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Bioresource Technology 176 (2015) 233–241

Contents lists available at ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Early prediction of Biochemical Methane Potential through statistical


and kinetic modelling of initial gas production
Sten Strömberg a,⇑, Mihaela Nistor b, Jing Liu a,b
a
Department of Biotechnology, Lund University, Getingevägen 60, 221 00 Lund, Sweden
b
Bioprocess Control AB, Scheelevägen 22, 223 63 Lund, Sweden

h i g h l i g h t s

 BMP can be predicted at a much earlier stage into a test.


 BMP data from 138 samples divided into five groups are presented.
 61 different prediction algorithms are evaluated for best performance.
 Linear regression of previous test results are important for accurate predictions.

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

Article history: A major drawback of Biochemical Methane Potential (BMP) tests is their long test duration, which could
Received 29 September 2014 be reduced substantially if the final gas production could be predicted at an earlier stage. For this pur-
Received in revised form 6 November 2014 pose, this study evaluates 61 different algorithms for their capability to predict the final BMP and
Accepted 8 November 2014
required degradation time based on data from 138 BMP tests of various substrate types. By combining
Available online 15 November 2014
the best algorithms it was possible to predict the BMP with a relative root mean squared error (rRMSE)
of less than 10% just 6 days after initiation of the experiment. The results from this study indicate that
Keywords:
there is a possibility to shorten the test length substantially by combining laboratory tests and intelligent
Anaerobic digestion
Biochemical Methane Potential
prediction algorithms. Shorter test duration may widen the possible applications for BMP tests in full-
Biogas scale biogas plants, allowing for a better selection and proper pricing of biomass.
Kinetic model Ó 2014 Elsevier Ltd. All rights reserved.
Predicting BMP

1. Introduction conditions (Angelidaki et al., 2009). The BMP test provides infor-
mation on the extent of the process and decomposition rate of a
With an increasing demand for efficient waste handling and material for biogas production, which are valuable parameters in
fossil fuel replacement, anaerobic digestion has gained a lot of the design and operation of a biogas plant (Chynoweth et al.,
attention in the recent time. In Europe, the biogas production has 1993; Lesteur et al., 2010; Moody et al., 2009; Raposo et al., 2011).
increased substantially in the last few years with a rise from One major drawback with conventional BMP tests is their long
3.8 Mtoe in 2003 to 12.0 Mtoe in 2012 (EurObserv’ER, 2005, duration. Often 30–60 and sometimes up to 100 days are necessary
2013). The growing interest for production of biogas by anaerobic to obtain the required results, which means that there is an exten-
digestion has led to an increased demand for finding and evaluat- sive delay before actions can be taken (Lesteur et al., 2011; Ponsá
ing new types of suitable feedstock. et al., 2011). Consequently, the tests are mainly used for pre-stud-
A method to source and determine the feasibility of a material ies, mandatory degradation tests or various scientific applications.
to serve as a substrate in anaerobic digestion is represented by However, if results could be obtained faster, BMP tests would likely
the Biochemical Methane Potential (BMP) test. Such a test moni- be of interest for industrial biogas producers as well, as this would
tors the gas production following the incubation of an organic allow them to use the test for quality checks and pricing of
material with an anaerobic bacteria mixture under well-controlled substrates.
Previously suggested approaches to obtain quick BMP results
are the use of empirical relationships based on the material’s
⇑ Corresponding author. Tel.: +46 222 81 93; fax: +46 222 47 13.
chemical and biochemical composition (Thomsen et al., 2014) or
E-mail addresses: sten.stromberg@biotek.lu.se (S. Strömberg), mn@bioprocess-
control.com (M. Nistor), jing.liu@biotek.lu.se (J. Liu).
respirometric activity (Scaglia et al., 2010) as well as methods

http://dx.doi.org/10.1016/j.biortech.2014.11.033
0960-8524/Ó 2014 Elsevier Ltd. All rights reserved.
234 S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241

using Near-Infrared Spectroscopy (NIRS) (Doublet et al., 2013). A cellulose, starch, gelatine), household waste (e.g. fruit and vegetable
more general overview of each technique can be found in the waste, milk waste, meat waste, co-digestion mixtures), agricultural
review article by Lesteur et al. (2010). These approaches show waste (e.g. wheat straw, bamboo waste, banana stem), sewage
great potential as they allow immediate results within reasonable sludge (e.g. primary and secondary sludge, co-digestion mixtures)
error margins. However, as their predictions are based on time and lipid rich waste (e.g. butter waste, oil waste). The majority of
independent measurements, these techniques do not offer any the BMP tests were performed using inoculum collected from a
information regarding the kinetic degradation of the material. sewage treatment plant (Ellinge sewage plant, Sweden), which
Moreover, the absence of a biological anaerobic degradation pro- receives municipal wastewater and vegetable residues from the
cess, limits the information about the toxicity and loading rate of food industry and operates at mesophilic temperatures.
the substrate. Sodium hydroxide (reagent grade 97%, Sigma–Aldrich) and thy-
An alternative method to obtain quick BMP results, with the molphthalein pH indicator (dye content 95%, Sigma–Aldrich) were
kinetic and biological degradability information included, is the used for the preparation of 3 M alkaline solution for CO2 fixation.
combination of conventional BMP tests and numerical prediction N2 gas (Air Liquid Gas AB, Sweden) was used to obtain anaerobic
models. Promising results in this regard have been achieved by conditions during the sample preparation phase.
Ponsá et al. (2011), observing strong linear correlations between
the biogas production at different times in a test and the final value
2.3. Experimental procedure
for different types of organic fraction of municipal solid wastes
(OFMSW). This suggests that, given a big enough database, it is
The biodegradability of the samples was determined using BMP
possible to statistically predict the final BMP of a sample.
assays as described in Strömberg et al. (2014b). The majority of the
It is commonly known that well-controlled batch degradations
tests were performed at 37 °C with an inoculum to substrate ratio
follow certain kinetic patterns that can be modelled using suitable
of 2 based on volatile solids (VS) amount. An active volume of
kinetic models. For complex materials, limited by hydrolytic degra-
400 ml in 500 ml bottles was used in all tests and mixing was per-
dation of particulate matter, a first order rate equation is generally
formed mechanically, either intermittently or continuously. Blanks
used to describe the degradation profile (Shahriari et al., 2012).
containing only inoculum were included in every test and used to
Several other model types have also been proposed as more accu-
deduct the background gas production from the inoculum. No
rate alternatives for different types of substrates (Beuvink and
external nutrients or trace elements were added to the reactors
Kogut, 1993; Koch and Drewes, 2014; Rincón et al., 2010). This sug-
before starting the BMP tests. All data was sampled with 10 mL
gests that, given a reliable set of initial data and an accurate kinetic
resolution and converted to hourly basis (i.e. one data point per
model, it is possible to predict the remaining methane potential for
hour). The BMP (adjusted to 0 °C, 1 atm and dry condition) was cal-
many different types of materials. As this approach includes the
culated by subtracting the gas production of the inoculum from the
biochemical aspects of anaerobic digestion, key information about
gas production of the sample and dividing it by the amount of VS
the material’s toxicity and loading strain on the microbial popula-
added.
tion is also obtained. The recent development of specialised labora-
tory equipment, such as Automatic Methane Potential Test System
(AMPTS) II, which allows automatic and reliable gas measurements 2.4. Numerical and statistical details
with high resolution, makes an approach based on real-time pre-
diction with mathematical models highly feasible. 2.4.1. Data structure
The current study evaluates 61 different algorithms for their In total 380 sample datasets from 138 individual samples,
ability to predict the BMP of various substrate types. Special spread over six groups, were included in the study. The samples
emphasis is directed towards finding the most suitable model in each sample group were further randomly divided into a calibra-
and the time required to produce estimations within an acceptable tion and a validation set containing 67% and 33% of the samples,
error range. respectively. This procedure was repeated five times so that the
samples were represented in both the calibration and validation
set several times. All results presented in this study are based on
2. Methods the average of these five validation sets.

2.1. Equipment
2.4.2. Statistical parameters
The Automatic Methane Potential Test System II (AMPTS II, Three statistical parameters (i.e. relative root mean squared
Bioprocess Control Sweden AB) was used for the BMP analysis of error of prediction (rRMSE), relative absolute error (rAE) and the
the target substrates. The AMPTS II is a standardised laboratory coefficient of determination (R2)) were calculated according to
set-up specially designed for automatic BMP determination of Eqs. (1)–(3):
any biodegradable material. The gas is measured through water qP
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi2ffi
^i Þ
ðyi y
displacement using pre-calibrated flow cells that give a signal for n
each 10 mL of produced gas. Temperature and pressure sensors rRMSE ¼ ð1Þ

y
are used to normalise the gas volume to 0 °C, 1 atm and dry gas
conditions at each measurement point. P jyi y^i j
yi
rAE ¼ ð2Þ
2.2. Materials n

P
The BMP was investigated for 138 individual samples divided ^ i Þ2
ðy  y
R2 ¼ 1  P i ð3Þ
into six different groups. In order to describe the experimental var-  Þ2
ðyi  y
iation in a BMP test each replicate (in most cases triplicates) of a
sample was included in the study, making a total of 380 investi- ^i are the experimental and predicted values,
In Eqs. (1)–(3), yi and y
gated datasets. The studied sample groups were anaerobic sludge respectively, for sample i, n is the number of samples and y  is the
(i.e. effluent from anaerobic digesters), standard compounds (e.g. mean of the experimental values.
S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241 235

2.4.3. Prediction target kinetic prediction acts on the dynamic profile of the gas production
The objective of the prediction algorithm was to estimate the to fine-tune this estimation. As the predictions are continuously
final BMP and time to reach this state. For standardisation pur- updated for each new measurement, the accuracy is naturally
poses, the final BMP was expressed as BMP1%, which corresponds increasing as the test progress.
to the value obtained the first day when the average daily produc-
tion is less than 1% of the total/accumulated BMP (VDI 4630, 2006). 3.1. Statistical prediction
This criterion is necessary as it allows for a standardised way of
expressing final BMP and necessary test time, which otherwise The statistical prediction estimates the BMP1% and test time by
can be a rather subjective procedure where the reported BMP value cross-referencing the registered BMP profile of the target sample
and, especially, the test duration depends on how long time the with the corresponding profiles of the samples in a database. By
process is left to run. utilising similarities in the dynamic profile from previous tests, a
It was expected that the model predictions would improve with reasonable estimation of the target sample’s BMP profile is
the experiment time as more data is available and the process is assumed to be achievable. The database consists of data from pre-
closer to the end. Thus, to cope with this fact, the prediction perfor- viously performed BMP tests and is further organised according to
mance was evaluated by measuring the time necessary to reach the sample groups presented in Section 2.2.
two criteria: (i) one based on the time necessary to reach less than For predictions of BMP1% the database samples are used to make
10% in rRMSE and (ii) one based on the time necessary to reach an a linear regression, passing through origin, between the produced
R2 higher than 0.9. The criterion for rRMSE was seen as the most BMP during the last half of the test (i.e. BMP(t)  BMP(0.5t);
important one as it describes the actual error between experimen- t = last recorded experimental time of the on-going test) and the
tal and predicted values. The R2 criterion was included as it indi- BMP1%. To remove deviating samples, only 10% of the database
cates how well the algorithm describes the variation in the data. samples, based on the smallest rRMSE vs. the target sample, are
used in the regression analysis. In similar fashion, the test time is
2.4.4. Numerical calculations predicted by making a linear regression between the time points
All calculations were performed with MatlabÒ where functions when each database sample reach the same relative daily BMP pro-
nlncon and fmincon were used for fitting model parameters for sin- duction as the target sample and their total test times.
gle- and multi-variable problems, respectively.
3.2. Kinetic prediction
3. Prediction model theory
The kinetic prediction is performed by minimising the differ-
In this section all evaluated aspects of the prediction algorithm ence between the output from a kinetic model and the gas profile
are described in detail. In order to have a better understanding of of the target sample. The idea is to utilise the fact that most degra-
the prediction process, the BMP profiles of three different sub- dation profiles are determined by a rate-limiting step, which can
strates are presented in Fig. 1 together with the predicted profiles be described by rather simple models. However, as this might
based on the data collected during the first 3 days of the test. not always be the case, two aspects of the kinetic prediction pro-
All evaluated prediction algorithms in this study estimate the cess were investigated in order to find the most favourable option:
final BMP and required test time of a target sample according to (i) kinetic model, different types of kinetic models to cover the var-
the following two-step approach: (i) statistical prediction, first a ious types of degradation profiles and (ii) data management, differ-
statistical method is used to estimate a preliminary BMP value ent options for managing the gas production data.
based on a regression analysis of the registered methane produc-
tion from the on-going test and corresponding test data from a 3.2.1. Kinetic models
database; (ii) kinetic prediction, the preliminary estimated BMP In total six different kinetic models (M1–M6) were evaluated for
value is in a second step used as boundary condition for a simple their accuracy to predict the BMP1% and test time based on the
kinetic model that predicts the remaining part of the degradation dynamical gas profile: M1 – a first order rate model (Eq. (4)), M2
based on non-linear fitting of the registered methane production – a first order rate model with variable order of time dependency
data up until that time point. In general terms, the statistical pre- (Eq. (5)), M3 – a combination of two first order rate models (Eq.
diction ensures that a reasonable estimation is provided while the (6)), M4 – a Monod type model (Eq. (7)), M5 – a quadratic Monod

1000 Household waste Agricultural waste Lipid rich waste


Experimental data Predicted data

800
BMP (Nml/gVS)

600

400

200

0
0 5 10 15 20 25
Time (days)

Fig. 1. Accumulated specific methane production for three different samples (i.e. mixed food waste as a household waste, banana stem as an agricultural waste, and butter
residues as a lipid rich waste). The experimental data is represented by the solid line, while the predicted gas profile is showed by the striped line.
236 S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241

type model (Eq. (8)) and M6 – a modified Gompertz model (Eq. 3.3. Evaluation of the prediction algorithms
(9)):
Three factorial design experiments were used to evaluate the
M1 : BMPðtÞ ¼ BMP1  ð1  expðk1  tÞÞ ð4Þ
impact of the individual model aspect (i.e. kinetic model type, data
management and omission of either the statistical or kinetic pre-
M2 : BMPðtÞ ¼ BMP1  ð1  expðk1  t c ÞÞ ð5Þ diction step). This served as an initial scanning process to identify
which model aspects had a positive respectively negative impact as
M3 : BMPðtÞ well as to learn more about its role in the prediction process. For
¼ BMP1  ð1  X  expðk1  tÞ  ð1  XÞ  expðk2  tÞÞ ð6Þ each investigated aspect, an effect (E) was calculated as the aver-
age difference of a response parameter with and without the model
  aspect included in the prediction algorithm (Eqs. (10)–(12)). The
k1  t
M4 : BMPðtÞ ¼ BMP1  ð7Þ response parameter (Y) was set as the mean value (n = 6) of the
1 þ k1  t
average rRMSE for the predicted BMP1% at 1–2, 3–5, 6–9, 10–15
  and 16–30 days after initiation of the experiment.
t2
M5 : BMPðtÞ ¼ BMP1  ð8Þ Using all possible combinations of a kinetic model, data man-
t 2 þ k1  t þ k2 agement strategy and active or inactive kinetic and statistical pre-
diction step generated a total of 61 possible combinations for the
M6 : BMPðtÞ prediction algorithm, see Table 1.
 
h1  expðk1  tÞ h2  expðk2  tÞ The effects for the three investigated factorial designs were cal-
¼ BMP1  exp   ð9Þ culated according to Eqs. (10)–(12) with the distribution: (i) com-
k1 k2
paring the performance of the prediction with or without the
In Eqs. (4)–(9), BMP1 is the ultimate BMP (NmL/gVS), BMP (t) is the statistical prediction step (Eq. (10)), (ii) comparing the six kinetic
BMP value at time t (day), k1 and k2 (1/day) are rate constants, c (–) models (Eq. (11)) and (iii) comparing the five different variants of
is the order of the time dependence, X (–) is the fraction of readily data management (Eq. (12)).
degradable material and h1 and h2 (1/day) describe the lag period !
for the modified Gompertz model. 1 X X X X
EDB ¼   Y i;j;DB  Y i;j;0 ð10Þ
30 i¼M1:M6 j¼D1:D5 i¼M1:M6 j¼D1:D5
3.2.2. Data management
As the kinetic models predictions often varies depending on !
1 X X X
which part of the gas profile is included in the fitting process, three EM1 ¼  5 Y M1;j;DB  Y i;j;DB ;
25
different alternatives for data selection were evaluated: all – utilis- j¼D1:D5 i¼M2:M6 j¼D1:D5
!
ing all registered data, half – utilising the last half of the registered 1 X X X
data and variable – a variable approach that selects the fraction of EM2 ¼   5 Y M2;j;DB  Y i;j;DB ; . . . ð11Þ
25 j¼D1:D5 i¼M1;M3:M6 j¼D1:D5
data giving the most accurate prediction of the last recorded gas
production. By only utilising data from the later part of the test it !
is possible to avoid negative influence from lag phases and also 1 X X X
ED1 ¼  4 Y i;D1;DB  Y i;j;DB ;
have the model calibrated on the most recent kinetic trend, which, 24 i¼M1:M6 i¼M1:M6 j¼D2:D5
in many cases, should serve to better describe the remaining gas !
1 X X X
production. ED2 ¼  4 Y i;D2;DB  Y i;j;DB ; . . . ð12Þ
The variable procedure is initiated by dividing all registered 24 i¼M1:M6 i¼M1:M6 j¼D1;D3:D5
data into ten different datasets, each including 10% of the data.
The kinetic model is then calibrated with the second last dataset In Eqs. (10)–(12), EDB (%) is the effect for the statistical predic-
and evaluated on how well it predicts the last one (having the most tion step using a database, EM1 and EM2 are the effects for kinetic
recent registered data). This is then compared with the predictions models M1 and M2, ED1 and ED2 are the effects for data manage-
based on data from both the second and third last dataset. If this ment method D1 and D2, Yi,j,DB and Yi,j,0 are the response parame-
expansion of the calibration data improves the prediction, based ters with (DB) and without (0) the statistical prediction step for
on the rRMSE, an additional model calibration is performed involv- kinetic model i and data management method j, see Table 1. For
ing three datasets. This cyclic procedure is repeated until either the Eqs. (11) and (12), an effect is calculated for each kinetic model
expansion of the calibration data leads to a worse fit or all datasets (i.e. M1–M6) and data management strategy (i.e. D1–D5), respec-
are utilised. Finally, the datasets for calibration are combined with tively, by rotating i and j so that the evaluated segment is always
the validation data (last data set) and used to predict the remain- subtracted by all the other segments.
ing, unknown, data.
The kinetic models were also investigated using two different 4. Results and discussion
initial points (i.e. time point when t = 0): original – time zero is
the experimental start time and shifted – time zero is the first data 4.1. Sample characterisation
point used for calibrating the model. A shifted initial point is
included as it makes it possible to utilise the initial dynamic prop- The distribution of BMP1% and degradation time for the different
erties of the model (i.e. model output for small values of t) also at a sample groups are presented with box plots in Fig. 2. As seen,
later stage in the process. anaerobic sludge has the lowest BMP values whereas the lipid rich
In total five combinations of data management strategies were waste has the highest ones. Most variation is observed for house-
investigated: D1 – utilising all registered data with the original hold waste, making it the most representable group for this study.
starting point, D2 – utilising half of the data with the original start- In comparison, the low variation and number of samples for agri-
ing point, D3 – utilising half of the data with a shifted starting cultural waste and lipid rich waste suggests that these sample
point, D4 – utilising the variable data selection approach with groups are less significant for the study. It should be pointed out
the original starting point and D5 – utilising the variable data that even though some points are shown as outliers they are still
selection approach with a shifted starting point. included in the study.
S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241 237

Table 1
Overview of all evaluated combinations of model aspects for the prediction algorithm.

Statistical prediction Kinetic prediction Indicator No.


Status Status Kinetic model Data handling
Active Active 6 5 DB 30
Active Inactive – – 1
Inactive Active 6 5 0 30
Indicator M1–M6 D1–D5 Total 61

BMP1% 891.3 27.6 Test time 16.2


1000 460.9 (52.1) 40 (4.8) 30.7 (8.5)
(146.7) 27.2 (2.4)
(3.3)
12.1
800 361.3 10.1 (4.4)
(199.8) 30 (3.9)
BMP1% (Nml/gVS)

Test time (days)


12.6
600 (4.1)
360.7 353.1
(26.8) (63.2) 20
224.1
400 (41.4)

73.2 10
200 (21.7)

0 0

Fig. 2. Box plots showing the distribution of BMP1% and necessary degradation time to reach BMP1% for the six investigated sample groups and all samples combined. The
central line corresponds to the median of the group, the top and bottom represents the 75th and 25th percentile, the top and bottom whisker corresponds to the 1.5 times the
difference between the 75th and 25th percentile and, finally, the black dots represents the outliers placed outside of these percentiles. Average values and standard deviations
(in parenthesis) for each sample group are given above each box.

With regard to the test duration, the spread of the data is (Koch and Drewes, 2014). The poor performance of the modified
greater in comparison to the BMP, with many groups having Gompertz model is somewhat surprising as this model was previ-
around 5 days between the 25th and 75th percentiles. A distinct ously found to be the most accurate kinetic model in describing the
separation is observed between anaerobic sludge, agricultural degradation kinetics of a large set of samples (Strömberg et al.,
waste and the lipid rich waste, requiring 20–30 days to reach 2014a). Clearly, there are different requirements for fitting a
BMP1%, and the standard compounds, household waste and sewage kinetic model to a full dynamic BMP profile compared to predicting
sludge, which mostly require 10–15 days to reach the same level of the same profile based on an initial fraction of the same data.
biodegradation. With regard to data management, the factorial design results
reveal that a variable approach with a shifted initial point (D5) is
4.2. Evaluation of the prediction algorithms the best alternative for predicting the BMP of the majority of the
substrate groups. Moreover, using half of the data with a shifted
The results from the factorial design experiments are presented initial point (D3) also provides good results, indicating that a mod-
in Fig. 3 where higher positive values correspond to more accurate ified starting point is the most important feature for good predic-
predictions of BMP1%. As seen by the relatively large positive bars tions. Including all data (D1) has a clear negative effect on the
in the bottom left graph, including the statistical prediction step performance, suggesting that large parts of the early obtained data
generally gives more accurate BMP1% predictions compared to compromise the prediction accuracy.
not including it. Only lipid rich waste samples are negatively As the factorial design is a method that combines the sum of
impacted with this step activated. Thus, the linear regression based several combinations, the results might not reflect the truly best
on the information in the BMP database is important for the perfor- options for prediction of BMP. This approach should more appro-
mance of the prediction algorithm. priately be used to acquire a general idea on how the individual
A significant difference in the performance of the investigated options influence the performance of the prediction. The most
kinetic models is observed, with the Monod type (M4), quadratic successful prediction algorithm combinations are instead better
Monod type (M5) and first order with variable time dependency represented by the lowest value of the response parameter (Y),
(M2) generally giving positive effects on predictions of BMP1% which is presented in Table 2.
while the first order (M1), two combined first order (M3) and the As seen in Table 2, the statistical prediction step is included for
modified Gompertz (M6) have a negative impact. The three more all samples groups except lipid rich waste, once again demonstrat-
successful models allow for a slower decline in gas production in ing the importance of this step for accurate predictions. This is
the later parts of the degradation process, which is beneficial for further strengthened by the fact that the kinetic prediction step is
samples with high contents of slow degradable complex materials inactivated in the best performing prediction algorithm for
238 S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241

Anaerobic sludge Standard compounds Household waste


Agricultural waste Sewage slduge Lipid rich waste

3
Kinetic models

1
Effect (%)

-1

-2

-3 M1 M2 M3 M4 M5 M6
First order First order First order Monod type Monod type Modified
variable time two combined quadratic Gompertz
dependency

Statistical
prediction Data management
6 3

4 2
Effect (%)

2 1
Effect (%)

0 0

-2 -1

-4 -2

-6 DB -3
Statistical prediction D1 D2 D3 D4 D5
All Half Half Variable Variable
Original Shifted Original Shifted

Fig. 3. Calculated effects from factorial design experiments evaluating the six different kinetic models (top graph), impact of the statistical prediction step (bottom left graph)
and the five different ways of managing the gas production data (bottom right graph).

Table 2
Best settings for predictions of BMP1% for each sample group based on the response parameter Y, described in Section 3.3.

Sample group Statistical prediction Kinetic model Data management Y (%)


Anaerobic sludge Yes – – 9.9
Standard compounds Yes First order variable time dep. (M2) Variable – shifted (D5) 5.8
Household waste Yes Quadratic Monod type (M5) Variable – shifted (D5) 10.4
Agricultural waste Yes – – 13.5
Sewage sludge Yes – – 4.1
Lipid rich waste No Quadratic Monod type (M5) Half – shifted (D3) 6.3

anaerobic sludge, agricultural waste and sewage sludge. These find- the initiation of the BMP test vs. the expected BMP1% are presented
ings are quite interesting as they imply that reasonable predictions in Fig. 4. As is clear from the figure, the model predictions improve
could be obtained with only the statistical prediction step activated, significantly as the experiment progresses. After 1 day, the predic-
which would reduce the computational power demand signifi- tions are rather widely spread, especially for household waste, and
cantly. In fact, the response parameter values (Y) with only the cannot be regarded as accurate. However, already 5 days into the
statistical prediction step activated for standard compounds, house- experiment the predictions are considerably better, shown by the
hold waste and lipid rich waste are 5.9%, 12.0% and 12.7%, respec- more uniform distribution of data points along the line. Letting
tively. Thus, with exception for lipid rich waste, the statistical the test run for 10 days assures rather accurate predictions of
prediction step performs rather well as a standalone step in the pre- BMP1% for most samples with the exception of lipid rich waste.
diction algorithm. As the lipid rich waste group is the smallest In fact, the predictions of lipid rich waste are rather inaccurate
(n = 6) sample group, a better performance by the statistical predic- even with 15 days of experimental data and thus, as the predic-
tion step is expected if more BMP test data are added to the group. tions are not improved with time, it can be concluded that the
prediction algorithm is not performing well for this sample group.

4.3. Assessment of the prediction accuracy


4.3.2. Overall performance
4.3.1. Experimental results vs. predictions The overall rRMSE, rAE and R2 for the prediction of BMP1% and
By utilising the best prediction algorithm versions, as given in test time are plotted against the duration of a test in Fig. 5. As
Table 2, the predicted BMP1% values after 1, 5, 10 and 15 days from expected, the predictions of both parameters improve with time,
S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241 239

Anaerobic sludge Standard compunds Household waste


Agricultural waste Sewage sludge Lipid rich waste

1200 1200
Day 1 Day 5
1000 1000
Predicted BMP1% (Nml/gVS)

Predicted BMP1% (Nml/gVS)


800 800

600 600

400 400

200 200

0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Experimental BMP1% (Nml/gVS) Experimental BMP1% (Nml/gVS)

1200 1200
Day 10 Day 15
1000 1000
Predicted BMP1% (Nml/gVS)

Predicted BMP1% (Nml/gVS)

800 800

600 600

400 400

200 200

0 0
0 200 400 600 800 1000 1200 0 200 400 600 800 1000 1200
Experimental BMP1% (Nml/gVS) Experimental BMP1% (Nml/gVS)

Fig. 4. Predicted vs. experimental BMP1% for the six studied sample groups at 1, 5, 10 and 15 days from the initiation of the BMP test.

as shown by the decreasing errors and increasing coefficient of 1 day is required for the lipid rich waste, whereas 8 days are nec-
determination along the time axis. With regard to BMP1%, the essary for the agricultural waste. Most interestingly, the predic-
R2 > 0.9 criterion is fulfilled already 3 days after starting the test tions of the most variable group (i.e. household waste) require
whereas reaching rRMSE < 10% demands about 6 days. This shows only 6 days to reach both criteria, demonstrating that the tech-
that the prediction of BMP1% is rather successful on an overall level. nique works for sample groups with high variation in data. It also
However, with regard to predictions of the test time, the two crite- suggests that a large number of samples are important for good
ria are met much later into the test (i.e. 18 days for R2 > 0.9 and prediction accuracy.
25 days for rRMSE < 10%) suggesting that this parameter cannot The obtained results show that it is possible to predict the BMP
be predicted accurately enough, at least not within a reasonable at an earlier stage into the test. However, as the study is performed
time. One of the major reasons for this is that the predicted test under very limited conditions, with mainly one type inoculum and
time is very dependent on the kinetic parameters and fairly small process temperature, it should primarily be regarded as a proof of
errors in their values will propagate to large effects on the pre- principle and not something widely applicable. In order to have a
dicted test time. Another factor that makes the prediction of the full understanding of the process, much more test data, investigat-
test time difficult is the fact that only a small deviation in the mea- ing more conditions, are certainly necessary.
sured gas production might be sufficient to reduce the flow rate
enough to meet the BMP1% criterion and, as a consequence, reach 4.4. Comparison with literature data
it earlier than expected. As rate constants are known to vary quite
heavily between different samples and test conditions, accurate A summary of the results from previous studies related to pre-
predictions of the experiment time, based on kinetic models, have diction of the BMP of an organic material is presented in Table 4. As
to be considered a great challenge. seen, most studies with higher rRMSE have lower R2 compared to
In Table 3, the time necessary to reach both the R2 > 0.9 and the criteria used in this study. In fact, almost all reported values
rRMSE < 10% criteria for each sample group is presented. As seen, are reached by the prediction algorithm after 6 days or less. The
the results vary considerably depending on the type of sample only exception is the prediction accuracy achieved by Kandel
under investigation. In order to reach the rRMSE criterion, only et al. (2013), which requires 8 days to reach a lower rRMSE.
240 S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241

40
30
20
10
0 10.6
0.9
0.8
0.7
rRMSE rAE R^2

BMP1% Test time


40 1 40 1

30 0.9 30 0.9
rRMSE and rAE (%)

rRMSE and rAE (%)


R2

R2
20 0.8 20 0.8

10 0.7 10 0.7

0 0.6 0 0.6
0 5 10 15 20 25 30 0 5 10 15 20 25 30
Time (days) Time (days)

Fig. 5. rRMSE, rAE and R2 vs. time into the test for predictions of BMP1% and test time of all studied samples. The solid horizontal lines represent a R2 of 0.9 and the striped
horizontal line represents a rRMSE and rAE of 10%.

Table 3
Time required and statistical parameters when rRMSE < 10% and R2 > 0.9 are fulfilled for each sample group.

Sample group rRMSE < 10% R2 > 0.9


2
Time (day) rAE (%) R Time (day) rAE (%) rRMSE (%)
Anaerobic sludge 7 7.7 0.88 9 5.9 7.4
Standard compounds 4 6.7 0.05 15 0.5 2.0
Household waste 6 4.8 0.93 6 4.8 8.6
Agricultural waste 8 5.8 0.75 8 5.8 8.1
Sewage sludge 3 6.5 0.56 6 2.6 4.1
Lipid rich waste 1 7.0 1.51 1 7.0 8.7
All 6 5.4 0.98 3 10.7 17.4

Table 4
Compilation of literature data related to prediction of BMP. Also presented is the time necessary (tPA) by the prediction algorithm to reach the reported rRMSE and R2 for each
study.

Reference Sample type n rRMSE (%) R2 tPA (days)


Biochemical composition
Amon et al. (2007) Maize samples 12 9.4a 0.54 6
Gunaseelan (2007) FVW 24 18.8a 1.25a 3
Gunaseelan, 2009 Solid wastes 32 18.4a 0.02a 3
Triolo et al. (2011) Animal slurries, energy crops, FVW 65 26.5 – 2
Thomsen et al. (2014) Solid wastes 64 19.7 0.96 6
Respirometric activity
Schievano et al. (2008) OFMSW + digestate 46 24.8 0.92 4
Schievano et al. (2009) Solid wastes 81 27.4 – 2
Scaglia et al. (2010) MSW – 23.4b 0.89 3
Near infrared spectroscopy (NIRS)
Lesteur et al. (2011) MSW + lignocellulosic wastes 102 12.3c 0.76 4
Raju et al. (2011) Meadow grasses 95 11.1c,d 0.69 6
Doublet et al., 2013 14 Different types of waste 296 12.6c 0.85 4
Kandel et al. (2013) Reed canary grass 98 7.3c 0.26 8
Triolo et al. (2014) Plant biomass 88 14.5c 0.84 4

Acronyms: FVW – fruit and vegetable waste, MSW – municipal solid waste.
a
Calculated from reported values.
b
Biogas potential of dry matter.
c
Recalculated from average and RMSE.
d
Results from calibration curve.

However, the low R2 reported for this study and the fact that only gated 296 samples divided into 12 groups. As seen in Table 4, the
reed canary grass samples were investigated, implies that the low prediction algorithm presented in this study requires 4 days to
errors might be explained by a lower sample diversity. The most reach similar accuracy for the predictions, which is more than
comparable study is the one by Doublet et al. (2013) that investi- the 2–3 days that is necessary for the sample preparation and
S. Strömberg et al. / Bioresource Technology 176 (2015) 233–241 241

NIR analysis used by Doublet et al. (2013). However, it should be Kandel, T.P., Gislum, R., Jørgensen, U., Lærke, P.E., 2013. Prediction of biogas yield
and its kinetics in reed canary grass using near infrared reflectance
mentioned that information given from the first 4 days of anaero-
spectroscopy and chemometrics. Bioresour. Technol. 146, 282–287.
bic biological degradation might disclose much information about Koch, K., Drewes, J.E., 2014. Alternative approach to estimate the hydrolysis rate
possible toxic effects and the rate of the degradation process. Fur- constant of particulate material from batch data. Appl. Energy 120, 11–15.
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J.P., 2010. Alternative methods for determining anaerobic biodegradability: a
the users will always have the option to leave an ongoing experi- review. Process Biochem. 45, 431–440.
ment to continue longer until their own accuracy requirements Lesteur, M., Latrille, E., Bellon Maurel, V., Roger, J.M., Gonzalez, C., Junqua, G., Steyer,
are met. J.P., 2011. First step towards a fast analytical method for the determination of
biochemical methane potential of solid wastes by near infrared spectroscopy.
Bioresour. Technol. 102, 2280–2288.
5. Conclusions Moody, L., Burns, R., Wu-Haan, W., Spajić, R., 2009. Use of biochemical methane
potential (BMP) assays for predicting and enhancing anaerobic digester
performance. In: 44th Croatian & 4th International Symposium on
This study demonstrates that mathematical prediction models, Agriculture, Opatija, Croatia, 16–20 February, 2009.
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1124.
able error margins (i.e. rRMSE < 10%) for the prediction of BMP1% Raju, C.A., Ward, A.J., Nielsen, L., Møller, H.B., 2011. Comparison of near infra-red
are achieved only 6 days after starting the test. The results also spectroscopy, neutral detergent fibre assay and in-vitro organic matter
show that linear regression based on data from previous tests digestibility assay for rapid determination of the biochemical methane
potential of meadow grasses. Bioresour. Technol. 102, 7835–7839.
improves the predictions significantly compared to kinetic model- Raposo, F., De La Rubia, M.A., Fernández-Cegrí, V., Borja, R., 2011. Anaerobic
ling. However, as this study only evaluates 138 sample types, using digestion of solid organic substrates in batch mode: an overview relating to
mainly one type of inoculum at mesophilic temperatures, exten- methane yields and experimental procedures. Renew. Sustain. Energy Rev. 16,
861–877.
sive additional testing remains necessary to verify this technical Rincón, B., Banks, C.J., Heaven, S., 2010. Biochemical methane potential of winter
approach on a wide-scale level. wheat (Triticum aestivum L.): influence of growth stage and storage practice.
Bioresour. Technol. 101, 8179–8184.
Scaglia, B., Confalonieri, R., D’Imporzano, G., Adani, F., 2010. Estimating biogas
Acknowledgements production of biologically treated municipal solid waste. Bioresour. Technol.
101, 945–952.
The authors would like to express their gratitude to the Swedish Schievano, A., Pognani, M., D’Imporzano, G., Adani, F., 2008. Predicting anaerobic
biogasification potential of ingestates and digestates of a full-scale biogas plant
Energy Agency (2008-000449) and Swedish Research Links pro-
using chemical and biological parameters. Bioresour. Technol. 99, 8112–8117.
gramme (348-2011-7347) for financial support of this study. Schievano, A., Scaglia, B., D’Imporzano, G., Malagutti, L., Gozzi, A., Adani, F., 2009.
Prediction of biogas potentials using quick laboratory analyses: upgrading
previous models for application to heterogeneous organic matrices. Bioresour.
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