ur

and floors and foundations. Both Category 2 and Category 3 residues and soil may be
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recycled under increasingly stringent criteria.

Judging from the range of upper limits defined in these six countries, we recommend

that the maximum allowable limits for each of the heavy metals shown in Table 6 should

be adopted. Most of these recommendations were based on the limits set in Denmark,

Finland, France, Italy and Sweden – countries with strong records on environmental

protection and commitment to sustainable development.

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5. Biochar used as activated carbon

Biochar, with high surface area and well pore structure, can be potentially used as a

low-cost activated carbon (Inyang et al., 2016). However, through conventional

pyrolysis/gasification treating of waste biomass, the resulted biochar usually showed

poorer pore properties than the commercial activated carbon. Therefore, various physical

and chemical treatment methods were proposed to convert raw biomass or low grade char

into activated carbon (Jin et al., 2013). Generally, physical activation needs high

of
temperature in the presence of steam, air, CO2, N2 and inert gases, and chemical

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activation was carried out using nitric acid, phosphoric acid, sulphuric acid and potassium

-p
hydroxide, etc. (Coetzee et al., 2017; Ge et al., 2016; Liu et al., 2018). However, the high
re
energy consumption for physical activation and hazardous chemicals usage during

chemical activation are major drawbacks for these technologies. In Singapore, two case
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studies were carried out to convert low grade carbon and waste biomass into activated
na

carbon, which has various industry applications, including adsorbent for waste water

treatment, gas purification, pollutant removal, electrode material for energy storage
ur

systems and so on.


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Firstly, a technology has been developed by a spinoff company of CBE Eco-

Solutions Pte. Ltd. to convert low grade carbon such as biochar or petroleum coke into

activated carbon. As shown in Fig. 2a, the energy efficient and environmentally friendly

process could increase the surface area of low-grade carbon from 100 m2/g to larger than

800 m2/g with the combination of optimized heating program and a green catalyst. In this

process, the catalyst can act as a pore forming agent and mild oxidizing agent without

releasing any hazardous gases due to the non-toxic nature of the catalyst. The process

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could simultaneously increase the pore volumes and surface functionalize the pores. Due

to the synergetic effect of tuning the pore size and enhanced functional groups inside the

pores, the synthesized activated carbon could achieve high adsorption capacities for both

organic pollutants and inorganic pollutants in wastewater, as shown in Fig. 2b. In

addition, the activation temperature could be lowered from 800 °C to 400 °C, which leads

to increased biochar yield from 60% to 85%. Because the solid carbon could be

converted to gaseous species as yield loss in a high temperature activation process.

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With good texture properties such as high surface area and good pore structure,

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biochar or modified biocahr is potential to be used to remove heavy metals from

-p
wastewater for the reduce of threatens to our human health. In order to improve the
re
adsorption capacity of heavy metals, many modification methods are tried and developed

for biochar, such as minerals impregnation, surface oxidation, treating by oxidant


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solutions and gaseous, microwave oxidation, to enhance the ion exchange capacity and
na

texture properties of biochar (Wang et al., 2019b). Both physical adsorption and chemical

adsorption reactions can be occurred during heavy metal removal process by biochar (Liu
ur

et al., 2020). While the used biochar which retained the heavy metals may turn into
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hazardous materials without proper disposal. Therefore, it is important to find efficient

ways for the modification and upgrading of biochar to improve the heavy metal removal

ability and the recyclability or reusability of used biochar.

Biochar can be used as a multifunctional material that addresses several challenges

in the present day (Chen et al., 2020). Apart from its use as an adsorbent, activated

carbon derived from biochar could also be used as an additive to electrodes for energy

storage systems. One of the major application is lithium ion batteries. Porous activated

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carbon has attracted much attention due to its cost effectiveness, natural abundance and

high porosity (Hsu et al., 2020). Lithium oxygen batteries have become a potential

candidate for energy storage device, the theoretical energy density (11680 Wh/kg) is

similar to gasoline (Starr et al., 2012). In practice, the discharge capacity is lower than the

theoretical value. Various electro-catalysts have been investigated to improve the

electrochemical performance of the Li−O2 batteries, including metal oxides (Trahey et al.,

2013), polymers (Zhao et al., 2012), noble metals (Huang et al., 2013) and carbon based

of
materials like graphene and doped carbon (Akhtar et al., 2020; Huang et al., 2020; Zhu et

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al., 2020). These electro-catalysts are not cost effective and nowadays researchers are

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focusing on biomass derived activated carbon for the energy applications. The activated
re
carbon has large surface area and high porosity, which leads to promising energy

performance for Li−O2 batteries with high energy density and excellent recyclability (Wu
lP

et al., 2017).
na

(a)
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(b)

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(c)

-p
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na
ur
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Fig. 2. Demonstration for circular economy in Singapore via biochar production and used

as activated carbon: a) General routes for production of activated carbon (AC) from

carbon-contained waste/biochar; b) Comparison of adsorption performance of produced

activated carbon with commercial activated carbon; c) Unit price of activated carbon

based on its iodine number.

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The conversion of biochar to activated carbon could emit large amount of

greenhouse gases, which are the main source for global warming. Average greenhouse

gas emissions were calculated as 6.6 kg CO2eq/kg for production of activated carbon

(Alhashimi & Aktas, 2017). During the activation process, the oxidizing gas agents react

with solid carbon to produce carbon dioxide through thermal chemical process, leading to

creation and widening of the porous structure. In addition, the physical and chemical

characteristics of activated carbon play important roles in determining its performance in

of
energy and environmental applications. It is necessary to set a standard for activated

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carbon (derived from any source of carbon) industry to implement a more

-p
environmentally friendly production process. The proposed activated carbon standard is
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listed in Table 7. The measurement of listed properties should be conducted based on

ATSM standard.
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Table 7. Properties of biochar to be used as activated carbon proposed for Singapore.


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Specs
Items
1st class 2nd class
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Physical properties Iodine number (mg/g) ≥ 1000 700


Methylene blue adsorption 120 100
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capacity, ml/g ≥
Moisture (%) ≤ 5 10
Ash content (%) ≤ 2 5
Pour density (g/mL) 0.3 - 0.5 0.3 - 0.5
Pore Volume cm3/g ≥ 1 0.75
Anion (mg/g) Sulphate (as SO42-) (mg/g) ≤ 10 20
Chloride (mg/g) ≤ 10 20
Nitrate (NO3-) (mg/g) ≤ 10 20
Metals Fe (mg/kg) ≤ 0.05 0.1

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Ni (mg/kg) ≤ 0.05 0.1


Co (mg/kg) ≤ 0.02 0.05
Cu (mg/kg) ≤ 0.02 0.05
Na (mg/kg) ≤ 0.1 0.2
K (mg/kg) ≤ 0.1 0.2
Al (mg/kg) ≤ 0.02 0.05
Emission of exhaust gas CO2 (mg/g final product) ≤ 1500 1500
during the production
of activated carbon SO2 (mg/g final product) ≤ 20 20

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In addition, the commercial value of activated carbon was investigated. The unit

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price and iodine number of different activated carbon powder products were collected by

-p
Li et al. (2020) from the Alibaba website, as shown in Fig. 2c. Iodine number is
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commonly used as a measure of activity level and it indicates the microporosity of

activated carbon.
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Secondly, chicken manure is a waste raising great attention from all over the world.
na

These large amounts of the unfavorable waste should be properly managed and converted.

Biochar has attracted great attention due to its high surface area and surface properties,
ur

making it a good resource to produce activated carbon with low environmental harm. Li
Jo

et al. (2020) has reported on the production of high-quality biochar by catalytic pyrolysis

of algae bloom and water hyacinth. This study found that the higher the temperature, the

higher the surface area of the biochar. Moreover, the largest biochar SSA reached 600.52

m2/g under the optimum condition of 500 °C, algae ratio of 0.4, catalyst ratio of 0.95,

CO2 flow rate of 40 mL/min and steam ratio of 3.75. It has been reported that activated

carbon produced from solid residue could effectively adsorb the dye via steam activation.

Activated carbon exhibited the highest adsorption performance of 189.83 mg/g

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(Maneerung et al., 2016). It is clear that activated carbon derived from biochar exhibits a

high potential for adsorption of pollutants and environmental sustainability.

The current potential feedstock, technology and condition for activated carbon

production has been summarized in the following Table 8. It is evident that the

characteristics and application of the activated carbon varied greatly with different

feedstock like wood, algae and sewage sludge; technology like pyrolysis, gasification,

microwave-assisted pyrolysis and hydrothermal carbonization; and production condition

of
and so on. The information is applicable in a Singaporean context and could definitely

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contribute to the future Singaporean market. Thus, it is essential to make a standard and

-p
code of industry practice in the application of the activated carbon, particularly for

Singapore’s circumstances.
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Table 8. Activated carbon derived from biochar for use under different reaction conditions.

No. Source Technology Condition Porosity Use Efficiency/Capacity Reference


2
1 Algae bloom Pyrolysis 500 °C, algae ratio of 0.4, 600.52m /g Li et al. (2020)
and water catalyst ratio of 0.95,

f
hyacinth CO2 flow rate of 40

o
mL/min and steam ratio
of 3.75
2 Sewage sludge Pyrolysis 500 °C, 5h, N2 2
35.66 m /g

r
Adsorption
o of 6.23 L kg−1 for phenanthrene Zielińska &

p
−1 −1
630 mL min phenanthrene and and 6.52 L kg for pyrene Oleszczuk

3 Sludge cake Pyrolysis 700 °C

e - pyrene
Removal of non-polar Greater that 50%
(2015)
Sullivan et al.

P r PAHs and petroleum


compounds
(2019)

4 Sludge cake Pyrolysis 400 °C

a l Pore
15.49 nm, pore
sizes Removal of phenolic
compounds
Greater that 76% Sullivan et al.
(2019)

rn
volumes 0.01
cm3/g
5 Carbon residue Gasification
u
900 °C, steam activation

o
776.46 m2/g Dye adsorption 189.83 mg/g Maneerung et
al. (2016)
6 Pine nutshell Steam activation
J 850 °C, 80 min activation
time and 1.5 ratio of
steam/biochar
1057.8 m /g 2
Iodine adsorption 958.9 mg/g Chen
(2016)
et al.

7 Wood 1500 m2/g Supercapacitors 4.5 V Koutcheiko &


Iodine number Vorontsov
1200 mg/g (2013)
2 −1
8 Corn stover Microwave and slow 600 °C,1 h and 820◦C for 1671 m /g Supercapacitors 245.9 F g Jin et al.

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pyrolysis 1 h to achieve activation Pore sizes 2.13 (2014)


nm, pore
volumes 0.762
cm3/g
9 Coconut shells NaOH-activated 700 °C,1.5 h 372 m2/g, Adsorbent for Toxic 22.30 mg g−1. Cazetta et al.

f
carbon pore sizes 2.26 Dyes (2016)

o
nm, pore

o
volumes 0.210

10 70% wood Gasification and KOH 850 °C,2h


cm3/g
1408 m2/g

p r
CO2 capture 2.92 mol/kg Dissanayake et
chips and 30% activation and a

e - al. (2020)

r
chicken manure combination of KOH
and CO2 activation
11 Hickory wood Pyrolysis 600 °C

l P
221.5 m2/g Removal
organic compounds
volatile 23.4–103.4 mg/g. Xiang
(2020)
et al.

12 Hydrochar Hydrothermal

n a
600oC,1h, liquid-to-solid Adsorbent material Shao et al.

r
from Green carbonization ratio of 8:1. (2019)

u
waste (fallen

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leaves and
deadwood)
13 Waste-derived Gasification, Green synthesis 28 m2/g Removal of 520, 83, 7.46, and 922mg/g for Ramanayaka et
dendro biochar mechanical grinding oxytetracycline, oxytetracycline, glyphosate, al. (2020)
and facile synthesis glyphosate, hexavalent hexavalent chromium and
chromium and cadmium, respectively
cadmium
14 Banana peel Green chemical 500 °C,1h Removal of dye 862 mg/g Zhang et al.
synthesis substances (2020c)

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To comply with the discharge limits set by Singapore National Environment Agency,

the leachate from activated carbon under prescribed operating conditions should contain

the least amount of undesirable substances. It is recommended that the leachate from

activated carbon (obtained by leaching with deionized water at prescribed operating

conditions) contain no more than 10% of the maximum limit specified by National

Environment Agency for discharge into a controlled watercourse. Therefore, based on

these allowable limits (National Environment Agency), the maximum concentration of

of
contaminants of biochar to be used as an adsorbent for water/gas treatment were specified

ro
in Table 9.

-p
Table 9. Suggested maximum concentration of contaminants in biochar as activated

carbona.
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Contaminant Units Allowable limits in biochar


Lead mg/L 0.01
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Cadmium mg/L NIL


Mercury mg/L NIL
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Arsenic mg/L 0.001


Copper mg/L 0.01
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Nickel mg/L 0.01


Zinc mg/L 0.05
Chromium mg/L 0.005
Chloride ion mg/L 25
Sulphate ion mg/L 20
Sulfur mg/L 0.02
Cyanide mg/L 0.01
Barium mg/L 0.1
Tin mg/L 0.5

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Iron mg/L 0.1


Beryllium mg/L 0.05
Boron mg/L 0.05
Manganese mg/L 0.05
Phenolic compounds mg/L NIL
Selenium mg/L 0.001
Silver mg/L 0.01
Chlorine (Free) mg/L 0.1

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Phosphate ion mg/L 0.2

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Calcium mg/L 15
Magnesium mg/L <15
Nitrate mg/L -p <2
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a
The concentration of metals should be tested following the microwave acid digestion
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with HF/HNO3 and determination of the metals with inductively coupled plasma method

(DIN EN ISO 17294-2).


na

6. Biochar used in anaerobic digestion

Anaerobic digestion (AD) is a significant technology for organic waste treatment


ur

and bioenergy recovery, thereby playing a vital role in developing the world circular
Jo

economy (Fagerström et al., 2018). For instance, approximately 744,000 tons of food

waste (FW) was generated annually in Singapore (National Environment Agency, 2020).

It has been reported that the recycled FW presents a huge energy potential if AD

technology is adopted in Singapore (Tong et al., 2018). Indeed, AD technology can help

mitigate emission of greenhouse gas, extract energy from the organic compounds via

functional microorganisms, avoid release of hazardous odor and substances into the

environment, and recycle nutrients in the form of organic fertilizers (Sharma et al., 2020;

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Sherwood, 2020; Wainaina et al., 2020). Recent studies on AD technology focused on the

enhancement of the AD process efficiency for bioenergy production, due to the fact that

AD operations frequently encountered issues in terms of process stability during the long

term operation, especially at a relatively high organic loading rate (Shamurad et al., 2020).

In order to enhance the process efficiency of AD processes, various enhancing strategies

have been explored in recent years (Zhang et al., 2019). Therein, supplementation of

conductive materials such as biochar and activated carbon was identified as a promising

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strategy to enhance the AD process (Dang et al., 2016), as this strategy did not involve

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modification of the infrastructures. It has been demonstrated that biochar derived from

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gasification or pyrolysis processes can be added in anaerobic digesters to improve the AD
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process stability and enhance methane production, as shown in Table 10.

Table 10. Information on some application of the use of biochar in anaerobic digestion.
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Feedstock, and Anaerobic Anaerobic Working Dosage Enhancing Reference


Biochar Digestion Digestion Volume performance
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production Operation Feedstock


temperature
Waste wood Semi- Food 1000 L 15 g/L Increased Zhang et
pellet, 700- continuous, waste organic loading al.
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800 °C thermophilic rate (2020b)


Municipal Semi- Food 1.5 L 0.25 g/day Improved Giwa et
Sludge, 500 °C continuous, waste stability, 5% al. (2019)
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mesophilic enhanced
methane yield
Algal Biomass, Semi- Algal 0.8 L 7.5 to 15 g/L 12-54% Zhang et
500-600 °C continuous, biomass & enhanced al.
mesophilic and food waste methane yield (2020a)
thermophilic
Corn Stover, Semi- Sewage 0.4 L 0.25 to 1.0 g/d 28.5% Pecchi &
600-900 °C continuous, 2- sludge enhanced Baratieri
stage methane yield (2019)
(mesophilic to
thermophilic)
Pine-wood, Semi- Sewage 0.4 L - 9.0% enhanced Pecchi &
500-850 °C continuous, 2- sludge methane yield Baratieri
stage (2019)
(mesophilic to
thermophilic)

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Indeed, biochar has been validated to be capable of enhancing the AD process

through several mechanisms. More specifically, it has been found that biochar plays a

crucial role in enhanced AD through several mechanisms, including 1) promoting direct

interspecies electron transfer in AD process among different microbial species due to

biochar’s good conductivity (Liu et al., 2012), 2) enhancing microbial growth through

biochar’s immobilization effect (Fidel et al., 2017), 3) adsorbing inhibitive compounds

like heavy metals, ammonia and volatile fatty acids in anaerobic bioreactor (Mumme et

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al., 2014; Sunyoto et al., 2016), and 4) increasing bioreactor buffering capability by

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virtue of biochar’s relatively high alkalinity (Fidel et al., 2017). In addition, the economic

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feasibility of biochar addition strategy with a dosage of 15 g/L in AD processes for
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enhancing methane yield has been validated (Zhang et al., 2020b). The aforementioned

enhancing mechanisms of biochar in AD processes are shown in Fig. 3.


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Fig. 3. (a) Enhancing mechanisms of pyrolysis/gasification biochar for application in AD

processes. (b) Schematic diagram of a 1000 L pilot-scale anaerobic digestion set-up in


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Singapore.

Furthermore, the studies have also reported that the addition of biochar could
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improve the micro and macro nutrients of the digestate (Giwa et al., 2019; Zhang et al.,
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2020a). However, similarly with the usage in agriculture, the use of biochar should also

be regulated due to the fact that the biochars with different physiochemical properties

could exhibit significantly different enhancing performance in AD processes. More

specifically, the properties related to the enhancing mechanisms of biochar (see Fig. 3)

frequently played a crucial role, thereby need to be regulated for production of biochar.

Regarding biochar application in AD, dosage and particle size are two most important

parameters. Previous studies demonstrated that 7.5 to 15 g biochar per working volume

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could be an appropriate dosage for application in AD bioreactors for enhanced

biomethane production (Zhang et al., 2020b). In addition, effects of different biochar

particle sizes on biomethane production during the AD of food waste were also evaluated,

results of which showed that supplementation of biochar with a particle size less than 1

cm was a promising option. Too large particle sizes (e.g. > 1 cm) of biochar could lead to

floating of the large particles as the biochar density was frequently lower than water

(Zhang et al., 2020b). In addition, as biochar was derived from the pyrolysis or

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gasification of wastes, it may contain some toxic metal elements such as Cu, Cd and Pb,

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etc. Thus, supplementation of biochar to the AD bioreactors may introduce some heavy

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metals in the subsequent digestate. The metal concentration of biochar depends on the
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feedstock and production conditions of biochar. More recently, it was reported that algal

biochar enhanced biomethane production by 12 to 54% and improved the nutrition


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components (e.g. NPK) in anaerobic digestate for fertilizer utilization (Zhang et al.,
na

2020a) (see Section 2. Biochar used in agriculture and horticulture). Nevertheless, the

biochar derived from other municipal organic wastes may contain different level of heavy
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metals. Hence, the effluent of the anaerobic digestion, to be used as bio-fertilizers, should
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be subjected to a Toxicity Characteristic Leaching Procedure (TCLP) test to ensure that

contaminants, if any, are not bioavailable. Taken together, several key criteria for

qualified biochar to be used in anaerobic digestion are proposed in Table 11. A TCLP

test is suggested when converting biochar amended digestate into bio-fertilizers. In

addition, prior to practical application of the derived bio-fertilizer, its quality should be

tested according to the standards for biochar as a soil amendment proposed in this study

(see Section 2).

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Table 11. Suggested key criteria for qualified biochar to be used in anaerobic digestion.

Properties of biochar Units Biochar for anaerobic digesters


pH - Between 7 and 12
Dosage g per L working volume Between 7.5 and 15
Particle size cm Diameter < 1
Impurities (e.g. glass) wt% < 0.1, the little the better
Surface area m2/g > 150, the larger the better
Zn wt% < 0.5

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Cu wt% < 0.5

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Fe wt% < 0.5
Mn wt% < 0.5
Mg wt% -p < 0.5
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Ca wt% < 0.5
Co wt% < 0.5
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7. Feedback from industry and government agencies


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The feedback for the survey of the code of practice presented in this paper from
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some industry companies indicate that it is crucial to have a standard so the industrial
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players have the benchmark and can adopt the same standard. The development of a

biochar production and application standard can help to simplify the biochar production

process to meet the requirement of the market and reduce the time to market. The

majority of the companies investigated explained that they can satisfy the standard and

continue to operate under the guidance of this standard. They also considered that it

largely depends on the feedstock input to achieve the biochar properties that can satisfy

the different criteria in this standard. The providing of the homogenous raw wastes in

Singapore may be the challenge to satisfy the regulations in this standard. However, the

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emissions from the biochar production process, heavy metal contents in biochar, and

toxicity to environment should be compulsory regulations for the companies to comply

with.

The tripartite meeting conducted among research institute, company, and

government specified that a biochar standard proposed in this paper is significant to the

biochar industry in Singapore. The intended outcome of the standard of biochar in

Singapore is to have a streamlined process control for consistent product quality in

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compliance with the minimum requirements and guidance for product use. A new work

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item proposal will be submitted to Singapore Enterprise for assessment, and then a

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working group needs to be formed to draft and comment for the standard to build
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consensus and seek approval from standard committee.
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8. Summary and future perspectives


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Waste to biochar as a by-product via pyrolysis/gasification instead of incineration

sequesters carbon in an end product which alleviates climate change, contributes to


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environmental sustainability, and helps to develop a circular economy. A consolidated


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standard is needed for a healthy and sustainable development of biochar industry. In this

Review, the specification for production and application of biochar was proposed as

Singapore biochar standard which regulates the specific requirements of the production

and subsequent application in agriculture and horticulture, and in anaerobic digestion, as

construction material and activated carbon in Singapore. The proposed standard can act

as the guideline for biochar market and ensure a safe and healthy environment.

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However, some challenges impede the development of a biochar-based circular

economy. Firstly, the relationships between biochar production and its subsequent

application are insufficiently documented in the literature. The relationship between

production technologies and the properties of the biochar, and between biochar properties

and the results of the various applications, need to be further explored. Further studies

regarding the production, modification and application of biochar can facilitate its cost-

effective application for environmental sustainability and zero-waste development

of
purposes. Secondly, it is difficult to obtain homogenous biochar with desired properties

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for different applications with the current production technologies where feedstock is

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varying. The development of sorting, pretreating and production technology for waste is
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urgently needed for biochar industry to ensure the properties of biochar can meet the

proposed standard. Thirdly, currently most studies about the application of biochar are
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conducted in small-scale laboratories. More efforts should be paid on real in-situ and
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large-scale environment applications of biochar to reduce the uncertainty of

environmental impact. The actual effect of biochar on the environment needs to be


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elucidated in-depth. Fourthly, the information about long-term cycle over decades or even
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hundred years of biochar in ecological system is lacking. This limits the accuracy of the

proposed parameters of biochar in the standard. Potential threat exists for the application

and reutilization of biochar, and the disposal of spent biochar. The knowledge gaps

including long-term carbon sequestration, contaminants release and impact of biochar on

ecological system are urgently needed to be filled up. Fifthly, the cooperation among

biochar industry, third-party testing and certification body, and government is expected to

strengthen for the creating of the biochar-based circular economy market.

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In this context, the novel commercial models should be introduced into the biochar-

based circular economy. More efforts should be paid for the research, innovation, and

creation of biochar industry in response to the changing markets. We further suggest that

greater collaboration between researchers, biochar producer and consumer, and

government is required to advance the research and promote the biochar-based circular

economy technology at a global scale.

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Acknowledgement

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This research program is funded by the National Research Foundation (NRF), Prime

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Minister’s Office, Singapore, under its Campus for Research Excellence and
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Technological Enterprise (CREATE) program, grant Number R-706-001-102-281. The

authors acknowledge the technical input by Dr. Xin He on Figure 2(c). Any opinions,
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findings and conclusions or recommendations expressed in this material are those of the
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author(s) and do not reflect the views of the National Environment Agency Singapore,

Public Utilities Board, Singapore, National Park Board, Singapore, Singapore Food
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Agency, and Enterprise Singapore.


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References

Akhtar, A., Sarmah, A.K. 2018. Novel biochar-concrete composites: Manufacturing,


characterization and evaluation of the mechanical properties. Science of the Total
Environment, 616, 408-416.
Akhtar, M., Pradhan, S.K., Chang, J.-K., Majumder, S.B. 2020. A lithium ion rechargeable full
cell using flower-like Na3V2(PO4)3@C cathode and Li4Ti5O12 anode. ACS Sustainable
Chemistry & Engineering, 19, 7523-7535.
Alhashimi, H.A., Aktas, C.B. 2017. Life cycle environmental and economic performance of
biochar compared with activated carbon: a meta-analysis. Resources, Conservation and
Recycling, 118, 13-26.
ASTM, A. 2012. C143/C143M-12-Standard Test Method for Slump of Hydraulic-Cement
Concrete. USA: ASTM International.

44
Journal Pre-proof

ASTM, C. 2007. Standard test method for flow of hydraulic cement mortar. C1437.
ASTM, C‐15. 2015. Standard specification for silica fume used in cementitious mixtures, ASTM
International West Conshohocken, PA.
Cazetta, A.L., Pezoti, O., Bedin, K.C., Silva, T.L., Paesano Junior, A., Asefa, T., Almeida, V.C.
2016. Magnetic activated carbon derived from biomass waste by concurrent synthesis:
efficient adsorbent for toxic dyes. ACS Sustainable Chemistry & Engineering, 4(3), 1058-
1068.
Cha, J.S., Park, S.H., Jung, S.-C., Ryu, C., Jeon, J.-K., Shin, M.-C., Park, Y.-K. 2016. Production
and utilization of biochar: A review. Journal of Industrial and Engineering Chemistry, 40,
1-15.
Chen, D., Chen, X., Sun, J., Zheng, Z., Fu, K. 2016. Pyrolysis polygeneration of pine nut shell:
quality of pyrolysis products and study on the preparation of activated carbon from
biochar. Bioresource Technology, 216, 629-636.
Chen, S.S., Cao, Y., Tsang, D.C., Tessonnier, J.-P., Shang, J., Hou, D., Shen, Z., Zhang, S., Ok,

of
Y.S., Wu, K.C.-W. 2020. Effective dispersion of MgO nanostructure on biochar support
as a basic catalyst for glucose isomerization. ACS Sustainable Chemistry & Engineering,
8(18), 6990-7001.

ro
Coetzee, G.H., Sakurovs, R., Neomagus, H.W., Everson, R.C., Mathews, J.P., Bunt, J.R. 2017.
Particle size influence on the pore development of nanopores in coal gasification chars:

-p
From micron to millimeter particles. Carbon, 112, 37-46.
Czekała, W., Malińska, K., Cáceres, R., Janczak, D., Dach, J., Lewicki, A. 2016. Co-composting
of poultry manure mixtures amended with biochar – The effect of biochar on temperature
re
and C-CO2 emission. Bioresource technology, 200, 921-927.
Dang, Y., Holmes, D.E., Zhao, Z., Woodard, T.L., Zhang, Y., Sun, D., Wang, L.-Y., Nevin, K.P.,
Lovley, D.R. 2016. Enhancing anaerobic digestion of complex organic waste with
lP

carbon-based conductive materials. Bioresource Technology, 220, 516-522.


Dissanayake, P.D., Choi, S.W., Igalavithana, A.D., Yang, X., Tsang, D.C.W., Wang, C.-H., Kua,
H.W., Lee, K.B., Ok, Y.S. 2020. Sustainable gasification biochar as a high efficiency
na

adsorbent for CO2 capture: A facile method to designer biochar fabrication. Renewable
and Sustainable Energy Reviews, 124, 109785.
Dixit, A., Gupta, S., Dai Pang, S., Kua, H.W. 2019. Waste Valorisation using biochar for cement
replacement and internal curing in ultra-high performance concrete. Journal of Cleaner
ur

Production, 238, 117876.


EBC. 2012. European Biochar Certificate - Guidelines for a Sustainable Production of Biochar,
Jo

European Biochar Foundation (EBC). Arbaz, Switzerland. DOI:


10.13140/RG.2.1.4658.7043
Fagerström, A., Al Seadi, T., Rasi, S., Briseid, T. 2018. The role of anaerobic digestion and
biogas in the circular economy. IEA Bioenergy.
Fidel, R.B., Laird, D.A., Thompson, M.L., Lawrinenko, M. 2017. Characterization and
quantification of biochar alkalinity. Chemosphere, 167, 367-373.
Ge, X., Wu, Z., Wu, Z., Yan, Y., Cravotto, G., Ye, B.-C. 2016. Microwave-assisted modification
of activated carbon with ammonia for efficient pyrene adsorption. Journal of Industrial
and Engineering Chemistry, 39, 27-36.
Ghosh, S., Scharenbroch, B. C., Burcham, D., Ow, L. F., Shenbagavalli, S., Mahimairaja, S. 2016.
Influence of soil properties on street tree attributes in Singapore. Urban ecosystems, 19(2),
949-967.
Giwa, A.S., Xu, H., Chang, F., Wu, J., Li, Y., Ali, N., Ding, S., Wang, K. 2019. Effect of biochar
on reactor performance and methane generation during the anaerobic digestion of food
waste treatment at long-run operations. Journal of Environmental Chemical Engineering,
7(4), 103067.

45
Journal Pre-proof

Glaser, B., Lehmann, J., Zech, W. 2002. Ameliorating physical and chemical properties of highly
weathered soils in the tropics with charcoal–a review. Biology and fertility of soils, 35(4),
219–230.
Godlewska, Paulina, Ok, Yong Sik, & Oleszczuk, Patryk. 2021. THE DARK SIDE OF BLACK
GOLD: Ecotoxicological aspects of biochar and biochar-amended soils. Journal of
Hazardous Materials, 403, 123833.
Gupta, S. and Kua, H.W., 2020. Application of rice husk biochar as filler in cenosphere modified
mortar: Preparation, characterization and performance under elevated temperature.
Construction and Building Materials, 253, 119083
Gupta, S., Kua, H.W. 2019. Carbonaceous micro-filler for cement: Effect of particle size and
dosage of biochar on fresh and hardened properties of cement mortar. Science of the Total
Environment, 662, 952-962.
Gupta, S., Kua, H.W. 2018. Effect of water entrainment by pre-soaked biochar particles on
strength and permeability of cement mortar. Construction and Building Materials, 159,

of
107-125.
Gupta, S., Kua, H.W. 2017. Factors determining the potential of biochar as a carbon capturing
and sequestering construction material: a critical review. Journal of Materials in Civil

ro
Engineering, 29(9), 1-14.
Gupta, S., Kua, H.W., Koh, H.J. 2018a. Application of biochar from food and wood waste as

-p
green admixture for cement mortar. Science of The Total Environment, 619, 419-435.
Gupta, S., Kua, H.W., Pang, S.D. 2018b. Biochar-mortar composite: Manufacturing, evaluation
of physical properties and economic viability. Construction and Building Materials, 167,
re
874-889.
Hsu, C.-H., Pan, Z.-B., Chen, C.-R., Wei, M.-X., Chen, C.-A., Lin, H.-P., Hsu, C.-H. 2020.
Synthesis of Multiporous Carbons from the Water Caltrop Shell for High-Performance
lP

Supercapacitors. ACS Omega.


Huang, X., Zeng, Z., Bao, S., Wang, M., Qi, X., Fan, Z., Zhang, H. 2013. Solution-phase epitaxial
growth of noble metal nanostructures on dispersible single-layer molybdenum disulfide
na

nanosheets. Nature communications, 4(1), 1-8.


Huang, Y., Peng, J., Luo, J., Li, W., Wu, Z., shi, m., Li, X., Li, N., Chang, B., Wang, X. 2020.
Spherical Gr/Si/GO/C composite as High-Performance Anode Material for Lithium-Ion
Batteries. Energy & Fuels.
ur

Inyang, M.I., Gao, B., Yao, Y., Xue, Y., Zimmerman, A., Mosa, A., Pullammanappallil, P., Ok,
Y.S., Cao, X. 2016. A review of biochar as a low-cost adsorbent for aqueous heavy metal
Jo

removal. Critical Reviews in Environmental Science and Technology, 46(4), 406-433.


Jin, H., Wang, X., Gu, Z., Polin, J. 2013. Carbon materials from high ash biochar for
supercapacitor and improvement of capacitance with HNO3 surface oxidation. Journal of
Power Sources, 236, 285-292.
Jin, H., Wang, X., Shen, Y., Gu, Z. 2014. A high-performance carbon derived from corn stover
via microwave and slow pyrolysis for supercapacitors. Journal of Analytical and Applied
Pyrolysis, 110, 18-23.
Kah, M., Sigmund, G., Xiao, F., Hofmann, T. 2017. Sorption of ionizable and ionic organic
compounds to biochar, activated carbon and other carbonaceous materials. Water
Research, 124, 673-692.
Kamran, M., Malik, Z., Parveen, A., Huang, L., Riaz, M., Bashir, S., Mustafa, A., Abbasi, G.H.,
Xue, B., Ali, U. 2020. Ameliorative Effects of Biochar on Rapeseed (Brassica napus L.)
Growth and Heavy Metal Immobilization in Soil Irrigated with Untreated Wastewater.
Journal of Plant Growth Regulation, 39(1), 266-281.
Khan, A.Z., Ding, X.D., Khan, S., Ayaz, T., Fidel, R., Khan, M.A. 2020. Biochar efficacy for
reducing heavy metals uptake by Cilantro (Coriandrum sativum) and spinach (Spinaccia
oleracea) to minimize human health risk. Chemosphere, 244, 125543.

46
Journal Pre-proof

Kim, J.-Y., Oh, S., Park, Y.-K. 2020. Overview of biochar production from preservative-treated
wood with detailed analysis of biochar characteristics, heavy metals behaviors, and their
ecotoxicity. Journal of Hazardous Materials, 384, 121356.
Kirkelund, G.M., Jørgensen, A.S., Ingeman-Nielsen, T., Villumsen, A. 2012. Characterization of
MSWI bottom ash for potential use as subbase in greenlandic road construction, 4th
International Conference on Engineering for Waste and Biomass Valorization, pp. 835-
840.
Koutcheiko, S., Vorontsov, V. 2013. Activated carbon derived from wood biochar and its
application in supercapacitors. Journal of Biobased Materials and Bioenergy, 7(6), 733-
740.
Kua, H.W., Gupta, S., Koh, S.T., 2021. Chapter 10. Application of biochar as a sustainable
admixture in cement and the evaluation of its potential as a coating on PVA fiber in
mortar, In Biochar: Emerging Applications, IOP Publishing, Bristol, United Kingdom,
forthcoming.

of
Lee, J.H., Bang, K.W. 2000. Characterization of urban stormwater runoff. Water Research, 34(6),
1773-1780.
Li, F., He, X., Shoemaker, C.A., Wang, C.-H. 2020. Experimental and numerical study of

ro
biomass catalytic pyrolysis using Ni2P-loaded zeolite: Product distribution,
characterization and overall benefit. Energy Conversion and Management, 208, 112581.

-p
Liu, F., Rotaru, A.-E., Shrestha, P.M., Malvankar, N.S., Nevin, K.P., Lovley, D.R. 2012.
Promoting direct interspecies electron transfer with activated carbon. Energy &
Environmental Science, 5(10), 8982-8989.
re
Liu, J., Liu, Y., Peng, J., Liu, Z., Jiang, Y., Meng, M., Zhang, W., Ni, L. 2018. Preparation of
high surface area oxidized activated carbon from peanut shell and application for the
removal of organic pollutants and heavy metal ions. Water, Air, & Soil Pollution, 229(12),
lP

391.
Liu, J., Ren, S., Cao, J., Tsang, D. C., Beiyuan, J., Peng, Y., ... & Wang, J. 2020. Highly efficient
removal of thallium in wastewater by MnFe2O4-biochar composite. Journal of
na

Hazardous Materials, 401, 123311.


Maneerung, T., Liew, J., Dai, Y., Kawi, S., Chong, C., Wang, C.-H. 2016. Activated carbon
derived from carbon residue from biomass gasification and its application for dye
adsorption: Kinetics, isotherms and thermodynamic studies. Bioresource Technology, 200,
ur

350-359.
Matrapazi, V.K., Zabaniotou, A. 2020. Experimental and feasibility study of spent coffee grounds
Jo

upscaling via pyrolysis towards proposing an eco-social innovation circular economy


solution. Science of The Total Environment, 718, 137316.
Mohamed, B.A., Ellis, N., Kim, C.S., Bi, X., Emam, A.E.-r. 2016. Engineered biochar from
microwave-assisted catalytic pyrolysis of switchgrass for increasing water-holding
capacity and fertility of sandy soil. Science of The Total Environment, 566-567, 387–397.
Mumme, J., Srocke, F., Heeg, K., Werner, M. 2014. Use of biochars in anaerobic digestion.
Bioresource Technology, 164, 189-197.
Muthukrishnan, S., Gupta, S., Kua, H.W. 2019. Application of rice husk biochar and thermally
treated low silica rice husk ash to improve physical properties of cement mortar.
Theoretical and Applied Fracture Mechanics, 104, 102376.
National Environment Agency, Singapore. Allowable Limits for Trade Effluent Discharge to
Watercourse or Controlled Watercourse. https://www.nea.gov.sg/our-services/pollution-
control/water-quality/allowable-limits-for-trade-effluent-discharge-to-watercourse-or-
controlled-watercourse.
National Environment Agency, Singapore. 2015. Singapore's Efforts in Addressing Climate
Change. https://www.nea.gov.sg/our-services/climate-change-energy-efficiency/climate-
change/singapore's-efforts-in-addressing-climate-change.

47
Journal Pre-proof

National Environment Agency, Singapore. 2020. Waste Statistics and Overall Recycling.
https://www.nea.gov.sg/our-services/waste-management/waste-statistics-and-overall-
recycling.
Nejad, Z.D., Jung, M.C., Kim, K.H. 2018. Remediation of soils contaminated with heavy metals
with an emphasis on immobilization technology. Environmental Geochemistry and
Health, 40(3), 927-953.
Oleszczuk, P., Jośko, I., Kuśmierz, M. 2013. Biochar properties regarding to contaminants
content and ecotoxicological assessment. Journal of Hazardous Materials, 260, 375-382.
Pan, J., Ma, J., Zhai, L., Luo, T., Mei, Z., Liu, H. 2019. Achievements of biochar application for
enhanced anaerobic digestion: A review. Bioresource Technology, 292, 122058.
Pandit, N.R., Mulder, J., Hale, S.E., Martinsen, V., Schmidt, H.P., Cornelissen, G. 2018. Biochar
improves maize growth by alleviation of nutrient stress in a moderately acidic low-input
Nepalese soil. Science of The Total Environment, 625, 1380–1389.
Paul, S., Kauser, H., Jain, M.S., Khwairakpam, M., Kalamdhad, A.S. 2020. Biogenic stabilization

of
and heavy metal immobilization during vermicomposting of vegetable waste with biochar
amendment. Journal of Hazardous Materials, 390, 121366.
Pecchi, M., Baratieri, M. 2019. Coupling anaerobic digestion with gasification, pyrolysis or

ro
hydrothermal carbonization: A review. Renewable and Sustainable Energy Reviews, 105,
462-475.

-p
Prodana, M., Silva, C., Gravato, C., Verheijen, F.G.A., Keizer, J.J., Soares, A., Loureiro, S.,
Bastos, A.C. 2019. Influence of biochar particle size on biota responses. Ecotoxicology
and Environmental Safety, 174, 120-128.
re
Purakayastha, T.J., Bera, T., Bhaduri, D., Sarkar, B., Mandal, S., Wade, P., Kumari, S., Biswas,
S., Menon, M., Pathak, H., Tsang, D.C.W. 2019. A review on biochar modulated soil
condition improvements and nutrient dynamics concerning crop yields: Pathways to
lP

climate change mitigation and global food security. Chemosphere, 227, 345–365.
Qian, T.-T., Wu, P., Qin, Q.-Y., Huang, Y.-N., Wang, Y.-J., Zhou, D.-M. 2019. Screening of
wheat straw biochars for the remediation of soils polluted with Zn (II) and Cd (II).
na

Journal of Hazardous Materials, 362, 311-317.


Qin, J., Niu, A., Liu, Y., Lin, C. 2021. Arsenic in leafy vegetable plants grown on mine water-
contaminated soils: Uptake, human health risk and remedial effects of biochar. Journal of
Hazardous Materials, 402, 123488.
ur

Ramanayaka, S., Tsang, D.C.W., Hou, D., Ok, Y.S., Vithanage, M. 2020. Green synthesis of
graphitic nanobiochar for the removal of emerging contaminants in aqueous media.
Jo

Science of The Total Environment, 706, 135725.


Rizwan, M., Ali, S., Qayyum, M.F., Ibrahim, M., Zia-ur-Rehman, M., Abbas, T., Ok, Y.S. 2016.
Mechanisms of biochar-mediated alleviation of toxicity of trace elements in plants: a
critical review. Environmental Science and Pollution Research, 23(3), 2230–2248.
Rizwan, M., Ali, S., Zia ur Rehman, M., Rinklebe, J., Tsang, D.C.W., Bashir, A., Maqbool, A.,
Tack, F.M.G., Ok, Y.S. 2018. Cadmium phytoremediation potential of Brassica crop
species: A review. Science of The Total Environment, 631-632, 1175–1191.
Roberts, K.G., Gloy, B.A., Joseph, S., Scott, N.R., Lehmann, J. 2010. Life cycle assessment of
biochar systems: estimating the energetic, economic, and climate change potential.
Environmental Science & Technology, 44(2), 827-833.
Ruzickova, J., Koval, S., Raclavska, H., Kucbel, M., Svedova, B., Raclavsky, K., Juchelkova, D.,
Scala, F. 2020. A comprehensive assessment of potential hazard caused by organic
compounds in biochar for agricultural use. Journal of Hazardous Materials, 403, 123644.
Sanchez-Monedero, M. A., Cayuela, M. L., Roig, A., Jindo, K., Mondini, C., Bolan, N. 2018.
Role of biochar as an additive in organic waste composting. Bioresource Technology, 247,
1155-1164.

48
Journal Pre-proof

Shakoor, M. B., Ali, S., Rizwan, M., Abbas, F., Bibi, I., Riaz, M., ... & Rinklebe, J. (2020). A
review of biochar-based sorbents for separation of heavy metals from water.
International Journal of Phytoremediation, 22(2), 111-126.
Shamurad, B., Sallis, P., Petropoulos, E., Tabraiz, S., Ospina, C., Leary, P., Dolfing, J., Gray, N.
2020. Stable biogas production from single-stage anaerobic digestion of food waste.
Applied Energy, 263, 114609.
Shao, Y., Long, Y., Wang, H., Liu, D., Shen, D., Chen, T. 2019. Hydrochar derived from green
waste by microwave hydrothermal carbonization. Renewable energy, 135, 1327-1334.
Sharma, H.B., Panigrahi, S., Sarmah, A.K., Dubey, B.K. 2020. Downstream augmentation of
hydrothermal carbonization with anaerobic digestion for integrated biogas and hydrochar
production from the organic fraction of municipal solid waste: A circular economy
concept. Science of The Total Environment, 706, 135907.
Shen, Y., Song, S., Thian, B.W.Y., Fong, S.L., Ee, A.W.L., Arora, S., Ghosh, S., Li, S.F.Y., Tan,
H.T.W., Dai, Y., Wang, C.-H. 2020. Impacts of biochar concentration on the growth

of
performance of a leafy vegetable in a tropical city and its global warming potential.
Journal of Cleaner Production, 264, 121678.
Sherwood, J. 2020. The significance of biomass in a circular economy. Bioresource Technology,

ro
300, 122755.
Sim, J. W. S., Tan, H. T. W., Turner, I. M. 1992. Adinandra belukar: an anthropogenic heath

-p
forest in Singapore. Vegetatio, 102(2), 125-137.
Song, S., Arora, S., Laserna, A.K.C., Shen, Y., Thian, B.W.Y., Cheong, J.C., Tan, J.K.N., Chiam,
Z., Fong, S.L., Ghosh, S., Ok, Y.S., Li, S.F.Y., Tan, H.T.W., Dai, Y., Wang, C.-H. 2020.
re
Biochar for urban agriculture: Impacts on soil chemical characteristics and on Brassica
rapa growth, nutrient content and metabolism over multiple growth cycles. Science of The
Total Environment, 727, 138742.
lP

Sormo, E., Silvani, L., Thune, G., Gerber, H., Schmidt, H.P., Smebye, A.B., Cornelissen, G. 2020.
Waste timber pyrolysis in a medium-scale unit: Emission budgets and biochar quality.
Science of the Total Environment, 718, 137335.
na

Spokas, K.A. 2010. Review of the stability of biochar in soils: predictability of O: C molar ratios.
Carbon Management, 1(2), 289-303.
IBI Standard. 2015. IBI Biochar Certification Program Manual: Requirements and Procedures for
IBI Biochar Certification, 2015. https://www.biochar-international.org/wp-
ur

content/uploads/2018/05/IBI_Biochar_Certification_Program_Manual_V2.1_Final.pdf.
Korea Fertilizer Standard. 2019. ENFORCEMENT DECREE OF THE FERTILIZER CONTROL
Jo

ACT. http://www.law.go.kr/LSW/eng/engLsSc.do?menuId=2&query=FERTILIZER%20
CONTROL%20ACT#liBgcolor0.
Starr, K., Gabarrell, X., Villalba, G., Talens, L., Lombardi, L. 2012. Life cycle assessment of
biogas upgrading technologies. Waste Management, 32(5), 991-999.
Sullivan, G.L., Prigmore, R.M., Knight, P., Godfrey, A.R. 2019. Activated carbon biochar from
municipal waste as a sorptive agent for the removal of polyaromatic hydrocarbons
(PAHs), phenols and petroleum based compounds in contaminated liquids. Journal of
Environmental Management, 251, 109551.
Sunyoto, N.M.S., Zhu, M., Zhang, Z., Zhang, D. 2016. Effect of biochar addition on hydrogen
and methane production in two-phase anaerobic digestion of aqueous carbohydrates food
waste. Bioresource Technology, 219, 29-36.
Tong, H., Yao, Z., Lim, J.W., Mao, L., Zhang, J., Ge, T.S., Peng, Y.H., Wang, C.-H., Tong, Y.W.
2018. Harvest green energy through energy recovery from waste: A technology review
and an assessment of Singapore. Renewable and Sustainable Energy Reviews, 98, 163-
178.
Trahey, L., Karan, N.K., Chan, M.K., Lu, J., Ren, Y., Greeley, J., Balasubramanian, M., Burrell,
A.K., Curtiss, L.A., Thackeray, M.M. 2013. Synthesis, Characterization, and Structural

49
Journal Pre-proof

Modeling of High‐Capacity, Dual Functioning MnO2 Electrode/Electrocatalysts for Li‐


O2 Cells. Advanced Energy Materials, 3(1), 75-84.
Tratsch, M.V.M., Ceretta, C.A., Silva, L.S.d., Ferreira, P.A.A., Brunetto, G. 2019. Composition
and mineralization of organic compost derived from composting of fruit and vegetable
waste. Revista Ceres, 66, 307-315.
Wainaina, S., Awasthi, M.K., Sarsaiya, S., Chen, H., Singh, E., Kumar, A., Ravindran, B.,
Awasthi, S.K., Liu, T., Duan, Y., Kumar, S., Zhang, Z., Taherzadeh, M.J. 2020. Resource
recovery and circular economy from organic solid waste using aerobic and anaerobic
digestion technologies. Bioresource Technology, 301, 122778.
Wang, D., Jiang, P., Zhang, H., Yuan, W. 2020a. Biochar production and applications in agro and
forestry systems: A review. Science of The Total Environment, 723, 137775.
Wang, J., Wang, S. 2019. Preparation, modification and environmental application of biochar: A
review. Journal of Cleaner Production, 227, 1002-1022.
Wang, L., Chen, L., Tsang, D.C.W., Kua, H.W., Yang, J., Ok, Y.S., Ding, S., Hou, D., Poon, C.S.

of
2019a. The roles of biochar as green admixture for sediment-based construction products.
Cement and Concrete Composites, 104, 103348.
Wang, L., Wang, Y., Ma, F., Tankpa, V., Bai, S., Guo, X., Wang, X. 2019b. Mechanisms and

ro
reutilization of modified biochar used for removal of heavy metals from wastewater: a
review. Science of the total environment, 668, 1298-1309.

-p
Wang, S., Dai, G., Yang, H., Luo, Z. 2017. Lignocellulosic biomass pyrolysis mechanism: A
state-of-the-art review. Progress in Energy and Combustion Science, 62, 33-86.
Wang, T., Jiang, Z., Zhao, B., Gu, Y., Liou, K.-N., Kalandiyur, N., Zhang, D., Zhu, Y. 2020b.
re
Health co-benefits of achieving sustainable net-zero greenhouse gas emissions in
California. Nature Sustainability, 1-9.
Weng, Z., Van Zwieten, L., Singh, B.P., Tavakkoli, E., Joseph, S., Macdonald, L.M., Rose, T.J.,
lP

Rose, M.T., Kimber, S.W.L., Morris, S., Cozzolino, D., Araujo, J.R., Archanjo, B.S.,
Cowie, A. 2017. Biochar built soil carbon over a decade by stabilizing rhizodeposits.
Nature Climate Change, 7(5), 371-376.
na

Woolf, D., Amonette, J.E., Street-Perrott, F.A., Lehmann, J., Joseph, S. 2010. Sustainable biochar
to mitigate global climate change. Nature Communications, 1(1), 56.
Woolf, D., Lehmann, J., Lee, D.R. 2016. Optimal bioenergy power generation for climate change
mitigation with or without carbon sequestration. Nature Communications, 7(1), 13160.
ur

Wu, X., Fan, L., Wang, M., Cheng, J., Wu, H., Guan, B., Zhang, N., Sun, K. 2017. Long-life
lithium–sulfur battery derived from nori-based nitrogen and oxygen dual-doped 3D
Jo

hierarchical biochar. ACS applied materials & interfaces, 9(22), 18889-18896.


Xiang, W., Zhang, X., Chen, K., Fang, J., He, F., Hu, X., Tsang, D.C.W., Ok, Y.S., Gao, B. 2020.
Enhanced adsorption performance and governing mechanisms of ball-milled biochar for
the removal of volatile organic compounds (VOCs). Chemical Engineering Journal, 385,
123842.
Yang, X., Ng, W., Wong, B.S.E., Baeg, G.H., Wang, C.-H., Ok, Y.S. 2019a. Characterization and
ecotoxicological investigation of biochar produced via slow pyrolysis: Effect of feedstock
composition and pyrolysis conditions. Journal of Hazardous Materials, 365, 178-185.
Yang, X., Tsibart, A., Nam, H., Hur, J., El-Naggar, A., Tack, F.M.G., Wang, C.-H., Lee, Y.H.,
Tsang, D.C.W., Ok, Y.S. 2019b. Effect of gasification biochar application on soil quality:
Trace metal behavior, microbial community, and soil dissolved organic matter. Journal of
Hazardous Materials, 365, 684–694.
Yang, Z., Koh, S.K., Ng, W.C., Lim, R.C.J., Tan, H.T.W., Tong, Y.W., Dai, Y., Chong, C., Wang,
C.-H. 2016. Potential application of gasification to recycle food waste and rehabilitate
acidic soil from secondary forests on degraded land in Southeast Asia. Journal of
Environmental Management, 172, 40-48.

50
Journal Pre-proof

Zeeshan, M., Ahmad, W., Hussain, F., Ahamd, W., Numan, M., Shah, M., Ahmad, I. 2020.
Phytostabalization of the heavy metals in the soil with biochar applications, the impact on
chlorophyll, carotene, soil fertility and tomato crop yield. Journal of Cleaner Production,
255, 120318.
Zhang, L., Li, F., Kuroki, A., Loh, K.-C., Wang, C.-H., Dai, Y., Tong, Y.W. 2020a. Methane
yield enhancement of mesophilic and thermophilic anaerobic co-digestion of algal
biomass and food waste using algal biochar: Semi-continuous operation and microbial
community analysis. Bioresource Technology, 302, 122892.
Zhang, L., Lim, E.Y., Loh, K.-C., Ok, Y.S., Lee, J.T.E., Shen, Y., Wang, C.-H., Dai, Y., Tong,
Y.W. 2020b. Biochar enhanced thermophilic anaerobic digestion of food waste: Focusing
on biochar particle size, microbial community analysis and pilot-scale application.
Energy Conversion and Management, 209, 112654.
Zhang, L., Loh, K.-C., Zhang, J. 2019. Enhanced biogas production from anaerobic digestion of
solid organic wastes: Current status and prospects. Bioresource Technology Reports, 5,

of
280-296.
Zhang, L., Sun, X. 2014. Changes in physical, chemical, and microbiological properties during
the two-stage co-composting of green waste with spent mushroom compost and biochar.

ro
Bioresource technology, 171, 274-284.
Zhang, P., O’Connor, D., Wang, Y., Jiang, L., Xia, T., Wang, L., Tsang, D.C.W., Ok, Y.S., Hou,

Hazardous Materials, 384, 121286.


-p
D. 2020c. A green biochar/iron oxide composite for methylene blue removal. Journal of

Zhao, L., Cao, X., Mašek, O., Zimmerman, A. 2013. Heterogeneity of biochar properties as a
re
function of feedstock sources and production temperatures. Journal of Hazardous
Materials, 256, 1-9.
Zhao, Y., Watanabe, K., Hashimoto, K. 2012. Poly (bis-2, 6-diaminopyridinesulfoxide) as an
lP

active and stable electrocatalyst for oxygen reduction reaction. Journal of Materials
Chemistry, 22(24), 12263-12267.
Zhu, J., Tu, W., Pan, H., Zhang, H., Liu, B., Cheng, Y., Deng, Z., Zhang, H. 2020. Self-
na

Templating Synthesis of Hollow Co3O4 Nanoparticles Embedded in N, S-Dual-Doped


Reduced Graphene Oxide for Lithium Ion Batteries. ACS nano, 14(5), 5780-5787.
Zielińska, A., Oleszczuk, P. 2015. Evaluation of sewage sludge and slow pyrolyzed sewage
sludge-derived biochar for adsorption of phenanthrene and pyrene. Bioresource
ur

Technology, 192, 618-626.


Zomeren, A.v., Hjelmar, O., Sloot, H.A.v.d., Hyks, J., Saveyn, H., Eder, P., Garbarino, E.,
Jo

Muchova, L., Oberender, A. 2014. Study on methodological aspects regarding limit


values for pollutants in aggregates in the context of the possible development of end-of-
waste criteria under the EU Waste Framework Directive. No. ECN-O--14-045. ECN.

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Author Contributions
Qiang Hu (Sections 1, 2, 7 & 8), Janelle Jung (Section 3), Dexiang Chen (Sections 3 & 7),

Ken Leong (Sections 1 & 7), Shuang Song (Sections 3 & 8), Fanghua Li (Section 3), Babu

Mohan (Section 5), Zhiyi Yao (Sections 5 & 7), Arun Kumar Prabhakar (Section 4), Xuan

Hao Lin (Section 3), Ee Yang Lim (Section 6), Le Zhang (Section 6), Gupta Souradeep

(Section 4) , Yong Sik Ok (Sections 2 & 7), Harn Wei Kua (Sections 4 & 7), Sam F. Y. Li

(Section 3), Hugh T. W. Tan (Section 3), Yanjun Dai (Sections 1 & 2), Yen Wah Tong

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(Sections 6 & 8), Yinghong Peng (Sections 1 & 8), Stephen Joseph (Sections 1, 2, 3, 7 & 8),

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Chi-Hwa Wang (Sections 1, 2, 7 & 8). All authors reviewed the revised manuscript.

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Declaration of competing interest

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

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Graphical abstract
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Highlights
 Waste to biochar is a sustainable partway to circular economy.

 Four key uses of the Singapore biochar industry are analyzed and reviewed.

 The code of practice for biochar application in Singapore is proposed.

 Future perspective of the research, innovation and development for biochar industry is

discussed.

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