Science of the Total Environment 914 (2024) 169607

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Science of the Total Environment

journal homepage: www.elsevier.com/locate/scitotenv

Comparative analysis of biochar carbon stability methods and implications

for carbon credits
Sirjana Adhikari a, b, *, Ellen Moon a, c, Jorge Paz-Ferreiro d, Wendy Timms a, b
a
School of Engineering, Deakin University, Geelong, Victoria 3216, Australia
b
Centre for Sustainable Bioproducts, Deakin University, Geelong, Victoria 3216, Australia
c
ARC Centre of Excellence for Enabling the Eco-efficient Beneficiation of Minerals, Deakin University, Geelong, Victoria 3216, Australia
d
School of Engineering, RMIT University, Melbourne, Victoria 3001, Australia

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Biochar carbon is highly stable and

provides confidence for carbon credits.
• Simple pyrolysis biochar has compara­
ble carbon stability to advanced
pyrolysis.
• Biochar feedstock is a primary factor
influencing carbon structural stability.
• Accepted method H:Corg requires revi­
sion, to include recent incubation tests
and their modeling results.
• Derived methods CS and R50 may pro­
vide certainty where biochar stability is
borderline.

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

Editor: Daniel CW Tsang Biochar is an emerging negative emission technology. Its ability to sequester carbon and subsequent carbon
credit valuation hinge on the stability of its carbon structure. The widely used indicators of carbon stability H:
Keywords: Corg and O:Corg provide conservative results as these are based on limited incubation experiments and associated
Soil carbon sequestration modeling results. The results from these accepted methods and other derived methods have not been compared
Soil carbon storage
as indicators of carbon stability in a variety of biochar samples. Furthermore, the influence of contrasting
Pyrolysis
feedstock and production techniques on biochar carbon stability is not well explored. Therefore, to address these
Feedstock
Recalcitrance index challenges, a comprehensive stability analysis of 21 different biochar samples with contrasting feedstocks and
Carbon credits pyrolysis techniques was conducted using a combination of instrumental methods and derived indicators of
carbon stability. Methods such as biochar carbon half-life, thermo-stable fraction, oxidation resistance (R50), and
carbon sequestration potential (CS) were used. Based on the initial carbon content of the biochar, simple py­
rolysis techniques have similar potential for carbon credits as biochar produced from advanced pyrolysis tech­
niques. Results indicate that the carbon stability of a biochar product is primarily a factor of feedstock type. We
found that biochar carbon stability is not related to volatile matter or fixed carbon content for biochar produced
using a simple pyrolysis technique and mixed feedstock. Biochars with H:Corg < 0.4 were deemed to have lower

* Corresponding author at: School of Engineering, Deakin University, 75 Pigdons Road, Waurn Ponds, Victoria 3216, Australia.
E-mail addresses: adhikaris@deakin.edu.au (S. Adhikari), ellen.moon@deakin.edu.au (E. Moon), jorge.paz-ferreiro@rmit.edu.au (J. Paz-Ferreiro), wendy.timms@
deakin.edu.au (W. Timms).

https://doi.org/10.1016/j.scitotenv.2023.169607
Received 16 October 2023; Received in revised form 3 December 2023; Accepted 20 December 2023
Available online 27 December 2023
0048-9697/© 2023 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

carbon stability when compared using different methods. No correlation was observed between the carbon
stability of biochar using H:Corg and other methods, however, correlations were observed between half-life, O:
Corg, fixed carbon, number of aromatic peaks in FTIR spectrum, R50, and CS. Therefore, it is recommended that
data from additional incubation and modeling studies need to be considered to increase the confidence in carbon
stability results having major implications to carbon credits.

1. Introduction 2011; Crombie et al., 2013; Song and Guo, 2012; Wei et al., 2019; Xu
et al., 2021), NaOH trap (Fang et al., 2014; Saleem et al., 2022; Wei
Considering the lowest greenhouse gas (GHG) emission scenario, et al., 2019) and biochar-derived dissolved organic carbon (Luo et al.,
there is at least a >50 % likelihood that global warming will reach or 2015) to evaluate carbon pool types and mineralization rate of carbon.
exceed 1.5 ◦ C by 2040 (IPCC, 2022b). A significant reduction in GHG This method provides overall information about the MRT (Mean Resi­
emissions is required to attain net zero or net negative emissions by dence Time or time that biochar carbon will remain in the environment)
2060 globally (Anderson and Peters, 2016; Fitch et al., 2022). Net zero and half-life of biochar carbon (the time it will take for half of the carbon
focuses on balancing emissions, whereas net negative includes an to be mineralized). The environmental factors influencing carbon sta­
additional removal of CO2 from the atmosphere. The use of conventional bility are included in the incubation and modeling technique, thus
emission reduction methods such as, along with engineered and hybrid providing a comprehensive indicator of carbon stability if the environ­
methods is essential to reach the required emission reduction targets. mental conditions are optimized accordingly (Leng et al., 2019). How­
Biochar is a material, sustainably sourced from residual biomass, that ever, this method is expensive, time-consuming, and labor-intensive.
enables long-term carbon capture and enhances mechanisms to reduce Thus, there is a need to identify instrumental methods that correlate
GHGs in soils. Globally, biochar has a significant carbon sequestration with results from incubation and modeling tests and can be widely used
potential (Fitch et al., 2022; IPCC, 2022a; Smith, 2016) of 0.2 to 6.6 Gt to determine biochar carbon stability.
CO2 eq yr− 1, which can contribute to a billion-dollar market worldwide. Some of the instrumental methods used to assess biochar carbon
Biochar reduces resource competition and provides multiple co-benefits stability are elemental analysis (Budai et al., 2013; Leng et al., 2019;
to soils and climate due to its highly stable carbon content, large surface Spokas, 2010; Xiao et al., 2016), proximate analysis (Enders et al.,
area, and enhanced pore structure (Spokas, 2013). The climate benefits 2012), nuclear magnetic resonance (NMR) (Baldock and Smernik, 2002;
of biochar include long-term (100 to 1000 years) stability of carbon, McBeath and Smernik, 2009), Fourier transform infrared spectroscopy
reduction of nitrous oxide emission from soil, stabilization, and build-up (FTIR) (McBeath et al., 2014; Singh et al., 2016), near-edge X-ray ab­
of soil organic matter (Joseph et al., 2021; Weng et al., 2022) as well as sorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron
avoided fossil fuel emissions and GHG emissions that would otherwise spectroscopy (XPS) and X-ray diffraction (XRD) (Almutairi et al., 2022).
occur due to the decomposition of biomass (Leng and Huang, 2018). Among these methods, elemental and proximate analysis is widely
Biochar is an affordable and scalable solution to combat climate change accepted as they are easily available, reliable, and cost-effective (Budai
(Leng et al., 2019; Masson-Delmotte et al., 2021), and is regarded as a et al., 2013).
negative emission technology (IPCC, 2018) for carbon dioxide removal In addition to the instrumental methods, there has been significant
and durable carbon sequestration. effort in the development of new models for carbon stability assessment
The net GHG emission reduction and removal by a project using of biochar before its land application. Based on the elemental compo­
biochar is evaluated using the data of emission removal and reduction at sition, (Harvey et al., 2012) have proposed a new index-based approach
stages such as sourcing, production, application, and post-application called recalcitrance index (R50). Klasson (2017) developed equations to
leakage. Despite the complex chemical and microbial interactions of predict the H:Corg ratio using volatile matter and fixed carbon, looking
biochar with soil during the application and post-application stages and for opportunities where proximate analysis can be a proxy for elemental
the potential implications for C and N biogeochemical cycling, it is the analysis. Zhao et al. (2013) showed that fixed carbon and carbon
thermo-chemical biochar carbon stability that is a critical element in sequestration were primarily influenced by biochar feedstock. They used
calculating the net GHG emissions at each of the lifecycle stages. This the term carbon sequestration potential (CS) as a function of the initial
thermo-chemical carbon stability is therefore the foundation of the mass of feedstock, yield of biochar, R50, and carbon content of feedstock
overall GHG emission reduction calculation (VCS, 2021), which ulti­ and biochar, to indicate a difference between carbon lost during pyrol­
mately determines the eligibility of biochar for carbon credits. ysis compared to initial carbon in the feedstock.
Even though the technological readiness to scale up the biochar in­ However, some studies have shown inconsistencies between the
dustry has reached the highest level of maturity, and the baseline cost of outcomes of different carbon stability measures. Inconsistency exists
production is reduced to $60 per tonne, commercial readiness is still between different measures of carbon stability in biochar before soil
ranked up to 4 out of 9 in Australia (Fitch et al., 2022; Fitch et al., 2023). application. The predictions between the aromaticity index from H:Corg
Major drivers for this include a lack of public awareness, and signifi­ versus the aromaticity index from O:Corg were not consistent (Xu et al.,
cantly, a lack of confidence in quantifying the inherent biochar carbon 2021). Incubation and modeling studies regarded as a base of instru­
stability. Current assessment indicators (H:Corg and O:Corg) (Spokas, mental carbon stability assessment have presented significant excep­
2010), fixed carbon, volatile matter (Enders et al., 2012) are qualitative tions and limitations, indicating the requirement for standardization and
and based predominantly on incubation studies of mostly lab-prepared strengthening of instrumental and derived methods (Woolf et al., 2021).
biochar and the results of associated modeling before 2012 (Leng For example, the stability index using volatile matter and H:Corg ratio by
et al., 2019). Extensive characterization of a wide range of feedstock and (Enders et al., 2012) does not work for feedstock such as poultry manure
pyrolysis methods (Singh et al., 2012) better representative of industrial and papermill sludge. Further, the derived indices such as CS and R50
biochar preparation, and critical comparison of the varying stability require an understanding of molecular configurations of biomass feed­
assessment methods (Leng et al., 2019), will strengthen confidence in stock, which is not always available to biochar producers (Zhao et al.,
the carbon stability assessment for biochar. 2013) and validation of biochar carbon stability classes requires larger
Biochar carbon stability is assessed using field and lab-based in­ datasets including new feedstock, production conditions (Singh et al.,
cubations, modeling, and/or instrumental analysis methods (Gross 2016). To the best of our knowledge, these instrumental methods, and
et al., 2021; Leng and Huang, 2018) depending on the type of stability derived methods for biochar carbon stability of contrasting biochar
analysis. Incubation tests use chemical oxidation (Calvelo Pereira et al., types have not yet been compared.

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The degree of carbonization during the pyrolysis process often differs 2.1.2. Standard (reference) biochar samples
due to the scale of production and the use (or absence) of purge gases to In contrast to the locally sourced biochar samples, the standard
limit oxygen. To our knowledge, the influence of this factor on the biochar was produced by the UKBRC for the standardization of biochar
carbon stability of biochar has also not yet been explored. Pyrolysis research. These biochars are produced using individual feedstock
methods are defined based on the capture of syngas and biofuels as including sewage sludge (SS), wheat straw (WSP), softwood (SW), rice
simple and advanced pyrolysis (Zilberman et al., 2023). It is also defined husk (RH), oil seed rape (OSR), and miscanthus straw (MSP) at two
as high-technology pyrolysis and low-technology pyrolysis based on different temperatures 550 ◦ C and 700 ◦ C. Biochar retained their names
reporting of pyrolysis temperature, ability to combust or recover py­ from the biochar library as SS550, SS700, WSP550, WSP700, SWP550,
rolysis gases, limiting emissions to the atmosphere, ability to utilize or SWP700, RH550, RH700, OSR550, OSR700, MSP550, MSP700 respec­
recover at least 70 % of waste heat during production (VCS, 2021). tively. The standard biochars and 4 of the locally sourced biochars (L-
These different pyrolysis methods account for emission reduction (and HW1, L-MF3, L-HW4, and L-MF5) were AP-biochar while the others
thus carbon credits), but any differences in the structural stability of were SP-biochar. The biochar samples were dried in the oven at 105 ◦ C
biochar carbon from pyrolysis methods have not yet been evaluated. for 24 h, ground, and sieved to 0.5–2 mm particle size before analysis.
Pyrolysis temperature was observed to be significantly related to the Due to the variability in sample type and sample size, statistical
stability indicators for biochar prepared in a muffle furnace (Chen et al., analysis was not appropriate, and visualization techniques have been
2021), however because of the above-mentioned gaps in knowledge, used to present the novel findings in this article.
evaluation of a wide range of biochar prepared at an industrial scale
with contrasting feedstock is also required. 2.2. General characterization
Therefore, despite methodological advances in the analysis of bio­
char carbon stability, there is still a need for a broad dataset comparing pH and EC of biochar were analyzed using an electrometric method
biochar carbon stability measures for biochar created from different (Singh et al., 2017). pH and electrical conductivity (EC) of biochar were
feedstocks under different types of pyrolysis. Such a dataset could enable measured using deionized water at a ratio of 1:10, after shaking in an
a realistic assessment of how different instrumental carbon stability orbital shaker for 1 h. Bulk density, Specific Surface Area (SSA), and
assessment methods correlate and whether those correlations hold other general characteristics are provided in (Adhikari et al., 2023).
across feedstock types of pyrolysis techniques. In this study, we evaluate Correlations between the carbon stability using contrasting methods
the carbon stability of biochar from simple and advanced pyrolysis were evaluated by Spearman's rank correlation.
(hereafter referred to as SP-biochar and AP-biochar) with contrasting
feedstocks using different qualitative and quantitative instrumental 2.3. Biochar carbon stability
stability analysis methods. The SP methods are relatively inexpensive
and can be operated for relatively small or large volumes of local The carbon stability assessment methods were chosen considering
biomass, whereas the AP methods can capture the by-products such as the advantages and disadvantages (Leng et al., 2019) regarding cost-
syn gas or bio-oil (Zilberman et al., 2023). Specifically, we aimed to (1) effectiveness, availability, reliability, and types of analysis (Budai
evaluate the carbon stability of 21 SP and AP biochar samples (2) et al., 2013). Methods from each category I (analysis of biochar C
compare the carbon stability of biochar using a range of qualitative and structures), II (analysis of biochar oxidation resistance), and III (analysis
quantitative methods and (3) provide recommendations on practical of biochar persistence) (Leng et al., 2019) and alpha (assessment of
and scientific viability of methods used to evaluate biochar carbon sta­ physical or chemical properties related to C stability using easily
bility. This study will contribute to the standardization of instrumental available methods), beta (quantifying stability relating to alpha
biochar stability assessment methods and recommend ways to methods), and gamma (measurement of molecular properties related to
strengthen the stability assessment as a fundamental step for opportu­ biochar C stability and relating to alpha and beta methods) (Budai et al.,
nities such as GHG emission reduction calculation and carbon credits. 2013) have been included in the analysis. Firstly, category I or alpha
methods include instrumental analysis such as elemental analysis i.e.,
2. Materials and methods the ratio of atomic hydrogen and organic carbon (H:Corg) which was
used to evaluate the aromaticity of biochar carbon. In addition, volatile
2.1. Sample preparation matter (VM) and fixed carbon (FC) from the proximate analysis was used
to evaluate the thermo-degradable fraction of biochar carbon. Category
Among the 21 biochar samples used, nine were locally sourced from II includes, derived indices, and evaluation of biochar half-life based on
the east coast of Australia, including commercial products, and 12 were results from alpha methods. For example, the TGA R50 method was used
the standard (reference) biochar samples from the UK Biochar Research to assess the thermal stability of biochar carbon (Harvey et al., 2012;
Centre (UKBRC). Saleem et al., 2022; Windeatt et al., 2014). Thirdly, category III or
gamma methods include solid state 13C direct polarization nuclear
2.1.1. Locally sourced biochar samples (L) magnetic resonance spectroscopy (13C DP NMR) and FTIR for further
Biochar samples were chosen according to the feedstock type and validation of the results.
production condition. Locally sourced biochar (L) was mostly prepared
in large-scale, industrial plants for commercial purposes. Details about 2.3.1. Elemental analysis
the pre-processing, production, and post-processing of biochar was ob­ Elemental analysis was conducted using Denver instrument micro­
tained from interviews with respective industry and is provided in A-1. balance and 2400 II CHNS/O Elemental Analyzer-Perkin Elmer in CHNS
Either hardwood (HW) or a mixture of municipal organic waste and mode in triplicates. Blanks and k-factors were run to minimize errors
other agricultural residues were used as feedstock for the locally sourced before sample analysis. Samples (1.5 to 2.5) mg were rapidly combusted
biochar. In this research, this mixture is abbreviated as mixed feedstock in a pure oxygen environment to measure the resultant gases (Baldock
(MF). The exact proportion of the mixture could not be identified, but and Smernik, 2002; Hammes et al., 2006). The values for the atomic
the MF implies that it has more than one type of woody or grass biomass ratio of H:Corg and O:Corg were used to determine the carbon seques­
included. Biochar samples were named as L-MF1, L-MF2, L-MF3, L-MF4, tration values of biochar carbon (Enders et al., 2012).
L-MF5, L-HW1, L-HW2, L-HW3, and L-HW4. As there were nine different
locally sourced biochar, the numbers 1 to 5 at the end of the names 2.3.2. Proximate analysis and thermostable fraction
indicate biochar from a different source. The percentage of moisture, ash, and VM was analyzed using a TA
Q50 thermogravimetric analyzer following (ASTM-D7582-15, 2015)

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methods and FC was determined by difference. 2.3.5. Solid state DP MAS 13C NMR
The thermostable fraction (TSF) is defined as the ratio of FC to the The aromaticity of biochar samples was analyzed using direct po­
sum of VM and FC (Cely et al., 2015) and was calculated using Eq. (1). larization 13C nuclear magnetic resonance spectroscopy with magic
angle spinning (DP/MAS 13C NMR) (Singh et al., 2012). Oven-dried,
Fixed carbon
Thermostable fraction (TSF) (%) = *100 powdered sample < 0.5 mm was filled in a 7 mm diameter cylindrical
Volatile matter + Fixed carbon
zirconia rotor and analyzed with a 4 mm HXY probe, 12 kHz MAS. 300
(1)
scans were analyzed using the long relaxation delay of 50 s. Data anal­
The results from the proximate analysis were combined with the ysis and interpretation of the spectra thus obtained from the analysis
results of the O:Corg to determine biochar half-life (Klasson, 2017; were conducted using the Bruker top spin 3.5 software. The relative
Spokas, 2010). carbon content present in each biochar sample was calculated after
Fixed carbon content in a year (y) for biochar based on feedstock and correcting the values for the mass of biochar used. Similarly, the per­
application (Ccy,t) was calculated as the product of mass, a permanence centage of different types of carbon present in each biochar was calcu­
factor, and organic carbon from elemental analysis (VCS, 2021) using lated by normalizing the integral values to 100.
Eq. (2).
3. Results and discussion
CCy,t = My,t *Fcp *PRde (2)

My,t represents the mass of biochar type applied to the respective end 3.1. Biochar general characteristics
use in the year (y), assumed to be 1 t. A permanence factor PRde is
applied according to its H:Corg ratio. For H:Corg < 0.4 a permanence General characteristics such as pH, EC, surface area, pore size, and
factor is 0.74, and for H:Corg > 0.4, a permanence factor of 0.56 is pore volume are provided in (Adhikari et al., 2023). pH ranged from 7.6
applied. Organic carbon Fcp, is obtained from elemental analysis. to 11.1 and EC ranged from 0.08 to 6.3 ds/cm in different biochar
samples. Surface area of these biochar ranges from 1.1 to 373 m2/g and
2.3.3. Biochar oxidation resistance: thermal degradation showed contrasting pore size distribution. Biochar carbon content was
Biochar oxidation resistance was quantified using thermogravimetric analyzed as elemental carbon and fixed carbon. The elemental carbon of
analysis by calculating the recalcitrance index (R50), which is widely biochar was in the range 30 to 80 %, fixed carbon was in the range of 1 to
documented (Ahmad et al., 2019; Harvey et al., 2012; Saleem et al., 90 %. The complete data for elemental carbon is shown in Fig. 1 and
2022). Biochar was thermally treated from 20 to 900 ◦ C under an oxygen fixed carbon is provided in Appendix A2.
atmosphere at the heating rate of 20 ◦ C per minute using a thermogra­
vimetric analyzer. From the raw data of the thermograph, the value of 3.2. Biochar carbon stability analysis
R50 was calculated using Eq. (3).
T50,x 3.2.1. Elemental analysis
R50 , x = × 100% (3) SP-biochar had a carbon content of over 65 %, whereas AP-biochar
T50,graphite
showed a carbon content ranging from 30 to 80 % (Fig. 1). Results
where T50, x, and T50, graphite are temperature values corresponding to indicate that regardless of the pyrolysis method, biochar carbon content
the 50 % oxidation or volatilization of biochar material (x) and graphite, depends on feedstock type. Most of the SP-biochar is prepared with
respectively. mixed grass and woody biomass and hardwood, whereas AP-biochar
These values were obtained directly from a thermograph obtained includes feedstock such as sewage sludge and straw-based materials.
after thermogravimetric analysis of biochars and graphite that has been H:Corg ratio of the biochar samples is <0.7, except L-HW4 (0.71),
corrected for water and ash (Harvey et al., 2012). A detailed method for meaning that almost all biochar falls under the classification of the In­
the correction of water and ash for the thermograms is provided in A-2. ternational Biochar Initiative (IBI), European Biochar Certificate (EBC),
Additionally, carbon sequestration potential (Zhao et al., 2013) was and Australia New Zealand Biochar Industry Group (ANZBIG) biochar
calculated using Eq. (4). standard. The value of H:Corg, has been linked with the stability of the %
of carbon present in the biochar, where H:Corg ≤ 0.4 or less shows that
Carbon sequestration potential (CS) =
M*ch*Cch*R50
(4) 70 % of carbon in biochar is highly stable and is likely to remain in the
M*Cf soil for 100 years (Budai et al., 2013), which is discussed further in
Section 3.2.5.
where, M = mass of feedstock, ch = yield of biochar, Cch = carbon
content of biochar, R50 = recalcitrance index of biochar, Cf = carbon 3.2.2. Thermal degradation (R50)
content of the feedstock. The mass of feedstock and yield of commercial Biochar carbon recalcitrance (R50) indicates the stability of biochar
biochar and standard biochar were obtained from biochar producers and relative to a common standardization factor (graphite) (Xu et al., 2021;
the standard biochar specifications respectively. Values for the carbon Yang et al., 2016). Specifically, R50 provides an index of energy required
content of different feedstock were obtained from (Woolf et al., 2021) as to oxidize biochar relative to the energy required to oxidize graphite. It
51 % for HW, 49 % for SW, 49 % for MF (mixture of garden waste, fallen is classified as class A (R50 ≥ 0.70) most resistant to degradation, class B
trees, and wood waste), 49 % for WS, MS, and OSR, and 48 % for RH and (0.5 ≤ R50 ≤ 0.70) slightly degradable, and class C (R50 < 0.50) most
51 % for SS. degradable (Harvey et al., 2012).
Among 21 biochar samples, none of the biochar samples were in class
2.3.4. Fourier transform infrared spectroscopy (FTIR) A, 13 were in class B and 8 were in class C. Detailed thermal degradation
FTIR spectra were obtained using Bruker Vertex 70 FTIR spectrom­ curves are provided in A-2. RH700 and L-HW2 were the most resistant
eter. A pellet was prepared using 2 % biochar and 98 % potassium biochar among the 21 biochars studied with R50 (0.58) and SS550 was
bromide (KBr) and stored at 105 ◦ C before analysis. Spectra were taken the least resistant biochar R50 (0.44). Biochar prepared from MF showed
between 400 and 4000 cm− 1, using 4 cm− 1 resolutions with 64 scans at that they are slightly degradable, but still resistant to degradation with
nitrogen atmosphere, and analyzed with OPUS software in duplicates. R50 values in the range of 0.51 to 0.58. The R50 values increased with an
Before each run, the pellet was introduced to a nitrogen environment for increase in pyrolysis temperature from 550 ◦ C to 700 ◦ C for all biochar
10 min to reduce the inference of moisture (Singh et al., 2016). except RH and OSR. Results showed that WSP500 had an R50 value of
0.47 and WSP700 had an R50 value of 0.57. Similar values were reported
by other researchers (Saleem et al., 2022; Windeatt et al., 2014). Even

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Fig. 1. Carbon (C), oxygen (O), hydrogen (H), and nitrogen (N) of biochar content in simple and advanced pyrolysis biochar.

though the elemental carbon is influenced by feedstock primarily, the et al., 2017; Klasson, 2017; Leng et al., 2019; Wei et al., 2019).
resistance to thermal degradation is primarily influenced by pyrolysis
temperature, corresponding to the results of (Chen et al., 2021). The 3.2.3. Proximate analysis
increase in pyrolysis temperature increases the aromaticity of the bio­ The VM and FC of SP-biochar and AP-biochar were significantly
char making it more resistant to thermal degradation. HW and SW different from each other, indicating the influence of the production
biochar showed greater susceptibility to degradation, whereas MF bio­ process and feedstock (Fig. 2). Factoring in ash content, three distinct
char showed higher resistance to degradation. These results are similar groupings emerge in Fig. 2: 1) The biochars, with VM in the range of 50
to the findings of other researchers (Almutairi et al., 2022; Domingues to 85 %, FC below 50 %, and ash content below 30 %. 2) The majority of

Fig. 2. Ternary diagram showing volatile matter, fixed carbon, and ash content for biochar prepared from simple (SP) and advanced (AP) pyrolysis methods.

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the AP-biochars, with VM below 20 %, FC above 60 %, and ash content Results show that SP-biochar produced from MF has a higher CS of
below 30 %. 3) AP-biochars made from RH and SS, with VM <30 %, FC 15–30 % compared to AP-biochar with a CS of 10–20 %. These small
<50 %, and ash content in the range of 45–70 %. According to previous differences are likely due to the wide range of production methods and
research, >80 % VM indicates no carbon sequestration potential, and feedstock between biochar samples. For example, L-MF5 was prepared
<80 % indicates high to moderate carbon sequestration potential of at a small scale in a muffle furnace using mixed woody and grass biomass
biochar (Enders et al., 2012). This division is indicated in Fig. 2 by a like the L-MF4 feedstock, however, the CS and R50 are significantly
dashed line. By this metric, one AP and one SP-biochar would be different between them (Fig. 3). The CS and R50 of L-MF4 are 28.64 %
considered to have no carbon sequestration potential (L-HW4 & L-MF2). and 0.48 and L-MF5 is 22.37 % and 0.56 respectively. This difference
In contrast, another grouping of biochar can be observed for AP-biochars might have occurred due to differences in the species or composition of
SWP, MSP, WSP, and OSR at both temperatures showing high FC (<60 feedstock in each biochar and the biochar production type as L-MF5 was
%) and low ash content <40 %. This has been indicated by a second prepared using advanced pyrolysis and L-MF4 was prepared using
dashed line as this biochar shows higher carbon sequestration potential simple pyrolysis technology. In general, low-temperature biochar has a
compared to other biochar samples in the study. We could observe that high biochar yield and low recalcitrance value, whereas high-
the samples are grouped according to the feedstock type. However, the temperature biochar shows a lower biochar yield but a high recalci­
fact that inorganic mineral components in ash content, their CEC, ash trance value, thus affecting the CS (Zhao et al., 2013). In terms of
content, and expansibility of the mineral components effect the biochar feedstock, cellulose-rich and SS biochar showed lower CS of 17.1 % and
carbon stability (Jing et al., 2022) cannot be overlooked. Presence of 14.8 % respectively. In addition, HW and MF biochar are most resistant
mineral such as montmorillonite increased the loss of carbon, whereas to degradation, corresponding to results from previous studies (Wind­
the mineral such as kaolinite reduced the decomposition of biochar, due eatt et al., 2014; Zhao et al., 2013).
to the type of H-bond present in these minerals. Therefore, the difference
in ash content and its composition may be of interest for designing 3.2.5. Comparison of different carbon stability assessment methods
biochar for enhanced carbon stability. Combining data from elemental analysis and proximate analysis
provides further qualitative information about the stability of biochar
3.2.4. Carbon sequestration potential (CS) carbon. Many indices have been developed and recommended consid­
CS is defined as the final biochar carbon that will be retained in the ering the data from incubation and modeling for this stability prediction
soil. It is a derived index that is calculated as the carbon lost during the (Klasson, 2017; Leng et al., 2019; Spokas, 2010). Figs. 3 and 4 illustrate
pyrolysis process compared to the initial carbon in the biomass (Zhao how these different measures of carbon stability combine for the bio­
et al., 2013). CS of all 21 biochar samples ranged between 8 and 30 % chars tested.
(Fig. 3). We observed a moderate correlation between CS and R50 (r = Fig. 3 shows R50, TSF, and CS for each of the 21 biochars. While an
0.48, p = 0.028). Generally, biochars with low R50 values also have low overall positive correlation between R50 and CS is evident, visualizing
CS%, and high R50 values have high CS%. The only exception to this the data in this way highlights several inconsistencies between the TSF
trend was L-MF5, which had one of the highest CS values, but one of the and other measures of carbon stability. L-MF2 and L-HW4 were deemed
lowest R50 values. The change in other factors such as composition of to have no carbon sequestration potential based on VM results (Enders
feedstock species, their carbon content, the biochar carbon content, and et al., 2012). However, considering the yield and carbon content of the
the pyrolysis technique may cause variations in the results of CS and feedstock and biomass (Zhao et al., 2013), their carbon sequestration
R50. potential is estimated to be around 15 to 18 %. This percentage is similar

Fig. 3. Figure showing the relationship between the stability of biochar from simple pyrolysis (SP) and advanced pyrolysis (AP) with recalcitrance index, ther­
mostable fraction, and carbon sequestration potential. The size of the bubbles shows % of the thermostable fraction of each biochar. Class A, B and C represents
recalcitrance classes.

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S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

Fig. 4. Visualization of indices for half-life and carbon sequestration potential of biochar samples. Index 1: Half-life according to O:Corg (Spokas, 2010) and Index 2:
carbon sequestration potential according to H:Corg, O:Corg and volatile matter (Enders et al., 2012).

to most AP-biochar with a high TSF. free mass. Therefore, VM is also used as a method to evaluate biochar
Despite having a high CS and R50, SP-biochar has lower TSF carbon stability, and forms part of a different method to measure the
compared to AP-biochar (Fig. 3). All the SP-biochar, were in class B of half-life of biochar carbon in soil (Enders et al., 2012). This is shown as
the recalcitrance index, showing that they are slightly degradable. index 2 in Fig. 4. Index 2 is based on carbon stability assessment method
However, the CS and TSF of this biochar were different from each other. by (Enders et al., 2012) which proposed that VM > 80 % (w/w biochar
This indicates that biochar produced using a simple pyrolysis method ash-free mass) indicates biochars with no C sequestration potential, VM
has comparable structural stability to biochar produced from advanced < 80 % (w/w biochar ash-free mass); a moderate C sequestration po­
pyrolysis methods. It was observed even if some biochar fell in class C, tential is indicated by an O:Corg > 0.2 (Spokas, 2010) or H:Corg > 0.4 and
meaning having comparable carbon sequestration potential to unchar­ VM < 80 % (w/w biochar ash-free mass): and a high C sequestration
red biomass, the other matrix thermostable fraction indicates that class potential is indicated by an O:Corg < 0.2 or H:Corg < 0.4. Biochars
C biochar also has equivalent TSF compared to class B biochar with located closest to the origin of Fig. 4 (O:Corg < 0.2 and H:Corg < 0.4) can
intermediate carbon sequestration potential compared to graphite be considered to have a condensed structure as they have a higher
(Harvey et al., 2012). Biochar prepared from sewage sludge falls in class proportion of C. These biochar samples are deemed by Enders et al.'s
C of the recalcitrance index and has CS <10 %. However, the thermo­ method (Enders et al., 2012) to have the highest C sequestration po­
stable fraction is around 45 to 55 %. This indicates that biochar may tential, but only where VM < 80 % (smaller data points).
seem to be stable and have high carbon sequestration potential or By index 1, two of the biochars (L-HW1 and L-HW3) have a half-life
thermally stable fraction using one matrix, but the results vary while of >1000 years. However, although these biochars have a very long half-
another matrix is used. Therefore, only one method to evaluate the life, index 2 indicates a difference between the carbon stability of these
structural stability of biochar, which is fundamental to GHG emission biochars. L-HW1 is observed to have a low carbon sequestration po­
calculation and carbon credits, seems less reliable. To explore oppor­ tential compared to L-HW3. These differences can be attributed to the H:
tunities for reliability in carbon stability methods, we further combine Corg of the biochars. Sample L-HW1 has H:Corg = 0.4, whereas sample L-
two additional indices. Index 1 is the half-life, this index is widely HW-3 has H:Corg = 0.16. Similarly, additional certainty of carbon sta­
accepted to evaluate the half-life of the biochar (Budai et al., 2013; bility is provided to the biochar samples with a half-life 100–1000 years
Spokas, 2010), using O:Corg. Index 2 is the measure of carbon seques­ by using index 2 where even if the half-life is 100–1000 years, the car­
tration ability/potential by combining H:Corg, O:Corg, and volatile mat­ bon sequestration potential may be low or negligible depending on the
ter (Enders et al., 2012). H:Corg or VM present in the biochar. All the biochar falling in the third
According to index 1, if the O:Corg is <0.2, then the biochar half-life section of Fig. 4, (<100 years) half-life, indicated a low carbon
may be considered >1000 years. If O:Corg 0.2 to 0.6 biochar may be sequestration potential.
considered as having a half-life of 100–1000 years, and O:Corg > 0.6 may All the SP-biochars and AP-biochars (excluding LHW4, SS550, and
be considered as having a half-life <100 years (Spokas, 2010). While the WSP550,) had H:Corg ratio of <0.4, implying 70 % of the carbon in these
molar ratios of H:Corg and O:Corg is used for biochar stability analysis, biochars is likely to remain in the soil for approximately 100 years,
both ratios are reported to be correlated to the VM content per unit ash- according to (Budai et al., 2013). However, in the case of LHW4, SS550,

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S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

and WSP550 only 50 % of the carbon present is estimated to remain for 3.2.6. Surface functional groups
approximately 100 years when applied to the soil (Fig. 4). Biochar The identification of the presence and intensity of carbon functional
samples such as L-HW1, L-MF1, SWP700, and WSP550 had H:Corg, be­ groups at different regions by FTIR in biochar agrees with the other
tween 0.39 and 0.41. These can be defined as having borderline H:Corg if measures of carbon stability. All the biochar samples showed peaks
used for calculations in carbon sequestration for carbon credit purposes. characteristic of aromatic compounds around 1595–1630 cm− 1 for
This type of biochar may be receiving false credits or missing out on C––C, and 1690–1710 cm− 1 for carboxylic-C, and ketones and esters
credits due to the standard cut-off of H:Corg at 0.4. Therefore, additional C––O (Cheng et al., 2006). However, the intensity of these peaks
methods are required to validate the carbon structural stability of these changed with biochar feedstock, temperature, and production methods
biochar. All four biochars tend to have low carbon sequestration po­ (Fig. 5). SP-biochar, prepared at ≤550 ◦ C, with MF showed multiple and
tential according to the index of (Enders et al., 2012), however, the sharp peaks at this wavelength. However, among the AP-biochar only
difference in VM in these four biochars can be seen in Fig. 4. L-MF1 and OSR550 and WSP550 showed sharp peaks in this region. The peaks were
L-HW1 have volatile matter content of 66 % and 70 % respectively, reduced in number and intensity with the increase in pyrolysis tem­
whereas SWP700 and WSP550 have volatile matter of 6.66 % and 10.55 perature from 550 ◦ C to 700 ◦ C. Single feedstock cellulosic biochars such
% respectively. The presence of VM in the biochar will certainly change as RH, SS, MSP, and SWP showed peaks of smaller intensity in the ar­
its structural stability. Therefore, there is a clear need to enhance con­ omatic region compared to all other biochars. This is supported by the
fidence in the assessment of carbon structural stability. fact that RH550, RH700, SS550, and SS700 have a half-life of <100
The half-life of biochar does not show any trend with production years. FTIR spectra of this biochar also indicate that there is a lower
type, however, can be feedstock-specific. Three of the SP-biochar and number of small peaks at the aromatic carbon region. The peaks were in
eight AP-biochar showed a half-life of 100–1000 years, whereas two SP- similar intensity in the aliphatic and fingerprint regions (Nandiyanto
biochar and eight AP-biochar show a half-life of <100 years. As shown et al., 2019) at 600–1500 cm− 1 for all biochar. The presence of metal
in Fig. 4, the majority of biochars meeting these criteria are derived from oxides M-O, C–O, C–H, and Si-O-Si was observed in this region for
hardwood or mixed feedstock rather than single feedstocks. Biochars almost all biochar, excluding L-MF1. The spectrum of SP-biochar, L-MF1
RH550, RH700, L-MF5, L-HW4, SS550, and SS700 have a lower pro­ is also different from other SP-biochar, which may be due to its post-
portion of C (less condensed) and correspondingly have a shorter C half- processing with some minerals during commercial production.
life in soil (despite having lower proportions of VM). Our results show L-HW1 and L-MF3 showed sharp peaks with high intensity at the
that the carbon structural stability depends on both pyrolysis tempera­ aromatic region and have shown a half-life of 100–1000 years. This
ture and feedstock. The standard biochar samples from UKBRC showed indicates a higher degree of aromaticity in these biochars and their as­
that an increase in pyrolysis temperature decreases the H:Corg for most sociation with lignin and cellulosic feedstock material coming from MF.
of the biochar samples, indicating increased C stability. However, SWP L-HW3 has a half-life of 100–1000 years, however, the FTIR spectra
showed an opposite pattern, where an increase in pyrolysis temperature show strong broad peaks in the aromatic and aliphatic region, indicating
increased the H:Corg from 0.38 for SWP550 to 0.40 for SWP700 which a higher degree of oxidation in the biochar. Abundance of surface
may have occurred due to subtle variations in elemental composition of functional groups may be an indication of higher change of oxidation
the feedstock. and decreased carbon stability; however, the aromatic functional groups
Carbon stability of naturally carbonized organic matter such as coal in particular indicate the stability of biochar carbon (He et al., 2021).
could be a useful analog for evaluating products from modern pyrolysis Our results show that FTIR analysis can be used as a method for carbon
techniques. The carbon structure of coal that is formed by high tem­ stability assessment in terms of surface functionality. However, to
peratures and pressures in underground environments that exclude ox­ represent a complete and comprehensive idea of stability of biochar in
ygen is subsequently stable for millions of years (i.e. Permian or Jurassic soil, other soil and environmental factors should be considered (Schmidt
age) (Petersen et al., 2023). The refractory index (R0), a common coal et al., 2011).
assay technique, can also be used to compare carbon stability in biochar
made from agricultural waste. A combination of carbon stability in­ 3.2.7. Solid state DP MAS 13C NMR
dicators, including R0, was thus used to evaluate biochar (Petersen et al., From NMR analysis, different carbon types were referenced to the
2023), with 97 % of the organic carbon considered long-term stability chemical shift as Alkyls (HCOH, CH2/CH, and CH3) 0–50 ppm, Ether/
with a mean R0 of around 4.55 %. They also reported that the carbon alcohol 50–70 ppm, Nitro-Alkyne groups 65–90 ppm, Aromatic alkene,
stability (increase in aromaticity and reflectance) of biochar was influ­ and nitrile groups 100–160 ppm, Aldehyde 185–210 ppm and Ketone
enced by both pyrolysis temperature and feedstock, consistent with the 200–220 ppm (Mao et al., 2012). Relative total carbon and percentage of
results of our study. The long-term stability of carbonized organic matter specific types of carbon present in each biochar in five categories after
where the microbial process is active (e.g., biochar in moist shallow soil) normalizing the value for 100 % are shown in Table 1. The NMR spec­
must also be considered. trum of all biochar samples is provided in A-3. All the biochar samples
As illustrated in Figs. 3 and 4, using different indices for carbon showed the presence of >80 % aromatic carbon in them. Relative to
stability provides contrasting and often inconsistent information about SS550, all other groups of biochar had high carbon content. L-HW1, L-
the stability of the same biochar. As alluded to by several carbon sta­ MF1, WSP550, and MSP550 had the highest relative carbon content. The
bility measures, at the core of carbon stability is the C-bonding envi­ aromaticity of the biochar carbon is related to higher thermal stability,
ronment of biochar. The degree of aromaticity and ring condensation are determining its thermal oxidation resistance (Xu et al., 2021). This is
considered to be key in the resistance of biochar to environmental also related to the surface area of the biochar as higher surface area
degradation (Schmidt et al., 2022), this aromaticity may also be influ­ indicates availability of space for oxidation process in the biochar sur­
enced by the choice of feedstock and production parameters (Enders face. However, in depth understanding and correlations are yet to be
et al., 2012; Singh et al., 2012). It is important to identify the fraction of identified.
carbon in biochar that is aromatic as the aromaticity of biochar is The SP-biochar has a high aromatic carbon content compared to AP-
strongly correlated to its stability (McBeath and Smernik, 2009; biochar. RH biochar showed the lowest % of aromatic carbon content 76
McBeath et al., 2014; McBeath et al., 2011). Therefore, molecular-level % and no carboxylic, amide, or ester groups. The triple bonded carbon
analyses, such as FTIR and NMR that provide information about the C such as aldehyde and ketone were only present when pyrolyzed at
bonding environment, can be used to assist in the interpretation of the 700 ◦ C. Alkyl carbon % was greater in cellulosic biochar such as RH550,
carbon bonding in the biochar. OSR550, and MSP550. However, no peaks were observed in this region
for L-HW2, L-HW3, SWP550, L-MF4, WSP700, OSR700, and SS700. This
indicates the influence of pyrolysis temperature and decomposition of

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S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

Fig. 5. FTIR spectra of 21 different biochar samples from contrasting feedstock produced using different pyrolysis methods.

Table 1
13
Total carbon and concentration of different carbon types in reference to the chemical shift from C DP NMR in biochar produced from different feedstock and
production conditions. Total carbon is calculated relative to the carbon signal from SS550 (*).
Pyrolysis Sample Relative 13C NMR carbon 0–50 50–70 65–90 100–160 160–180 185–210 200–220 Total
(%) ppm ppm ppm ppm ppm ppm ppm (%)

Simple L-MF1 288 5.05 – – 88.98 – – 5.97 100

Simple L-MF2 134 3.17 – – – 92.11 – 4.72 100
Simple L-MF4 128 – 1.55 5.32 82.9 – 1.34 8.9 100
Simple L-HW2 141 – 1.92 8.24 80.71 – 1.07 8.07 100
Simple L-HW3 162 – – 3.17 95.76 – – 1.07 100
Advanced L-HW1 398 7.72 0.51 0.65 80.59 1.46 1.26 7.81 100
Advanced L-HW4 160 0.68 0.04 1.06 94.1 – – 4.12 100
Advanced L-MF3 251 3.04 – – 91.46 5.2 – 0.3 100
Advanced L-MF5 213 3.40 1.2 5.24 90.16 – – – 100
Advanced SWP550 195 – – 5.33 87.92 – – 6.75 100
Advanced SWP700 166 0.73 0.12 0.49 96.1 – – 2.56 100
Advanced WSP550 269 1.49 – 2.03 89.56 – – 6.92 100
Advanced WSP700 182 – – 6.04 87.44 – – 6.53 100
Advanced RH550 193 6.47 5 11.79 76.74 – – – 100
Advanced RH700 99 – 0.57 6.6 79.77 – 1.21 11.85 100
Advanced MSP550 364 4.38 – – 87.37 3 – 5.25 100
Advanced MSP700 193 0.45 – 1.04 95.12 1.94 – 1.45 100
Advanced OSR550 250 3.18 – 0.18 86.96 7.96 – 1.72 100
Advanced OSR700 143 – 0.63 8.22 82.82 – – 8.33 100
Advanced SS550 96* 2.39 – 6.51 88.52 2.59 – – 100
Advanced SS700 151 – – 6.74 86.71 – – 6.55 100

alkyl carbon after an increase in temperature from 550 ◦ C to 700 ◦ C. SP- chloride. Peaks in the region 185–210 ppm were only observed for L-
biochar L-HW2 and L-MF4 also showed the presence of hemicellulose HW1, L-HW2, L-MF4, and RH700 indicating thermal degradation of
from the MF, which can be seen in low % in the AP-biochars except cellulose present in the feedstock and producing aldehydes. Peaks were
RH550. This is indicated by the presence of peaks between 50 and 70 present in the region of 200–220 ppm, indicating the presence of ketones
ppm. L-MF2 showed a high amount of carboxylic acid, as a strong peak in the biochar except L-MF5, RH550, and SS550. This indicates that the
was observed between 160 and 180 ppm. 92 % of carbon was associated biochar has been through longer residence times where larger organic
with this group. It may have occurred as L-MF2 biochar was mixed with molecules break down into smaller compounds.
fertilizers after production which may have influenced the carbon type.
In addition, only six other biochars showed the presence of carboxylic 3.3. Combining different measures of carbon stability
acid, amide, ester, and acyl chloride indicating the cleavage of C–C
bonds from the larger organic molecules along with reactions between We compared the stability of 21 biochar samples using accepted,
the previous functional groups and others such as amines, and thionyl additional, derived, and qualitative methods (Table 2). The complete

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S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

Table 2
Biochar carbon stability of different biochar samples using available carbon stability methods. Ccy,t
= fixed carbon remaining in the soil in year y and time t, TSF = thermostable fraction (%), t (1/2) =
half-life (years), R50 = recalcitrance class, CS = carbon sequestration potential (%), FTIR = abun­
dance of C peaks in FTIR spectrum, NMR C = aromatic carbon (%). Color dark green, light green,
and orange correspond to the highest, medium, and lowest carbon stability.

Accepted Additional Derived index Qualitative

Pyrolysis Sample H:Corga Ccy, tb O:Corg t 1/2 TSF CS R50 FTIR NMR
Simple L-MF1

Simple L-MF2
Simple L-MF4

Simple L-HW2

Simple L-HW3

Advanced L-HW1

Advanced L-HW4

Advanced L-MF3

Advanced L-MF5

Advanced SWP550

Advanced SWP700

Advanced WSP550

Advanced WSP700

Advanced RH550

Advanced RH700

Advanced MSP550

Advanced MSP700

Advanced OSR550

Advanced OSR700

Advanced SS550

Advanced SS700

a
Accepted by standards such as IBI, EBC and ANZBIG.
b
Accepted by Verra method for utilisation of biochar for soil and non-soil applications.

dataset and additional details are provided in A-4. removal. These uncertainties show the need for the addition of recent
Our results confirm that biochar can generally store carbon in a incubation and modeling data to revise the current index of carbon
stable and durable form and has implications for carbon credits. The stability assessment.
comparison of methods shown in Table 2, with current accepted analysis It was observed that there is a negative correlation between O:Corg
methods (H:Corg and Ccy,t) provide confidence in carbon durability for and VM (r = − 0.47, p = 0.031). Similarly, O:Corg ratio, half-life pre­
implication to carbon credits. H:Corg is the widely used and accepted dicted from the results of O:Corg, (Spokas, 2010) and recalcitrance po­
method for the analysis of biochar carbon stability. However, the ratio tential (R50) was observed to be significantly correlated to Ccy,t with
differentiating high and low carbon stability is fixed at 0.4 and 0.7. This correlation coefficients of (r = 0.965, p < 0.001), (r = 0.77, p < 0.001)
shows a broad approach to defining limits and is a conservative and (r = 0.48, p = 0.027) respectively. The R50 values were found to be
approach. Based on H:Corg and other factors (mass of biochar used in a correlated to carbon sequestration potential CS (r = 0.48, p = 0.028).
year, organic carbon content), the metric Ccy,t is used by Verra (VCS, The number of aromatic peaks obtained from FTIR showed a positive
2021) to provide carbon credit opportunities to the biochar producers correlation with the half-life predicted from O:Corg.
and users. However, an implication of this method is that some biochars The highly stable biochar L-MF4, L-HW2, L-HW1, SWP550, and
close to the defined H:Corg thresholds, such as L-MF1 (H:Corg = 0.39), L- RH550 were also shown to have high stability according to CS and R50.
HW1 (H:Corg = 0.4), SWP700 (H:Corg = 0.4), WSP550 = (H:Corg = 0.41) Similarly, less stable biochar L-HW4, WSP550, and SS550 were also
may miss out on carbon credits, or qualify for questionable carbon indicated to have low C stability by CS and R50. Some exceptions to this
credits, if not blended to create mixed biochars. However, if the biochar consistency in results from H:Corg and R50 were L-MF5, MSP550,
samples L-MF5, SWP700, WSP700, RH550, RH700, MSP700, SS550 and OSR550, and OSR700, which may have been due to the high O:Corg.
SS700 used the combination of methods (Ccy,t, CS and R50), then 25 % Results including relative carbon content from 13C NMR spectra, and
more carbon credits would be calculated compared to what it would biochar half-life appear to be consistent. Higher relative aromatic car­
have received if only Ccy,t was used. The 25 % difference is determined bon content in NMR analysis indicated a longer half-life of biochar
as the cut off for the permanence adjustment factor for calculation of carbon, and vice versa with some exceptions L-MF5 and OSR550. Even
Ccy,t is 0.56 and 0.74 for H:Corg values >0.4 and <0.4 respectively. though a correlation between results from NMR and biochar half-life is
Therefore, including R50, and CS as additional tests in scenarios where observed, NMR is relatively high cost and requires technical expertise
H:Corg ranges from 0.35 to 0.45 can be effective in improving confidence which may not be readily available to biochar producers and users.
in carbon credits to biochar producers and users. Soil carbon seques­ However, CS and R50 are derived from existing and available methods
tration, stability, and credits are major drivers for the industry to scale without additional costs and can be recommended to improve the reli­
up biochar production and use. Therefore, questionable, or missing ability of biochar stability assessment.
credits because of incomplete analysis or methodology limitations may Due to the contrasting feedstock and production parameters of bio­
produce uncertain results and reduce confidence in biochar for carbon char, use of statistical analysis methods such as correlation test were

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S. Adhikari et al. Science of the Total Environment 914 (2024) 169607

only appropriate for this study. In this research there were five samples Acknowledgments
representing variations in the SP-biochar category. Following up on this
study, more evidence can be built for contrasting samples. This may This research was funded by Deakin University with a DUPRS
include meta-analysis using contrasting biochar types and their carbon Scholarship. The authors are thankful to the Institute of Frontier Mate­
stability to build up high confidence in the result validation process. rials, Deakin University, and RMIT University for access to laboratory
facilities. The authors would like to thank the anonymous reviewers for
4. Conclusion their constructive feedback in this article.

We assessed the stability of carbon structure, persistence, and Appendices. Supplementary data
oxidation resistance of 21 different biochar samples, focusing on the
structural stability of biochar carbon. A range of instrumental methods Supplementary data to this article can be found online at https://doi.
and derived indices were compared for the stability assessment, how­ org/10.1016/j.scitotenv.2023.169607.
ever, the full carbon sequestration after soil application was not
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