Bioresource Technology 102 (2011) 40984103

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

Real time monitoring of a biogas digester with gas chromatography,

near-infrared spectroscopy, and membrane-inlet mass spectrometry
Alastair James Ward a, Emiliano Bruni b, Morten K. Lykkegaard c, Anders Feilberg a,
Anders P.S. Adamsen a, Anders P. Jensen b, Allan K. Poulsen c,
a
Department of Biosystems Engineering, Faculty of Agricultural Sciences, Aarhus Univ., Blichers All 20, DK-8830 Tjele, Denmark
b
Xergi A/S, Burrehjvej 43, DK-8830 Tjele, Denmark
c
Danish Technological Institute, Centre of Chemistry and Biotechnology, Kongsvang All 29, DK-8000 Aarhus, Denmark

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

Article history: Four methods of monitoring the anaerobic digestion process were studied at pilot scale. The methods
Received 9 September 2010 employed were Micro Gas Chromatography (l-GC) and Membrane Inlet Mass Spectrometry (MIMS) for
Received in revised form 13 December 2010 measurements in the gas phase, Near Infrared Spectroscopy (NIRS) and pH in the liquid phase. Micro
Accepted 14 December 2010
Gas Chromatography accurately measured H2, CH4, H2S, N2 and O2 in the headspace whereas the MIMS
Available online 22 December 2010
accurately measured CH4, CO2, H2S, reduced organic sulfur compounds and p-cresol, also in the head-
space. In the liquid phase, NIRS was found to be suitable for estimating the concentrations of acetate, pro-
Keywords:
pionate and total volatile fatty acids (VFA) but the error of prediction was too large for accurate
MIMS
l-GC quantication. Both the l-GC and NIRS were low maintenance methods whereas the MIMS required fre-
NIR quent cleaning and background measurements.
On-line monitoring 2010 Elsevier Ltd. All rights reserved.
Biogas

1. Introduction
Anaerobic digestion of organic wastes or energy crops is an
effective method of producing renewable energy. However, many
biogas plants operate at sub optimal loading rates to ensure a
stable process (Costa et al., 2009) at the expense of digester pro-
ductivity. A major problem is the sensitivity and slow growth
rate of the methane producing organisms with a resulting risk
of process failure if loading rates vary or are increased rapidly.
A reliable method for on-line monitoring of key process variables
and automatic control are necessary for maximum loading whilst
maintaining a stable process (Steyer et al., 1999). A recent survey
of centralized biogas plants in Denmark has shown that poor
process monitoring was an important factor regarding process
imbalances and suboptimal conditions (Nielsen and Angelidaki,
2008).
Current practice for agricultural biogas plants is to use a super-
visory control and data acquisition (SCADA) system for basic plant
operating procedures only. This typically comprises only tempera-
ture and level control and logging of biogas ow rate and more
rarely also logging of pH in the digester. The decision making re-
lated to the loading and composition of the biomass input includ-
ing introduction of new and potentially toxic substrates is based on
Corresponding author. Tel.: +45 72201824; fax: +45 72201019.
E-mail address: akp@dti.dk (A.K. Poulsen).
the experience of the plant operator. Therefore there is a need for
monitoring and control systems at biogas plants treating manure
and solid wastes (Boe et al., 2008).
In a complicated biological process such as anaerobic digestion,
there are many factors which are indicative of the process state.
These factors can be grouped into liquid or gas phase measure-
ments. Volatile fatty acids (VFA) have been shown to be of key
importance as they are formed in excess as a result of process
imbalance (Ahring et al., 1995). Individual VFAs such as propionate
(Boe et al., 2008; Nielsen et al., 2007), butyrate and isobutyrate
(Ahring et al., 1995) have been put forward as being of particular
interest. However, there is no dened threshold inhibitory level
of any VFA species that is valid for all reactors (Angelidaki et al.,
1993) therefore VFA monitoring is preferable as an on-line applica-
tion to examine relative changes over time.
Gas phase parameters for monitoring the process can be either
the measurement of the biogas ow rate or of the gas composition.
Gas phase parameters alone have been criticized for being slow to
respond to changes in the liquid phase but when combined with
other parameters such as pH, biogas ow rate (Steyer et al.,
1999) and analysis of H2, CH4 and CO2 (Mathiot et al., 1992) have
proven to be suitable inputs for control systems. Membrane Inlet
Mass spectrometry (MIMS) has potential for investigating and on-
line monitoring of anaerobic bioreactors (Matz and Lenneman,
1996), monitoring of biological process activity with high specic-
ity and sensitivity (Lloyd et al., 2002) and also for detecting VFA in
the headspace with pH correction. MIMS was recently applied for

0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2010.12.052
 A.J. Ward et al. / Bioresource Technology 102 (2011) 40984103
monitoring biolter efciency with respect to e.g. VFA, phenols and
reduced organic sulfur compounds (Feilberg et al., 2010).
Normal practice for monitoring process parameters is the time
consuming method of sampling and laboratory analysis. VFAs are
normally measured off-line by gas chromatography (GC). On-line
systems for VFA measurement by GC have been developed (Pind
et al., 2003) which use microltration of a reactor sample. An on-
line VFA measurement system without ltration has also been
demonstrated which acidies a sample and measures VFA in the
headspace by GC. However, this system resulted in high variations
of sensor response at low VFA concentrations and problems related
to foaming and material resistance (Boe et al., 2007). NIR is a ro-
bust method that can measure VFA in the liquid phase (Hansson
et al., 2003; Holm-Nielsen et al., 2007), and is a promising tech-
nique for on-line applications. No commercial NIR systems are
yet available for process VFA monitoring.
Gas composition analysis is routinely carried out in laboratories
by GC (Nakakubo et al., 2008) although electrochemical cells are
available for on-line hydrogen sulde or hydrogen measurement
(Mathiot et al., 1992) and infrared sensors are available for meth-
ane and carbon dioxide (Holubar et al., 2002). However, a l-GC
is able to measure gas composition on-line and is more portable
than a regular GC and is therefore more suited to eld work (Sado-
wska-Rociek et al., 2009) or integration into an on-line process
monitoring system.
The work presented here compares different on-line methods
for the monitoring of process parameters in both the liquid and
gas phases of a pilot scale anaerobic digester. The methods con-
sisted of:
 A pH probe connected to data acquisition software.
 A near infrared spectrometer equipped with a diffuse reec-
tance probe situated in a re-circulation loop to monitor VFA in
the liquid phase.
 A MIMS to measure various gases in the headspace.
 A l-GC, calibrated for H2, CH4, CO2, H2S, N2 and O2 measure-
ments in the headspace.
The process was monitored for a period of 2 months (October
November 2009), during which the organic loading rate (OLR) was
increased. To our knowledge this is the rst time MIMS and l-GC
are used for on-line monitoring of biogas reactors.
2. Methods
2.1. Pilot-scale biogas plant
2.1.1. Substrate preparation
The substrate for the biogas process was a mixture of chicken
manure and pig manure in equal proportions (on a wet weight ba-
sis) which was further diluted with water at a manure to water ra-
tio of 0.35:1 w/w. The manures were kept frozen at 18 C until
use. The mixed substrate had TS (total solids) and VS (volatile sol-
ids) content of 6.7% and 5.3%, respectively, and TKN (total Kjeldahl
nitrogen) and ammoniacal nitrogen (NH4N) of 3.98 and 1.84 g L1,
respectively. The methane potential of the substrate was
272 8 mL CH4 (g VS)1.
2.1.2. Reactor set-up
A pilot-scale plant designed and built by Xergi A/S (Foulum,
Denmark) was used for the experiments. The reactor is shown
schematically in Fig. 1. The plant was composed of two stainless
steel tanks used as substrate storage and as digester, respectively.
The total volume of the reactor tank was 300 L, the working vol-
ume was 200 L and the headspace volume was 100 L. A vertical
4099
mixer rotating at 2 Hz (installed on both tanks) ensured continu-
ous mixing. The tanks were equipped with load cells for control
of feeding and of efuent removal. Eccentric pumps were used
for feeding and for efuent removal. The removal of the efuent
preceded the feeding by 15 min. The process temperature in the
biogas reactor was maintained at 52 0.5 C. The OLR was changed
in six steps from a starting point of 3.5 g VS (L d)1 to 4.9, 6.2, 8.6,
11.0, 8.2 g VS (L d)1 and nally to an extreme load of 26.5 g VS
(L d)1 on days 11, 18, 25, 32, 36 and 47, respectively. The changes
in OLR were achieved by modifying the hydraulic retention time
(HRT). This method prevented problems with pump blockage
which were expected from a substrate with an elevated dry matter
content and has previously been shown to be a suitable method of
varying process parameters for experimental purposes (Ahring
et al., 1995; Converti et al., 2009). A controller was used for auto-
matic control of temperature, efuent removal, feeding and for
data logging.
2.2. Analytical methods
TS, VS, total nitrogen TKN and ammonium nitrogen NH4N
(Kjeldahl-N method) were measured according to the standard
methods (APHA, 1998). The concentration of VFAs was measured
as described by Kaparaju et al. (2009). The methane concentration
of the biogas was also measured off-line with a gas chromatograph
equipped with a ame ionization detector (FID). The methane po-
tential was determined in batch assays (infusion bottles of 543 ml
total volume, 200 ml anaerobic inoculum from biogas plant digest-
ing cow manure, 5 g WW substrate, at 52 C) as described by Bruni
et al. (2010). The methane potential was calculated according to
Hansen et al. (2004). All gas readings were corrected to STP condi-
tions (standard temperature and pressure, 273 K, 101.3 kPa).
2.2.1. Sampling
An eccentric pump re-circulated the content of the reactor
through a loop from the bottom of the reactor back to the top of
the reactor with a ow rate of 10 L min1. Liquid sampling for
off-line VFA determination took place from a tap installed along
the re-circulation loop. The NIR probe was situated at a 90 bend
at the highest point of the re-circulation loop adjacent to the liquid
sampling point (Fig. 1). The probe was positioned to face down-
wards. The pH probe was inserted directly in the content of the
biogas reactor. The biogas production was measured with a ow
meter (Gallus 2100 G 1.6 TCE). The MIMS and l-GC inlets were
connected to the outlet biogas stream with the l-GC following a
silica gel lter (see Fig. 1) to prevent water intake in the GC-
columns.
2.2.2. Micro-gas chromatography
Micro-gas chromatography (l-GC, Agilent 3000) was used for
online determination of head space composition. The l-GC was
equipped with two parallel capillary columns containing different
coatings (MolSieve 5 PLOT, 10 m  0.32 mm  12 lm and PLOT
Q, 10 m  0.32 mm  10 lm. Both columns were connected to
thermal conductivity detectors (TCD) with argon applied as a car-
rier gas with a column pressure on 20 psi. Sampling was carried
out every 30 min with each sampling event lasting approximately
2 min. Every 14 days, the instrument was calibrated against a cer-
tied biogas standard with 1000 20 ppmv H2, 1000 30 ppmv
H2S, 40 0.79% CO2 and 50 1.0% CH4 (Air Liquide, Deutschland
GmbH).
2.2.3. Membrane-inlet mass spectrometry
For measuring a wider range of gases, including low concentration
gases (<10 ppmv), a MIMS (Balzers QMG 420) was connected to the
outlet biogas stream, sampling and measuring the headspace biogas
4100 A.J. Ward et al. / Bioresource Technology 102 (2011) 40984103
Fig. 1. A schematic presentation of the pilot plant and the monitoring of the process.
online (Fig. 1). The working principle is that a constant sample gas
ow (5060 mL/min) ows along a 50 lm thick silicone membrane
(SIL-TEC Sheeting, Technical Products Inc., USA), where volatile com-
pounds selectively are absorbed and diffuse across the membrane
and evaporate into the vacuum chamber (106 mbar) of the mass
spectrometer. The membrane inlet system was kept at 50 C. The
compounds were ionized by electron impact (70 eV) and separated
according to their mass-to-charge ratio (m/z) in the quadrupole mass
lter and detected by a secondary electron multiplier.
Gas was sampled every 2 h with automated background mea-
surements on a humidied certied biogas standard 60 0.6%
CH4, 1 0.01% O2, rest CO2 (Air Liquide, Deutschland GmbH) once
per day. The relatively low sampling frequency was selected in or-
der to minimize membrane and ion source fouling.
Additional characterization in terms of linearity and detection
limits of the MIMS system for measuring VFA was carried out by
using a calibration system based on permeation tubes (VICI, Swit-
zerland). The biogas standard was connected to a Dynacal 150 per-
meation oven (VICI, Switzerland) containing acetic acid, propanoic
acid, and butanoic acid in permeation tubes. The emission rates of
the permeation ovens were determined gravimetrically. The biogas
standard was humidied with a gas washing bottle and was used
for further dilutions of the output from the permeation oven. Con-
centrations in the range of 0.220 ppm ( < 10%) were generated.
The following masses were used to detect VFA: m/z 60 (acetic acid
and butanoic acid), m/z 73 (butanoic acid and propanoic acid), m/z
74 (propanoic acid) and m/z 88 (butanoic acid).
2.2.4. Near-infrared spectroscopy
An Antaris FT-NIR instrument (Thermo Scientic) recorded NIR
spectra in the liquid phase via a sapphire windowed diffuse reec-
tance probe, connected to the spectrometer by an optical ber
cable. The probe illuminated an area of approximately 0.1 cm2
and was set in a re-circulation loop to ensure constant ow of
material for a more representative measurement (Fig. 1).
The spectra collected were averaged over 100 scans which for
each sampling event took approximately 30 s using a spectral res-
olution of 16 cm1. Sampling was every 10 min. A reference spec-
trum, averaged over 200 scans, was periodically acquired using
spectralon, positioned in the probe holder, and as such accounts
for spectral contributions of the probe and optical cabling. The
raw spectra obtained were subsequently divided by this reference
spectrum to yield a reection value relative to the white-standard.
For technical and practical reasons white referencing was only per-
formed approximately once every 14 days as with the l-GC.
2.2.5. pH
A probe pHix compact (MJK Automation A/S) was used for on-
line pH measurements. The probe was calibrated every 14 days
at pH 4.01, 7.00, 10.00. Manual pH measurements took place once
per day. pH was measured mainly with the purpose of correcting
headspace VFA measurements.
2.2.6. Data treatment and monitoring
The subsequent VFA modeling using chemometrics was based
on manual VFA analysis by GC. Multivariate data analysis for mod-
el development was applied to the NIR data using TQ Analyst soft-
ware (Thermo Scientic). For detection and elimination of outliers,
principal component analysis (PCA) was applied to calculate prin-
cipal component (PC) scores together with a leverage diagnostic
and visual evaluation of the raw spectra. For computing prediction
models, partial least squares (PLS) regression was used. Absorption
values (A = log(1/R)) were computed from the reection values (R)
and multiplicative scatter correction (MSC) was applied to com-
pensate for scattering effects in the heterogeneous slurry. For mod-
el validation, segmented cross validation (segment of 10) was
applied and the quality was controlled and optimized in an itera-
tive manner by following (1) the root mean square error of cross
validation (RMSECV, the average error of the model), (2) the num-
ber of optimal principal components (PCs, these determine the
model complexity with fewer being preferred to reduce the risk
of model overtting), (3) the coefcient of determination (R2, the
proportion of variability accounted for by the model), and (4)
residual prediction deviation (RPD, the ratio of standard deviation
to RMSECV). In total, no more than 10% of the spectra were identi-
ed as outliers.
2.2.7. Data interface
In order to effectively compare the large amount of data from
the different analytical methods, a suitable MATLAB interface
was developed where relevant time intervals can be picked out
and as such compare the different data spot on for elucidating
interesting correlations.
 A.J. Ward et al. / Bioresource Technology 102 (2011) 40984103
3. Results and discussion
During the experiment there were no obvious problems or ma-
jor failures with any of the analytical equipment besides a few days
without measurements due to a power failure.
3.1. Gas phase
In Fig. 2 is seen a typical concentration prole of H2, N2, CH4,
CO2 and H2S measured with the l-GC during a period of 2 days.
It is possible to observe feeding events, carried out in the morning
and in the evening, which manifest as a rise in the N2 signal and a
decrease in the remaining signals. This was a result of ambient air
being drawn into the reactor during daily replacement of organic
material. The detection limit of the l-GC is approximately
10 ppmv.
The measurement of H2, H2S, CO2 and CH4 with MIMS along
with other gases such as VFAs, reduced organic sulfur compounds
(ROS) and p-cresol (4-methylphenol) was also attempted. The
MIMS signals were observed to be dependent on the pressure in
the detection chamber, which was higher when sampling humid
biogas compared to ambient air. This is mainly ascribed to high dif-
fusion rates of CH4 and H2O in the silicone membrane. Therefore,
all calibrations and baseline measurements were performed using
the previous mentioned humidied CH4/CO2 biogas standard. This
gave detection chamber pressures comparable to those observed
when sampling biogas. Some sensitivity drift was observed and
the data have therefore been normalized by the CO2 signal (m/z
44).
The MIMS measurements of CH4 and H2S were in good agree-
ment with the measurements obtained by l-GC (Fig. 3).
Feeding events resulted in a major increase in MIMS-signals as-
signed to dimethyl sulde (DMS; m/z 47 + 62) and methanethiol
(MT; m/z 47 + 48). During efuent removal, some air was sucked
into the digester from the biogas outlet. This can be observed as
a correlation between oxygen in the biogas and m/z 47 (DMS/MT)
(Fig. 4). The air that was introduced into the system during the
removal of the efuent diluted the other components of the biogas
such as CH4, CO2, H2 and H2S as shown in Fig. 2 yet the DMS/MT
concentrations apparently increased following efuent removal
and feeding. This probably can be attributed to a slight oversatura-
tion of DMS in the slurry, which is released during the small
Fig. 2. Concentration in ppmv of gases measured with the l-GC as function of time during a random period of one and a half day (Oct. 1718th). For clarity, O2 is not shown in
this gure but was also measured with l-GC. The vertical arrow shows an increase in OLR from 4.9 to 6.2 g VS (L d)1.
4101
vacuum during the efuent removal. Signals at m/z 107 and 108
were observed throughout the measurement period. These signals
are assigned to p-cresol based on the ratio of the signals and the
fact that this compound is generally observed to be present in slur-
ry systems due to degradation of the amino acid, tyrosine
(Hofmann and Hammer, 1999; Oneill and Phillips, 1992).
Due to an unusually high background signal at m/z 2 on the spe-
cic instrument used, it was not possible to quantify H2 by MIMS in
this study. Normally, however, mass spectrometry should be suit-
able for measuring H2, see e.g. Whitmore et al. (1987).
Additional characterization of MIMS sensitivity towards VFA
demonstrated a high degree of linearity of the method with
R2 > 0.995 for all masses monitored. The detection limits estimated
from replicate blank measurements were as follows: Acetic acid;
50 ppb, Propanoic acid; 20 ppb, Butanoic acid; 20 ppb. The calibra-
tion was not performed during the campaign and the response fac-
tors were therefore not used to convert corrected signals into gas
concentrations. For comparison, the equilibrium VFA concentra-
tions in units of ppb-by-volume, C eq
g , were calculated from the li-
quid phase concentrations by the following formula:
C aq 1 1
C eq
g    109 ;
MW  1000 1 10pHpka K 298
H  exp DHsol 1
 1
R T 298:15
where Caq is the measured liquid phase concentration (mg/liter),
MW is the molecular weight of the compound, K 298 H is the Henrys
law constant of the compound (M/atm), DHsol is the enthalpy of
solution, R is the gas constant, and T is the temperature of the reac-
tor. Henrys law constants including temperature dependences
from Sander (1999) were used as input values. The corresponding
average gas phase concentrations (one standard deviation) were:
Acetic acid; 49 23 ppb, propanoic acid; 27 18 ppb and butanoic
acid; 8 7 ppb. Consequently, the VFA-signals measured by MIMS
could only potentially (assuming equilibrium) have been above
the detection limits at high concentrations of VFA. MIMS-signals
higher than the detection limit (by a factor of 2) were observed
during periods with high liquid phase concentrations. However,
MIMS-signals were not observed to be correlated with liquid phase
VFA-concentrations. This could partly be explained by the signals
being close to the detection limit giving rise to a higher relative
uncertainty. In addition, it is possible that impedance in liquid-to-
gas exchange prevents the gas concentration from trailing the liquid
4102 A.J. Ward et al. / Bioresource Technology 102 (2011) 40984103

Fig. 3. Concentration developments for (A) H2S and (B) CH4 during a period of 33 days, starting October 17th, measured with l-GC and MIMS. The vertical arrows 15 show
OLR changes from 4.9 g VS (L d)1 to 6.2, 8.6, 11.0, 8.2 and 26.5 g VS (L d)1, respectively.

Fig. 4. Dimethyl sulde (DMS) and methanethiol (MT) measured with MIMS (B) during a period of 8 days in the latter part of the campaign. The O2 signal measured with l-
GC (A) is shown for comparison. The vertical arrow shows an increase in OLR from 8.2 to 26.5 g VS (L d)1.

phase concentration (mainly because of the pH of the liquid phase of measurement technique. The positioning of the probe in the recir-
the biogas digester). The MIMS was a labour intensive measurement culation loop could perhaps be improved: it has been reported that
method when applied to biogas processes as the instrument re- the ideal position for sample collection and therefore probe attach-
quired frequent cleaning and background measurements. ment to a pipe is a side valve in a vertical pipe section to improve
turbulence (and therefore mixing) and reduce gravitational segre-
gation (Holm-Nielsen et al., 2006). In this study the probe was
3.2. Liquid phase mounted vertically in a T-piece of tubing which formed a 90 bend
in the sample loop, see Fig. 1. Although this position would provide
The pH of the liquid phase of the biogas digester was between
7.54 and 7.89.
In the modeling of acetate, propionate and total VFA content,
Table 1
NIR data from the 2 months period with increased OLR has been
NIR VFA prediction model parameters. N is the number of samples used for the
used. The VFA prediction models compare reasonably well with calibration set, NPC is the number of principal components in the respective models.
previously reported NIR data (Holm-Nielsen et al., 2007; Jacobi
VFA species N NPC VFA range RMSECV R2 RPD
et al., 2009) in terms of R2 values (>0.80). However, the RMSECV
(g L1) (g L1)
values are large and subsequently the RPD values are low (Table 1),
below the recommended minimum of 2.5 suggested by Williams Acetate 111 11 05.4 0.80 0.84 1.83
Propionate 110 10 03.4 0.57 0.83 1.79
(2001) as being the lower limit for quantitative analysis. The Total VFA 113 10 09.4 1.53 0.84 1.82
reason for the relatively poor models could be due to the
 A.J. Ward et al. / Bioresource Technology 102 (2011) 40984103
a good deal of turbulence and therefore a representative sample it is
possible that gas in the pipe or large particles could become trapped
in front of the probe window causing erroneous measurements.
4. Conclusion
In this study it was found that l-GC accurately measured H2,
CH4, CO2, H2S, N2 and O2. MIMS accurately measured CH4, CO2,
H2S, reduced organic sulfur compounds, and p-cresol. Headspace
VFA measurement was also possible with MIMS but the data were
close to the detection limits and showed little relation to the liquid
phase VFA concentration. NIR gave an approximate indication of li-
quid phase VFA concentrations. NIR, l-GC and the pH probe proved
to be reliable and low maintenance. MIMS is considered not suit-
able for long term online measurements because it required fre-
quent cleaning and daily background measurements.
Acknowledgements
Thanks are due to Ejnar Paaske Jensen, Pia Jrgensen, Carsten
Siggaard, Adris Georgis Shlimon. Thanks to the lab technicians,
Britt Amby Malthesen and Heidi G. Christiansen, for excellent
assistance with sampling and analyses and to Energinet.dk, The
ForskEL programme, PSO 2008-1-0078 Real time control of biogas
reactors for nancially supporting the project with 384.358.
References
Ahring, B.K., Sandberg, M., Angelidaki, I., 1995. Volatile fatty acids as indicators of
process imbalance in anaerobic digesters. Appl. Microbiol. Biotechnol. 43, 559
565.
Angelidaki, I., Ellegaard, L., Ahring, B.K., 1993. A mathematical model for dynamic
simulation of anaerobic digestion of complex substratesfocusing on ammonia
inhibition. Biotechnol. Bioeng. 42, 159166.
APHA, 1998. Standard Methods for the Examination of Water and Wastewater, 20th
ed. American Public Health Association, Washington, DC.
Boe, K., Batstone, D.J., Angelidaki, I., 2007. An innovative online VFA monitoring
system for the anaerobic process, based on headspace gas chromatography.
Biotechnol. Bioeng. 96, 712721.
Boe, K., Steyer, J.P., Angelidaki, I., 2008. Monitoring and control of the biogas process
based on propionate concentration using online VFA measurement. Water Sci.
Technol. 57, 661666.
Bruni, E., Jensen, A.P., Angelidaki, I., 2010. Steam treatment of digested biobers for
increasing biogas production. Bioresour. Technol. 101, 76687671.
Converti, A., Oliveira, R.P.S., Torres, B.R., Lodi, A., Zilli, M., 2009. Biogas production
and valorization by means of a two-step biological process. Bioresour. Technol.
100, 57715776.
Costa, J.C., Moita, I., Abreu, A.A., Ferreira, E.C., Alves, M.M., 2009. Advanced
monitoring of high rate anaerobic reactors through quantitative image
analysis of granular sludge and multivariate statistical analysis. Biotechnol.
Bioeng. 102, 445456.
Feilberg, A., Adamsen, A.P.S., Lindholst, S., Lyngbye, M., Schfer, A., 2010. Evaluation
of biological air lters for livestock ventilation air by membrane inlet mass
spectrometry. J. Environ. Qual. 39, 10851096.
4103
Hansen, T.L., Schmidt, J.E., Angelidaki, I., Marca, E., la Cour Jansen, J., Mosbk, H.,
Christensen, T.H., 2004. Method for determination of methane potentials of
solid organic waste. Waste Manag. 24, 393400.
Hansson, M., Nordberg, A., Mathisen, B., 2003. On-line NIR monitoring during
anaerobic treatment of municipal solid waste. Water Sci. Technol. 48, 913.
Hofmann, K., Hammer, E., 1999. Anaerobic formation and degradation of toxic
aromatic compounds in agricultural and communal sewage deposits.
Chemosphere 38, 25612568.
Holm-Nielsen, J.B., Dahl, K.D., Esbensen, K.H., 2006. Representative sampling for
process analytical characterization of heterogeneous bioslurry systems- a
reference study of sampling issues in PAT. Chemom. Intell. Lab. Syst. 83, 114126.
Holm-Nielsen, J.B., Andree, H., Lindorfer, H., Esbensen, K.H., 2007. Transexive
embedded near infrared monitoring for key process intermediates in anaerobic
digestion / biogas production. J. Near Infrared Spectrosc. 15, 123135.
Holubar, P., Zani, L., Hager, M., Froschl, W., Radak, Z., Braun, R., 2002. Advanced
controlling of anaerobic digestion by means of hierarchical neural networks.
Water Res. 36, 25822588.
Jacobi, H.F., Moschner, C.R., Hartung, E., 2009. Use of near infrared spectroscopy in
monitoring of volatile fatty acids in anaerobic digestion. Water Sci. Tech. 60,
339346.
Kaparaju, P., Serrano, M., Thomsen, A.B., Konjan, P., Angelidaki, I., 2009. Bioethanol,
biohydrogen and biogas production from wheat straw in a biorenery concept.
Bioresour. Technol. 100, 25622568.
Lloyd, D., Thomas, K.L., Cowie, G., Tammam, J.D., Williams, A.G., 2002. Direct
interface of chemistry to microbiological systems: membrane inlet mass
spectrometry. J. Microbiol. Methods 48, 289302.
Mathiot, S., Esofer, Y., Ehlinger, F., Couderc, J.P., Leyris, J.P., Moletta, R., 1992.
Control parameter variations in an anaerobic uidized-bed reactor subjected to
organic shockloads. Water Sci. Technol. 25, 93101.
Matz, G., Lenneman, F., 1996. On-line monitoring of biotechnological processes by
gas-chromatographicmass spectrometric analysis of fermentation
suspensions. J. Chromatogr. 750, 141149.
Nakakubo, R., Mller, H.B., Nielsen, A.M., Matsuda, J., 2008. Ammonia inhibition of
methanogenesis and identication of process indicators during anaerobic
digestion. Environ. Eng. Sci. 25, 14871496.
Nielsen, H.B., Angelidaki, I., 2008. Codigestion of manure and industrial organic
waste at centralized biogas plants: process imbalances and limitations. Water
Sci. Technol. 58, 15211528.
Nielsen, H.B., Uellendahl, H., Ahring, B.K., 2007. Regulation and optimization of the
biogas process: propionate as a key parameter. Biomass Bioenerg. 31, 820830.
Oneill, D.H., Phillips, V.R., 1992. A review of the control of odor nuisance from livestock
buildings. 3. Properties of the odorous substances which have been identied in
livestock wastes or in the air around them. J. Agri. Eng. Res. 53, 2350.
Pind, P.F., Angelidaki, I., Ahring, B.K., 2003. A new VFA sensor technique for
anaerobic reactor systems. Biotechnol. Bioeng. 82, 5461.
Sadowska-Rociek, A., Kurdziel, M., Szczepaniec-Cieciak, E., Riensenmey, C., Vaillant,
H., Batton-Hubert, M., Piejko, K., 2009. Analysis of odorous compounds at
municipal landll sites. Waste Manag. Res. 27, 966975.
Sander, R. Compilation of Henrys Law Constants for inorganic and organic species
of potential importance in environmental chemistry. 1999. www.mpch-mainz.
mpg.de/~sander/res/henry.html (Accessed June 23 2010).
Steyer, J.-P., Bufre, P., Rolland, D., Moletta, R., 1999. Advanced control of anaerobic
digestion processes through disturbances monitoring. Water Res. 33, 20592068.
Whitmore, T.N., Lloyd, D., Jones, G., Williams, T.N., 1987. Hydrogen-dependent
control of the continuous anaerobic-digestion process. Appl. Microbiol.
Biotechnol. 26, 383388.
Williams, P.C., 2001. Implementation of near-infrared technology. In: Williams, P.C.,
Norris, K. (Eds.), Near-Infrared Technology in the Agricultural and Food
Industries, 2nd ed. American Association of Cereal Chemists Inc., St. Paul,
Minnesota, USA, pp. 145169.