Journal of Environmental Management 250 (2019) 109464

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Journal of Environmental Management

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Short communication

Determination of chemical oxygen demand of agricultural wastes by T

combining acid hydrolysis and commercial COD kit analysis
G. Cazaudehorea, B. Schraauwersa, C. Peyrelassea, C. Lagneta, F. Monlaua,∗
a
APESA Pôle Valorisation, Cap Ecologia, Avenue Joliot Curie, 64230 Lescar, France

ARTICLE INFO

Keywords: Chemical oxygen demand (COD) is an essential parameter in waste management, particularly for monitoring
Chemical oxygen demand bioprocess such as anaerobic digestion. Indeed, chemical oxygen demand (COD) is a key parameter that can
Acid hydrolysis prove useful for the evaluation of waste biodegradability and to evaluate mass and energetic balances of the
Solid wastes overall process. In this study, an adapted method to determine the COD of solid agricultural wastes was de-
Biodegradability
veloped. This method combined a double acid hydrolysis of the solid waste materials followed by commercial
Anaerobic digestion
COD tubes analysis. This method was compared to direct sampling after a standard dilution (3.5 g TS.L−1) and
analysis in commercial COD tubes. The method developed in this study allowed the COD of nine agricultural
wastes to be accurately predicted, with an absolute error of 7% compared to the theoretical COD. In comparison,
the method with only a prior water dilution resulted in higher absolute errors of 36% and 31% when sampling
was performed with pipette tips and cut pipette tips, respectively.

1. Introduction 2017). Nonetheless, development of this sector must also be accom-

Currently, the world is facing many challenges to answer to the
growing human population (Nizami et al., 2017). As a consequence
several environmental issues are resulting such as greenhouses gases
emissions and huge wastes generation of various origin (i.e animal,
agricultural, industrial, municipal wastes). If these wastes are disposed
without treatment, they may contribute to environmental hazards and
for this purposes several wastes treatment technologies are emerging
such as thermochemical and biological ones (Rao and Rathod, 2018;
Carrere et al., 2016).
Anaerobic Digestion (AD) which is a biological process by which
organic matter is transformed in the absence of oxygen into biogas (a
mixture of carbon dioxide and methane) is a promising technology for
treating organic wastes. The biogas that is produced can be valorized as
biomethane after epuration or converted into heat and electricity
through a Cogeneration Heat and Power (CHP) system (Angelidaki
et al., 2018). AD technology has, therefore, attracted these last decades
interest among the agricultural sector and the number of agricultural
biogas plants has been increasing throughout Europe (Carrere et al.,
2016; Dinuccio et al., 2010). These last decades, several studies have
investigated the anaerobic digestion for treating agricultural wastes and
demonstrated that AD process can be part of waste biorefineries
(Brémond et al., 2018; Castellano-Hinojosa et al., 2018; Paudel et al.,
panied by the establishment of indicators that allow the monitoring of
AD performances (André et al., 2016).
In this regard, chemical oxygen demand (COD) is a parameter that
could be useful for evaluation of waste biodegradability and also for
evaluating the mass or the energetic balance of the process. The COD
value provides relevant information about the efficiency of the AD
process (André et al., 2016; Harnadek et al., 2018). COD is defined as
the amount of oxygen required to oxidize an organic compound to
carbon dioxide, ammonia, and water, and it is used as one of the main
water quality parameters in wastewater treatment facilities. Initially,
the APHA–AWWA–WPCF method for COD determination was mostly
used for water and wastewater samples and it appeared to be unsuitable
for samples that have a high percentage of suspended solids (> 15% of
total solids) due to heterogeneity in the composition of solid substrates
(Raposo et al., 2008; Yadvika et al., 2006). In light of the recent interest
in the exploitation of agricultural by-products as a source of energy
through anaerobic digestion, and use of the COD as a widely balanced
unit in anaerobic reactors, reliable measurement of COD in solid sub-
strates has become a very important parameter for consideration
(Raposo et al., 2009). Reliable measurement of the COD of solid wastes
has, therefore, become an area of interest to many research groups and
laboratories involved in the characterization of organic matter (Raposo
et al., 2009; Yadvika et al., 2006). Nonetheless, most of the studies to

∗
Corresponding author.
E-mail address: florian.monlau@apesa.fr (F. Monlau).

https://doi.org/10.1016/j.jenvman.2019.109464
Received 22 February 2019; Received in revised form 25 July 2019; Accepted 22 August 2019
0301-4797/ © 2019 Elsevier Ltd. All rights reserved.
G. Cazaudehore, et al. Journal of Environmental Management 250 (2019) 109464

Abbreviations

Theoretical COD (mg COD.g−1 VS)

AD Anaerobic Digestion
CHP Cogeneration Heat and Power System
COD Chemical Oxygen Demand
RSD Relative Standard Deviation
TS Total Solids

( ± 18)
( ± 20)
( ± 44)
( ± 30)
( ± 58)
( ± 31)
( ± 56)
( ± 58)
( ± 23)
VS Volatile Solids

1522
1297
1225
1400
1330
1428
1515
1396
1238
date have used a standard titrimetric method and few of them have
sought to develop an adapted protocol for the evaluation of the COD by

CxHyOz (%VS)
commercial kits that are preferred by laboratories as they minimize the

( ± 0.2)
( ± 0.1)
( ± 0.4)
( ± 0.2)
( ± 0.3)
( ± 0.1)
( ± 0.4)
( ± 0.4)
( ± 0.3)
use of chemical reagents and they reduce the time involved (André
et al., 2016; Buffiere et al., 2006; Charnier et al., 2016). Among the

97.4
98.9
99.0
98.0
98.4
96.1
95.8
97.9
99.2
adapted protocols for COD commercial kits analysis, suspension of
freeze-dried ground samples in distilled water (Buffiere et al., 2006)
and more recently suspension of freeze-dried ground samples in sulfuric
acid (98% in mass) (Charnier et al., 2016) have been proposed. In

O (%TS) calculateda
parallel, André et al. (2016) have also proposed the use of a home-made
plastic weighing support to transfer directly the solid sample into COD

( ± 0.5)
( ± 0.5)
( ± 0.9)
( ± 0.5)
( ± 1.7)
( ± 0.6)
( ± 1.3)
( ± 1.6)
( ± 0.7)
tubes without a prior dilution. Nonetheless, most of these studies have
compared their experimental COD results with theoretical COD values

37.4
45.4
45.0
38.5
40.1
35.4
31.6
37.9
45.6
only on reference substrates (starch, glucose, KHphthalate, cellulose).
Up to date, a lack of data is available in literature on the comparison of
such methods with the theoretical COD of real solid substrates used in
AD process. According previous investigations from literature data, the

11.9 ( ± 0.1)
11.7 ( ± 1.2)
18.3 ( ± 0.2)
23.5 ( ± 0.8)
14.7 ( ± 1.1)
9.1 ( ± 0.3)
2.8 ( ± 0.1)
5.7 ( ± 0.0)

4.3 ( ± 0.0)
Ash (%TS)
main objectives of this research were:

• to develop an adapted method (Method 1) for determination of the

COD of solid samples by acid hydrolysis (Sluiter et al., 2008) fol-
lowed by COD analysis using commercial kits (Spectroquant®,
Merck, Germany).
( ± 0.0)
( ± 0.0)
( ± 0.1)
( ± 0.2)
( ± 0.1)
( ± 0.0)
( ± 0.0)
( ± 0.0)
( ± 0.0)
• to compare this method with two other ones that investigate sus-
S (%TS)

pension of solid substrates in distilled water. The liquid supernatant

0.2
0.1
0.2
0.3
0.3
0.7
0.5
0.3
0.2
was then sampled with a pipette (Method 2) or a pipette for which
the tip had been cut (Method 3) prior to COD kits analysis.
•
Elemental composition of the nine agricultural wastes and estimation of the theoretical COD.

to compare the results obtained with the theoretical oxygen demand

2.2 ( ± 0.1)

0.7 ( ± 0.2)
1.5 ( ± 0.0)
1.1 ( ± 0.2)
2.5 ( ± 0.0)
2.7 ( ± 0.2)
1.5 ( ± 0.3)
0.6 ( ± 0.3)

values evaluated on the basis of elemental analysis of the solid

1 ( ± 0.1)
N (%TS)

substrates.

2. Materials and methods

( ± 0.0)
( ± 0.1)
( ± 0.3)
( ± 0.2)
( ± 0.1)
( ± 0.1)
( ± 0.1)
( ± 0.1)
( ± 0.0)

2.1. Sample origin and preparation

H (%TS)

Nine agricultural samples (i.e., manure, straw, and silage) were

6.1
6.4
5.6
5.6
5.5
5.4
5.1
5.8
5.8

collected from various farm biogas plants in France (Table 1). The
samples were oven-dried at 65 °C until they reached a constant weight
and then milled using a centrifugal milling device (Retsch ZM 200,
( ± 0.0)
( ± 0.2)
( ± 0.2)
( ± 0.0)
( ± 0.2)
( ± 0.2)
( ± 0.2)
( ± 0.2)
( ± 0.3)

Haan, Germany) to a particle size of less than 1 mm. Total solids (TS),
C (%TS)

Volatile solids (VS), and ash content were determined in duplicate in

45.1
44.4
42.8
42.3
41.2
37.7
36.6
39.7
43.5

accordance to APHA standard methods (APHA, 2005). Cellulose (Sigma

Determined by O = 100–C–H–N–S–Ash.

Cell type 20, Sigma-Aldrich, USA) and Cellobiose powder (> 98%,
Sigma-Aldrich, USA) were used as control material.
( ± 0.9)
( ± 0.5)
( ± 0.6)
( ± 0.8)
( ± 1.3)
( ± 1.1)
( ± 0.3)
( ± 2.6)
( ± 0.2)

2.2. Protocol for determination of the COD of solid wastes

VS (%TS)

90.9
97.2
94.3
88.1
88.3
81.7
76.5
85,3
95,7

The COD was determined according to the three protocols detailed

below:
Method 1 (Fig. 1): Agricultural biomasses and control material
Chicken manure

were hydrolyzed according to a protocol adapted from the National

Sugar Sorghum
Turkey manure
Mix of silages

Cow manure

Renewable Energy Laboratory (Sluiter et al., 2008). Briefly, 80 mg of

Maize straw
Grass Silage
Substrates

Sorghum

samples were placed in 35 mL Pyrex glass tubes. Then, 0.85 mL of

Table 1

Grass

H2SO4 (72%) was added to each tube and the tubes were heated to
a

30 °C for 1 h under magnetic agitation (300 rpm). Finally, 23.8 mL of

2
G. Cazaudehore, et al.
Fig. 1. Pictures of devices used with the methodology developed in this study for estimation of the COD of agricultural wastes.
distilled water was added and the tubes were heated to 121 °C for 1 h.
After cooling, the supernatant liquids were analyzed for COD using
commercial kits (Spectroquant 14,155, Merck, Germany). The con-
centrations ranged from 500 to 10,000 mg COD.L−1. All of the analyses
were performed as quadruplicates for each sample. Briefly, 1 mL ali-
quots of supernatant liquids were placed in the commercial tubes. The
tubes were then heated to 148 °C in a preheated thermoreactor for
120 min. Finally, the COD was measured by an automatic spectro-
photometer (Photolab S6, WTW, Germany).
Method 2: Agricultural biomasses were diluted in distilled water at
a solid loading of 3.5 g TS.L-1. Each mixture was agitated manually and
the supernatant liquid was then sampled with a pipette for COD ana-
lysis as previously described. All of the analyses were performed in
quadruplicates for each of the samples.
Method 3: Agricultural biomasses were diluted in distilled water at
a solid loading of 3.5 g TS.L-1. Each mixture was agitated manually and,
before COD analysis, the supernatant liquid was sampled with a pipette
for which the tip had previously been cut (0.3 cm) to prevent clogging
by large-sized particles. All of the analyses were performed in quad-
ruplicates for each of the samples.
2.3. Theoretical COD
For all the samples (oven-dried and ground), the Carbon, Hydrogen,
Nitrogen, and Sulfur contents were determined using an elemental
analyzer (Elementar Vario Macro cube). Analyses were performed in
duplicate on 1.5 mg TS. The theoretical COD was determined using
equation (1) below (Wei et al., 2018):
4x + y 2z
CODt = 8 × g (COD ). g 1 (CxHyOz )
12x + y + 16z Equation 1
where x, y and z represent the amount of carbon, hydrogen and oxygen,
respectively.
2.4. Statistical analysis
Statistical analysis of the data was carried out on R. Normality and
variance homogeneity were verified using Shapiro and Bartlett test,
respectively. Anova and TukeyHSD test were performed to identify the
differences between the different methods used and compare them with
theoretical values, the confidence level considered was 95%.
3
Journal of Environmental Management 250 (2019) 109464
3. Results and discussion
3.1. Chemical composition of the nine agricultural wastes
The elemental compositions of the nine agricultural substrates that
were tested are presented in Table 1. The Volatile Solids content ranged
from 76.5% TS (for turkey manure) to 97.2% TS (for maize straw),
which is in agreement with previous investigations (Monlau et al.,
2012; Sambusiti et al., 2013). Ash content ranged from 2.8% TS (maize
straw) to 23.5% TS (turkey manures). The carbon content ranged from
36.6% TS (turkey manure) to 45.1% TS (grass silage). The nitrogen
content ranged from 0.6% TS (sugar sorghum) to 2.7% TS (turkey
manure), which is in agreement with the study by Monlau et al. (2012).
Finally, the highest content of S was found in manures with values
ranging from 0.5% TS to 0.7% TS. These elemental composition values
(for C, H, N, S, and O) are in accordance with previous publications
(Rambo et al., 2015; Raposo et al., 2009). Indeed, Rambo et al. (2015)
reported that the values for ten lignocellulosic substrates ranged from
38% to 48% for carbon and from 0.3% to 2.9% for nitrogen. Similarly,
in an inter-laboratory study of COD estimation, Raposo et al. (2009)
reported similar values for C, H, N, and S for the two solid wastes that
were investigated (i.e., Quinoa and sunflower oil cakes).
3.2. COD analysis using the various methods
Firstly, the theoretical COD values of the nine agricultural wastes
investigated were estimated on the basis of the elemental composition.
The theoretical values for the COD ranged from 1225 mg COD.g−1 VS
(mix of silage) to 1522 mg COD.g−1 VS (grass silage) (Table 2). Simi-
larly, Raposo et al. (2009) reported theoretical COD values that were
estimated based on the elemental composition of 1327 and 1345 mg
COD.g−1 TS for sunflower oil cake and quinoa samples, respectively.
Raposo et al. (2008) estimated that the theoretical COD can be con-
sidered as the assigned reference value (estimation of the true value of
the measurand).
In Fig. 2, the absolute errors of the theoretical COD values are re-
presented for the nine samples and the three methodologies in-
vestigated. It can be seen that Method 2 (sample dilution and sampling
with a pipette) and the Method 3 (sample dilution and sampling with a
pipette cut at the tip) were not particularly suitable for determination of
the COD. Indeed, COD estimation by methods 2 and 3 were significantly
G. Cazaudehore, et al. Journal of Environmental Management 250 (2019) 109464

Table 2
Comparison of the values of the theoretical COD and the experimental COD determined by the three methods.
Substrates Theoretical COD (mg COD.g−1 Mean COD by method 1 (mg COD.g−1 Mean COD by method 2 (mg COD.g−1 Mean COD by method 3 (mg COD.g−1
VS) VS) VS) VS)

Grass silage 1522 ( ± 18) 1416 ( ± 68) 798 ( ± 47) 956 ( ± 76)
Maize straw 1297 ( ± 20) 1264 ( ± 43) 1058 ( ± 94) 1067 ( ± 68)
Mix of silages 1225 ( ± 44) 1315 ( ± 62) 746 ( ± 148) 926 ( ± 91)
Sorghum 1400 ( ± 30) 1363 ( ± 104) 756 ( ± 39) 896 ( ± 202)
Cow manure 1330 ( ± 58) 1333 ( ± 132) 857 ( ± 93) 1099 ( ± 152)
Chicken manure 1428 ( ± 31) 1396 ( ± 97) 912 ( ± 82) 937 ( ± 220)
Turkey manure 1515 ( ± 56) 1452 ( ± 121) 930 ( ± 176) 1094 ( ± 157)
Grass 1396 ( ± 58) 1343 ( ± 82) 730 ( ± 38) 705 ( ± 64)
Sugar sorghum 1238 ( ± 23) 1301 ( ± 29) 803 ( ± 53) 885 ( ± 129)

different from the theoretical value for 8 of the 9 samples (TukeyHSD
test, p < 0.05). The only sample that was not significantly different
from the theoretical value was the cow manure COD estimated by the
method 3 (TukeyHSD test, p = 0.098). The mean absolute errors for the
samples using Method 2 and Method 3 were determined to be 39% and
31%, respectively. For Method 3, in which the pipette was cut to pre-
vent plugging by large-sized particles, the COD determination was
better than Method 2, but not significantly. However, as shown in
Table 2, the results remain unsatisfactory. These results are partially in
agreement with the interlaboratory study by Raposo et al. (2009) in-
volving COD estimation of quinoa solid substrates using commercial kit
brands (Hach and Merck) with an average recovery of 69%. Among four
laboratories using protocols similar to Method 2 and Method 3, two
reported unsatisfactory results that showed that such methodologies are
questionable.
Method 1 developed in this study, which consisted of a double acid
hydrolysis followed by COD analysis using commercial kits significantly
improved the results, as shown in Table 2 and Fig. 2. Indeed, no sig-
nificant difference could be measured between theoretical COD and
COD by method 1 (TukeyHSD test p > 0.05). The mean of the absolute
error ranged from 4% to 7% with a reliable repeatability of the measure
( ± 1–5%). The double acid hydrolysis adapted from Sluiter et al.
(2008) allowed for hydrolysis of cellulose and hemicelluloses, thereby
resulting in an improvement of the homogeneity of the solid wastes
during the sampling. The validity of the acid hydrolysis method was
verified on cellulose and cellobiose powders, for which the recovery
yields reached 103% ( ± 0.7%) and 100% ( ± 1.2%) of the theoretical
COD. These results were deemed to be satisfactory and they highlight
that such a methodology can be applied for the estimation of COD of
solid wastes that allows monitoring of AD performances by an accurate
mass balance based on the chemical oxygen demand (COD) entering
and exiting the system.
Several studies had investigated the development of new protocols
(André et al., 2016) or the upgrading of existing methodologies for
assessment of the COD of solid wastes (Noguerol-Arias et al., 2012;
Yadvika et al., 2006; Raposo et al., 2008). Noguero-Arias et al. (2012)
and Raposo et al. (2008) had developed two different titrimetric
methods adapted to COD determination of solid samples. These two
methods reported high accuracy and precision. Noguero-Arias et al.
(2012) had reported an accuracy of 1.9% and a precision of 1.4% (RSD)
measured on two certified reference material. While Raposo et al.
(2008) had reported an accuracy of 2% and a precision of 0.3% (RSD)
measure on five substrates (potassium hydrogen phthalate, cellulose
powder, sunflower oil cake, anaerobic sludge and certified reference
material sludge). Quite similar results were obtained by the method
developed here, with an accuracy of 1.9% and a precision of 0.7%
(RSD), measured on cellulose and cellobiose powders. The method
presented here has the additional advantage over the methods de-
scribed in Noguero-Arias et al. (2012) and Raposo et al. (2008) to use
commercial kits that most laboratories prefer to use in order to mini-
mize costs and chemical disposal.
Nonetheless, few studies to date have proposed an adapted protocol
for evaluation of the COD of solid wastes using the commercial kits.
Among these, André et al. (2017) have developed a COD determination
protocol using a homemade plastic weighing support to transfer the
solid sample into the apparatus of the commercial COD kits. Although

Fig. 2. Absolute error for the experimental COD determined according to the three methods compared to the theoretical COD.

4
G. Cazaudehore, et al.
few solid wastes were investigated, satisfactory and promising results
were obtained, with recovery yields of 93% ( ± 7%) and 95% ( ± 8%)
for glucose and cellulose, respectively. Charnier et al. (2016) reported
value of 94% and 104% of the theoretical one from cellobiose and
starch respectively by an adapted protocol coupling sulfuric acid hy-
drolysis of substrates followed by COD kits analysis. Similar recovery
yields and repeatability were obtained in this study with 100%
( ± 1.2%) and 103% ( ± 0.7%) for cellulose and cellobiose, respec-
tively.
3.3. Time and cost analysis of the methodology
As our results demonstrated that the method developed in this study
can be used to accurately determine the COD of various agricultural
wastes, information on the operating time and cost is also provided. In
regard to the operating time, the main procedures comprise the
weighing (5 min per sample), the double acid hydrolysis (5 min per
sample), the tube cleaning (5 min per sample), and the analysis using
COD kits (5 min per sample), which amount to approximately 20 min of
labor per sample. It is important to note that, in our experience, per-
forming tests on multiple samples at the same time reduces the overall
work time. In regard to the material investment to replicate the ex-
periment in the laboratory, the following items are required: Pyrex
glass tubes; a magnetic stirrer/heater; and a support for the glass tubes
that can resist high temperatures. As balances with accuracies of 10−4 g
are common in most laboratories, this cost has not been added in the
cost estimation. Similarly, the chemical reagent (H2SO4 72%) was not
taken into account due to the small amount required (0.85 mL per
sample, corresponding to 21c€ per sample). The cost of commercially
available kits was not included either, but this amounts to approxi-
mately 5€/kit. The investment cost for a test station of ten samples is
presented in Table 3. The total cost varies from 1050€ to 1850€ (data
from our laboratory's experience), which is reasonable and affordable
for most existing laboratories.
Table 3
Total investment required to apply the Method 1 developed in this
study.
Items Costa (in €)
Ten Pyrex glass tubes 50 €
A magnetic stirrer/heater 500-800 €
A support for the glass tubes 500-1000 €
Total investment cost (€) 1050–1850 €
a components of biomass residues for biorefinery opportunities. Talanta 144, 696–703.
Cost are based on our own experience but also from prices of
classical providers (VWR®, Fisher Scientific®, Legallais® …).
4. Conclusions
The adapted method for determination of the COD of solid samples
investigated in this study was found to be successful. For the entire
sample set that was tested, an absolute error of the experimental COD of
7% was noted compared to the theoretical COD. Compared to existing
protocols for COD analysis of solid substrates, such a method offers the
possibility of being able to relatively accurately assess the COD of
agricultural solid wastes using commercial kits that minimize the ana-
lysis time and that reduce the cost of the analysis by reducing chemical
reagent used. Future work will investigate the optimization of opera-
tional parameters (i.e duration of acid hydrolysis, and solid loading of
sample) along with measurement of the quantity of the initial sample
with a more accurate weighing scale. Furthermore, the application of
the methodology developed in this study will be investigated to other
Journal of Environmental Management 250 (2019) 109464
substrates like digestate, compost and algae samples.
Acknowledgments
Authors are grateful to the financial support of ADEME through the
SPIRALE project. We wish also to thank the Nouvelle Aquitaine region
(France) for its financial support through the FEDER program.
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