Bioresource Technology xxx (2017) xxxxxx

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

Review

Enhanced volatile fatty acids production from anaerobic fermentation of

food waste: A mini-review focusing on acidogenic metabolic pathways
Miaomiao Zhou a,b, Binghua Yan a,, Jonathan W.C. Wong c, Yang Zhang a
a
Lab of Waste Valorization and Water Reuse, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, 189 Songling Road, Laoshan District,
Qingdao 266101, PR China
b
University of Chinese Academy of Sciences, No.19A Yuquan Road, Beijing 100049, PR China
c
Sino-Forest Applied Research Centre for Pearl River Delta Environment, Department of Biology, Hong Kong Baptist University, PR China

h i g h l i g h t s

 Major acidogenic metabolic pathways during anaerobic fermentation of food waste were summarized.
 The intensification measures for enhancing each acidogenic metabolic pathway were discussed.
 The strategies for enhancing VFAs recovery during acidogenic fermentation of food waste were summarized.

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

Article history: Recently, efficient disposal of food waste (FW) with potential resource recovery has attracted great atten-
Received 30 April 2017 tions. Due to its easily biodegradable nature, rich nutrient availability and high moisture content, FW is
Received in revised form 21 June 2017 regarded as favorable substrate for anaerobic digestion (AD). Both waste disposal and energy recovery
Accepted 22 June 2017
can be fulfilled during AD of FW. Volatile fatty acids (VFAs) which are the products of the first-two stages
Available online xxxx
of AD, are widely applied in chemical industry as platform chemicals recently. Concentration and distri-
bution of VFAs is the result of acidogenic metabolic pathways, which can be affected by the micro-
Keywords:
environment (e.g. pH) in the digester. Hence, the clear elucidation of the acidogenic metabolic pathways
Volatile fatty acids (VFAs)
Food waste
is essential for optimization of acidogenic process for efficient product recovery. This review summarizes
Anaerobic fermentation major acidogenic metabolic pathways and regulating strategies for enhancing VFAs recovery during aci-
Metabolic pathway dogenic fermentation of FW.
2017 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.1. Food waste (FW) situation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
1.2. Anaerobic digestion (AD) of FW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
2. VFAs production during AD of FW . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3. Acidogenic metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.1. Acetate-ethanol type metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.2. Propionate-type metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.3. Butyrate-type metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.4. Mixed-acid metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.5. Lactate-type metabolic pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
3.6. Homoacetogenic fermentation pathway . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4. Strategies to enhance VFAs production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.1. Improving the hydrolysis rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2. Promoting the acidogenesis process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

Corresponding author.
E-mail address: yanbh@qibebt.ac.cn (B. Yan).

http://dx.doi.org/10.1016/j.biortech.2017.06.121
0960-8524/ 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
2 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx

4.2.1. Substrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2.2. Inoculum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2.3. pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2.4. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2.5. HRT and OLR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.2.6. Headspace gas pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
4.3. Removing inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
5. Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
6. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00

1. Introduction stringency of environmental standards (Lim et al., 2008; Wang

et al., 2014). Alternative methods which are more efficient and
1.1. Food waste (FW) situation environmentally sustainable are needed for disposal of FW.

With the development of economy and increment of popula-

tion, the generation of municipal solid waste (MSW) has been
increasing over the years (e.g. about 1.3 billion tons per year in
world and this quantity is expected to increase to 2.2 billion tons
by 2025), one third of which is food waste (Han et al., 2016). FW
contains uneaten food residues and discarded food during the
stage of production, processing, retailing and consumption. The
amount of FW is continuously increasing. By 2010, the generation
of FW in China reached 90 million tons per year (Zhang et al.,
2014). Without treatment FW can cause severe contamination of
air, water, and soil due to its odor, leachate and quick decomposi-
tion nature during the collection, transportation and storage (Han,
2004; He et al., 2012). Traditionally, food waste is reutilized and
disposed by feeding animals, composting to produce fertilizer,
landfilling and incineration; however, these methods have
disadvantages, i.e. feeding animals with untreated FW could make
animals prone to infection, composting and landfilling would
occupy large quantity of valuable land (Yan et al., 2014a) and
releases greenhouse gases (Li et al., 2010), incineration is energy-
intensive and unstable due to the high moisture content (MC) of
FW (Shen et al., 2013). Hence, traditional methods for disposal of
food waste become less feasible, in some regions even have been
forbidden due to public concerns of sustainability and the
1.2. Anaerobic digestion (AD) of FW
Characterization of food waste governs the choice of its disposal
strategy. According to the different eating habits, the FW from dif-
ferent sources showed varied characteristics (Table 1), such as pH
changing from 3.68 to 6.50, volatile solid to total solid ratio (VS/TS)
changing from 0.79 to 0.97, carbon-to-nitrogen ratio (C/N) chang-
ing from 9.20 to 63.60, and MC ranging from 70% to 93%. Although
there are some differences associated with sources and cultures,
FW do share similar characteristics, such as easy biodegradability,
rich nutrient availability and high moisture content, and because of
which, FW could be treated by biodegradation. At present, anaero-
bic digestion is preferred as an efficient strategy for resource recov-
ery in terms of biogas or high value-added liquid products from
FW. For example, there was 64.70 mL methane gas or 0.32 g vola-
tile fatty acids (VFAs) produced with one gram of volatile solid
feeding to the anaerobic digesting reactor (Jiang et al., 2013). The
products are used as either the fuel for supplying energy or the
platform chemicals in industrial production. Currently, AD of FW
for VFAs production has attracted increasing interests due to the
high added value of the products as well as high product to sub-
strate ratio.

Table 1
Characteristics of FW reported from different sources.

Regions Source pH VS/ C/N MC Lipid(g/L) Carbohydrate(g/ Protein(g/L) Reference

TS (%) L)
Yongin, Korea A restaurant of Myongji University 6.5 0.94 13.2 NA 23.3 NA 14.98 Zhang et al.
(2011)
Gwangju, Korea NA 4.5 0.89 9.2 87.6 NA NA NA Kim et al. (2006)
Kwangyang, A food waste-recycling plant 3.68 0.8 NA NA 17.7 17.5 21.7 Shin et al. (2010)
Korea
Daejeon, Korea A dining hall 5.8 0.94 18.3 93 NA 25.5 NA Shin (2004)
Daejeon, Korea A dining hall 4.6 0.96 NA 84 NA 84.9 g COD/L 37.7 g COD/L Kim et al. (2004)
Shanghai, China A dining hall of Tongji University 4.1 0.88 32 NA 13.6 135.6 42.3 Chen et al.
(2013c)
Shanghai, China A restaurant in Shanghai Jiao Tong University 3.9 0.97 49.9 87.1 10.6% TS 69.3% TS 16.1% TS Zhang et al.
(2005)
Beijing China A canteen in Beijing University of Chemical NA 0.87 63.6 81.8 24.11% dry 35.47% dry basis 14.42% dry He et al. (2012)
Technology basis basis
Beijing, China Cafeteria of Beijing University of Chemical NA 0.79 11.5 77.4 28.85% dry 41.89% dry basis 14.71% dry Shen et al. (2013)
Technology basis basis
Hangzhou, China A canteen of Zhenjiang Gongshang University 6.1 0.962 NA 86 NA 39.5% dry basis 11.0% dry basis Wang et al.
(2014)
Pullman, USA Regency Dinning Center at Washington State 4.2 0.89 NA NA 8% VS 59% VS 33% VS Li et al. (2010)
University
San Francisco, Restaurants, food markets, commercial sources NA 0.85 14.8 70 NA NA NA Zhang et al.
USA (2007)

NA- Not available.

Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx 3

2. VFAs production during AD of FW
Commonly, anaerobic digestion process consists of four steps,
hydrolysis, acidogenesis, acetogenesis and methanogenesis. Vola-
tile fatty acids are important intermediates produced in acidogen-
esis and acetogenesis step when organic materials are treated by
anaerobic digestion. VFAs as potentially renewable carbon sources,
have various applications, such as biological nitrogen removal (Lim
et al., 2006), production of biodiesel (Fei et al., 2011), generation of
electricity through microbial fuel cells (Chen et al., 2013c), and
synthesis of complex polymers (Chen et al., 2013a). Presently, VFAs
and their derivatives are widely used in food, textile, pharmaceuti-
cal, leather and plastics industries (den Boer et al., 2016). Besides
VFAs, hydrogen gas is also produced in the acidogenesis process
(Kim et al., 2011), which is known as an ideal, clean and renewable
energy due to only water generated after its oxidative combustion
(Guo et al., 2010). Comparing with gas, the storage and transporta-
tion of VFAs is easier and safer. In addition, the added value of VFAs
which is 50130 $/ton (Fei et al., 2015) is higher than that of
methane which is 0.72 $/m3 (Oleskowicz-Popiel et al., 2012).
Hence, VFAs are more attractive products proposed to recover from
anaerobic fermentation of FW.
Anaerobic generation of VFAs is processed through a series of
biochemical reactions catalyzed by acidogenic bacteria and aceto-
gens. Firstly acidogenic bacteria ferment the hydrolysate mono-
mers to acetate, propionate, butyrate, alcohols, H2, CO2, and other
solvents. Then, propionate, butyrate, alcohols and CO2 are further
converted to acetate through proton-reducing acetogenic path-
ways or homoacetogenic pathway (Stams et al., 2006). Commonly,
acetate, propionate, and butyrate are main VFAs products during
acidogenic fermentation of FW (Jiang et al., 2013). In addition to
industrial applications of mixed VFAs, individual component of
VFAs showed higher application potential, for example, butyrate
could be used as a building block for pharmaceuticals (Choudhari
et al., 2015). Generally, the value of VFA increases with the incre-
ment of carbon numbers, as the market prices of different VFAs
are following an order of butyric acid (2163 $/ton) > propionic acid
(2000 $/ton) > acetic acid (600 $/ton) (Calt, 2015). This might be
attributed to the wider industrial application of longer-chain fatty
acids, and production of which is usually more difficult than that of
short-chain ones (Stowers et al., 2014). Hence, propionate and
butyrate are more attractive products than acetate according to
their market values and applications. Concentrations and distribu-
tion of VFAs are the results of the prevailing acidogenic metabolic
pathways in the digester.
There are several metabolic pathways during acidogenic fer-
mentation because of the various components in FW and mixed
culture in anaerobic system. And the prevailing pathway changes
under different conditions, which has governing effect on the gen-
eration and distribution of VFAs. Therefore, it is important to illus-
trate the acidogenic metabolic pathways and potential regulations.
Investigation into acidogenic metabolic pathways during anaerobic
fermentation of food waste can not only give a clear demonstration
on the process of VFAs production, but also can be used as guid-
ance for the augmentation of VFAs production and selective
increase of high value-added acid by taking appropriate measures
(Chen et al., 2013b).
3. Acidogenic metabolic pathway
Acidogenic fermentation of FW could be carried out through a
series of chemical reactions catalyzed by different enzymes.
Numerous distinct pathways co-exist within the digester of anaer-
obic fermentation and they are taking a crucial role in the system
performance and resource recovery.
In the network of acidogenic metabolic pathways, pyruvate is
the pivotal control point which can be converted into a wide range
of products such as acetate, propionate, butyrate, ethanol, propa-
nol, butanol, H2 and CO2 (Chen et al., 2013c) (Fig. 1). Metabolic
pathways present in acidogenic reactor play a vital role in
determining overall conversion efficiency of FW. The proportions
of pyruvate directed to each pathway depend on the substrate
used, the environmental conditions, and the properties of strains.
Usually, the distributions of major soluble products reflect the

Fig. 1. Metabolic pathways of acidogenic fermentation. (AET, acetate-ethanol type fermentation; ABE, acetone-butanol-ethanol; PTF, propionate-type fermentation; BTF,
butyrate-type fermentation; MAF, mixed-acids fermentation; LTF lactate-type fermentation).

Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
4 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx

Table 2
Summary of reactions of metabolic pathways during acidogenic fermentation.

Metabolic pathway Reactions Major factors Yield Functional acidogens Reference

Acetate-ethanol type C6H12O6 + 2H2O ? 2CH3COOH Glucose concentration: Ethanol 77.84; acetate Aspergillus awamori Han et al. (2015)
(AET) metabolic + 2CO2 + 4H2 35.14 g/L; pH: 4.04.5 45.3 (mM)
pathway Eq. (1) HRT: 5 h; pH: 4.34.4 Ethanol 3.82; acetate NA Wang et al. (2013)
CH3CH2COOH + 2H2O ? CH3COOH 0.66 (gCOD/L)
+ CO2 + 3H2 Pre-treatment; inoculum 0.43 g ethanol/g total Saccaromyces cerevisiae Kim et al. (2011)
Eq. (2) solids
CH3CH2CH2COOH + 2H2O ?
2CH3COOH + 2H2
Eq. (3)
CH3CH2OH + 2H2O ? CH3COOH
+ 2H2
Eq. (4)
C6H12O6 + H2O ? CH3CH2OH
+ CH3COOH + 2H2 + 2 CO2
Eq. (5)
Acetone-butanol-ethanol C6H12O6 + H2O ? Substrate: glucose inhibitors Acetone-ethanol- Clostridium beijerinckii Ezeji et al. (2007)
(ABE) fermentation CH3COCH3 + 4H2 + 3CO2 butanol, 17.8 g/L BA101
Eq. (6) Substrate: maize; inoculum: Total solvents 12.91 g/L Clostridium Patakova et al. (2009)
C6H12O6 ? 2CH3CH2OH + 2CO2 acetobutylicum
Eq. (7)
C6H12O6 ? CH3CH2CH2 CH2OH
+ H2O + 2CO2
Eq. (8)
Propionate-type C6H12O6 + 2H2 ? 2CH3CH2COOH Substrate: Lactate: glucose 4 Propionate 30 g/L; Propionibacterium Martnez-Campos and
metabolic pathway + 2H2 Propionate/acetate 7.63 acidipropionici de la Torre (2002)
(PTF) Eq. (9) Substrate: mixed FW and Propionate 7.13 COD/L Propionibacterium Chen et al. (2013b)
3C6H12O6 ? 4CH3CH2COOH sludge; operation: two stage acidipropionici
+ 2CH3COOH + 2CO2 + 2H2O
Eq. (10)
Butyrate-type metabolic C6H12O6 ? CH3CH2CH2COOH pH 5.0 Butyrate > 85% of total NA Wang et al. (2014)
pathway (BTF) + 2CO2 + 2H2 VFAs
Eq. (11) Substrate: MRS media Butyrate 0.48 g/g Clostridium Liu et al. (2013)
4C6H12O6 ? glucose tyrobutyricum strain
8H2 + 8CO2 + 2CH3COOH + 3 RPT-4213
CH3CH2CH2COOH
Eq. (12)
Mixed-acid metabolic Glucose ? acetate + propionate pH: 6.5 VFAs and ethanol NA Zhu et al. (2009)
pathway (MAF) + butyrate + valerate + CO2 + H2 70 mM
Eq. (13)
Lactate-type metabolic C6H12O6 ? 2CH3CH(OH)COOH Temperature: 35 C Initial Lactic acid 14.7 g/L Mixed cultures Liang et al. (2014)
pathway (KTF) Eq. (14) solids loading: 60 g/L
C6H12O6 ? CH3CH(OH)COOH
+ CO2 + CH3CH2OH
Eq. (15)
Homoacetogenic 4H2 + 2CO2 ? CH3COOH + 2H2O Hydrogen partial pressure: Acetate 44 g/L Acetobacterium woodii Demler and Weuster-
fermentation pathway Eq. (16) 1700 mbar; pH7.0 Botz (2011)

NA-Not available.

prevailing metabolic pathways. Based on the distribution of major
liquid products, acidogenic metabolic pathways are generally clas-
sified as, (1) acetate-ethanol type, (2) propionate-type, (3)
butyrate-type, (4) mixed-acid, and (5) lactate-type metabolic path-
way. (6) Homoacetogenic fermentation pathway is also reviewed
for its increasing role in the acidogenic fermentation.
3.1. Acetate-ethanol type metabolic pathway
Fermentation pathway with acetate and ethanol as the main
products is termed as acetate-ethanol type (AET) fermentation
(Fig. 1). Acetate and ethanol are regarded as the most popular
intermediates during acidogenic fermentation of organic matters
and they usually come together in the fermentation for hydrogen
production (Zhang et al., 2017). Apparently, acetate is one of the
most important components of carboxylic platform. Hence, acido-
genic fermentation of food waste with the purpose of acetate pro-
duction would provide both economic and environmental benefits.
Acetate can not only be sourced from pyruvate through acetyl-CoA
pathway but also can be generated from the syntrophic oxidation
of ethanol or longer chain fatty acids such as propionate and buty-
rate (Table 2 and Eqs. (1)(4)). In essence, abundance of acetate in
AET fermentation is strongly associated with the functional
enzymes in acetyl-CoA pathway and syntrophic oxidation (Mller
et al., 2010). Ethanol is also one of the common products that
can be produced during fermentation of glucose or other organic
materials (Table 2 and Eq. (5)). The conversion of pyruvate to etha-
nol in Enterobacteriaceae needs three steps with acetyl-CoA and
acetaldehyde as the intermediates (Chaganti et al., 2011), whereas
there are only two crucial steps in the conversion of pyruvate to
ethanol by some other bacteria (Bensaid et al., 2015), which are
pyruvate decarboxylation to acetaldehyde and subsequent
acetaldehyde reduction to ethanol. The tendency of acetate pro-
duction is closely related to the micro-environments in the diges-
ter including substrate type, inoculum, pH, temperature,
configuration, organic loading rate (OLR), hydraulic retention time
(HRT), operational modes as well as headspace H2 pressure. The
composition of carbohydrate, protein and lipids in the food waste
really determines the distribution of fermentation products, e.g.
large portion of carbohydrate could promote the generation of

Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx
acetate (Shin and Youn, 2005). Anaerobic sourced inoculum usu-
ally leads to typical acetate accumulation during the start-up
anaerobic process (Charles et al., 2009). pH is always the crucial
factor that affects the shift of acidogenic metabolic pathway. It
was reported that increased pH from 4.0 to 7.0 could increase
the generation of acetate but decrease the production of butyrate
whereas the production of acetate and butyrate became equally
abundant in a pH range of 6.57.0 (Fang and Liu, 2002). Besides
operational parameters, metabolic engineering techniques such
as deletion, addition and modification of certain pathway could
also be measures for controlling acetate production pathway
(Vadali et al., 2004). Even though metabolic pathway with ethanol
production is recognized as one of the fermentative ways for cells
to cope with anaerobic environment, it is not regarded as the major
pathway during the acidogenic fermentation of FW. Accumulation
of ethanol in the digester would be toxic to the microbes and car-
bon recovery rate is low due to the loss of two carbon molecules
(Table 2 and Eq. (5)). Production of ethanol could be enhanced
under specific conditions, e.g. elevated H2 partial pressure in the
acidogenic headspace; however, this usually associates with low
energy recovery rate.
During ethanol-producing process, acetone and butanol can be
produced from glucose by some species in the genera of Clostridium
such as Clostridium acetobutylicum (Yen et al., 2011) and Clostrid-
ium beijerinckii, which is also called acetone-butanol-ethanol
(ABE) fermentation (Table 2 and Eqs. (6)(8)). The biosynthesis of
solvents shares the same metabolic pathway from glucose to
acetyl-CoA but branches into different pathways thereafter. Except
for ethanol production, acetyl-CoA is also converted to acetacetyl-
CoA for producing acetone and butanol. On the one hand,
acetacetyl-CoA is converted to acetone or further to isopropanol
occurred in some Clostridium beijerinckii strains. On the other hand,
butanol is produced from acetacetyl-CoA via the intermediates 3-
hydroxybutyl-CoA, crotonyl-CoA and butyl-CoA. Commonly, this
pathway produces solvents in a ratio of 3 parts of acetone, 6 parts
of butanol to 1 part of ethanol. It is believed that the ABE fermen-
tation was influenced by the substrates and inoculum (Patakova
et al., 2009). Commonly, the solvent-producing bacteria carry out
biphasic fermentation. In the first phase, organic acids are pro-
duced and accumulated; when the pH drops, solvents become
the main products in the second phase. The production of solvent
is stimulated by the accumulation of acids and the decrease of
pH. But up to now, it is still a challenge to maximize the yield of
solvents and minimize the production of undesired acids. In order
to reduce the products inhibition and make solvent-producing fer-
mentation profitable, separation and recovery unit should be
developed (Qureshi and Maddox, 2005).
3.2. Propionate-type metabolic pathway
Acidogenic metabolic pathway with propionate as the predom-
inant product is defined as propionate-type fermentation (PTF).
Propionate is another common fermentation product during
acidogenic fermentation of food waste. Theoretically, one mole of
glucose could generate two moles of propionate (Table 2 and Eq.
(9); Saady, 2013). However in practice, lots of anaerobic microbes
would ferment glucose to propionate with acetate production
(Table 2 and Eq. (10); Zhu et al., 2009). Propionate is produced
through two distinct pathways (Fig. 1). In one of them, propionate
comes from reduction of pyruvate with lactate as the intermediate:
firstly, lactate is produced by reduction of pyruvate with the
catalyzation of lactate dehydrogenase; then lactate is reduced to
propionate by the propionate dehydrogenase (Lee et al., 2008).
The other pathway for propionate production can be carried out
by acidogenic bacteria such as Corynebacteria, Propionibacterium
Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
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5
and Bifidobacterium via transcarboxylase cycle. All the reactions
of the transcarboxylase cycle are reversible.
Recently, the interest in the production of propionate from bio-
mass via fermentation has increased due to its high added value in
industrial application. Propionate can be used in the manufacture
of herbicides and chemical intermediates, and as preservatives
for conservation of food, animal feed, and grain (Posada and
Cardona, 2012). Propionate is also recognized as favorable carbon
source for enhancing municipal wastewater biological nutrient
removal (Zhang and Chen, 2009). There are various factors affect-
ing the production of propionate, such as pH, type of inoculum
and product inhibition (Jin and Yang, 1998). The acidogenic pro-
duction of propionate is favored at pH 4.04.5 and at pH 4.0 the
percentage of propionate can go up to 10% of the total VFAs
(Wang et al., 2014). Commonly, the yield of propionate during
anaerobic fermentation of organic materials is low, which is attrib-
uted to the fact that propionate-producing bacteria are strongly
inhibited by undissociated propionate, especially when the pH is
below 6.0 (Hsu and Yang, 1991). Acetate and CO2 are the common
byproducts of the propionate-type metabolic pathway which could
further reduce the substrate carbon for propionate production (Jin
and Yang, 1998). Previous research showed that the production of
propionate could be enhanced by using mixed lactate and glucose
as the substrates (Martnez-Campos and de la Torre, 2002). This
might because that lactate as an intermediate in the propionate-
type metabolic pathway could prompt the process of propionate
formation. There was also report for controlling the production of
propionate through adjusting the oxidation-reduction potential
(ORP), e.g. production of propionate can be reduced by elevated
ORP (Feng et al., 2014).
3.3. Butyrate-type metabolic pathway
Major acidogenic metabolic products of butyrate-type fermen-
tation (BTF) are butyrate and acetate. H2 is always the accompany-
ing product in butyrate-type metabolic pathway. Metabolic
reactions for butyrate production from glucose are present in
Table 2 Eqs. (11) and (12) (Saady, 2013). In butyrate-type meta-
bolic pathway, butyrate is synthesized by reduction and decar-
boxylation of pyruvate with the consumption of acetate (Fig. 1).
Firstly, pyruvate is converted to acetyl-CoA by pyruvate dehydro-
genase. Then, acetyl-CoA is converted to butyryl-CoA with
acetoacetyl-CoA, 3-hydroxybutyryl-CoA and crotonyl-CoA as inter-
mediates sequentially by the catalysis of thiolase, 3-
hydroxybutyryl-CoA dehydrogenase and butyryl-CoA dehydroge-
nase (Chaganti et al., 2011). The final step from butyryl-CoA to
butyrate is either catalyzed by enzymes phosphotransbutyrylase
and butyrate-kinase or catalyzed by the butyryl-CoA: acetate
CoA-transferase (Vital et al., 2014). During the process of butyrate
production, two NADH2 are consumed to reduce the intermediates.
As industrial feedstock in the pharmaceutical, cosmetic and
chemical industries, butyrate is a more attractive product than
acetate (Ganigue et al., 2015). In recent years, butyrate is also
attracting attention for its great potential in area of human health
care (Berni Canani et al., 2012). Besides the common critical factors
such as pH and temperature, reducing equivalent is also a crucial
factor that determines the efficiency of butyrate production. Com-
pared to the process of acetate production, two more NADH2 are
consumed to reduce the intermediates for butyrate formation,
which means that more reducing equivalents as NADH2 in the
digester could facilitate butyrate production. It was reported that
the production of butyrate increased with the increase of acetate
in the system (He et al., 2012). It might be due to the fact that high
acetic acid concentration not only has a reverse feedback to the
generation of acetate but also leads to a great surplus of NADH2.
6 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx

3.4. Mixed-acid metabolic pathway

In mixed-acid fermentation (MAF), acidogenic microbes could

ferment organic monomers to a mixture of acetate, propionate,
butyrate, and valerate, etc. with equal amount (Table 2 and Eq.
(13)) and the possibility of biogas formation (CO2 and H2)
(Fig. 1). Mixed-acid metabolic pathway is popular during acido-
genic fermentation of FW with acetate and butyrate as the major
metabolites (Jiang et al., 2013). The abundance of individual com-
ponent in the mixed acids can be affected by various factors such
as the concentration and characteristics of the substrates, pH,
redox potential, etc. (Riondet et al., 2000). For example, low pH
(<4.5) leads to the production of acetate, butyrate and ethanol as
the primary products, while a pH of >6.5 would induce the increase
of ethanol production and decrease of acid formation (Zhu et al.,
2009). In addition, the distribution of these metabolic products
depends on type of inoculum bacteria and the expression of func-
tional enzymes in the microbes. Methods which stimulate the
activities of enzymes involving in one branch or inhibit the activi-
ties of enzymes in the other branch could enhance the production
of specific acid.

3.5. Lactate-type metabolic pathway

Lactate-type fermentation (LTF) is a metabolic pathway to con-
vert glucose or other organic materials to lactic acid by bacteria
such as Lactobacillus acidophilus, Lactobacillus casei, Streptococcus
thermophilus, etc. During lactate-type fermentation, the pyruvate
produced by glycolysis is converted to lactate by lactate dehydro-
genase with the transformation of NADH2 to NAD+ (Fig. 1). Based
on the products, lactate-producing process can be divided into
two fermentation types, homolactate fermentation in which one
mole of glucose is converted to two moles of lactic acid (Table 2
and Eq. (14)), and heterolactate fermentation in which one mole
of lactic acid is produced along with CO2 and ethanol (Table 2
and Eq. (15)). (Castillo Martinez et al., 2013).
Lactic acid has been widely used in the food, pharmaceutical,
and cosmetic industries and also as a useful monomer for the pro-
duction of biodegradable polymers in chemical industry (Wee
Fig. 2. Homoacetogenic metabolic pathways of acetate production from CO2. (THF,
tetrahydrofolate; [Co-Protein], corrinoid enzyme).
Fig. 3. The Strategies to enhance VFAs production from anaerobic digestion of FW.
et al., 2006). The production of lactic acid from fermentation of
FW could be influenced by substrates, pre-treatment, pH, temper-
ature, etc. When potato peel waste was fermented to organic acids
by mixed cultures, lactic acid as the main product reached highest
value under the conditions of initial solid loading of 60 g/L and
temperature at 35 C (Liang et al., 2014).
3.6. Homoacetogenic fermentation pathway
In the anaerobic communities, there are a group of obligate
anaerobes which can use H2 as the electron donor to reduce CO2
to acetate (Siriwongrungson et al., 2007). This reaction is termed
as homoacetogenesis, and the group of bacteria are called
homoacetogens (Saady, 2013). Homoacetogens grow on CO2 and/
or organic compounds as sources of energy and carbon to produce
acetate. In autotrophic process, the homoacetogens are capable of
consuming the H2 and CO2 to produce acetate (Table 2 Eq. (19))
by homoacetogenic fermentation pathway which is also called
Wood-Ljungdahl pathway (Drake et al., 2006). The Wood-
Ljungdahl pathway is composed of two linear branches, the methyl
and carbonyl branch (Fig. 2). The methyl branch starts by consum-
ing 2 mol of reducing equivalents to reduce CO2 to formate by for-
mate dehydrogenase. After a series of reactions catalyzed by
successive enzymes formate dehydrogenase, methylene-H4F
reductase and metheyltransferase, the methyl group is synthe-
sized. In this branch, the synthesis of the methyl group totally con-
sumes 6 mol of reducing equivalents. The carbonyl branch is the
reduction of CO2 to carbon monoxide (CO) by acetyl-CoA synthase,
and this step consumes 2 mol of reducing equivalents. Then the
methyl group and CO are converted to Acetyl-CoA which is ulti-
mately either converted into acetate with ATP synthesis during
catabolism or to cell carbon during anabolism (Guo et al., 2010;
Siriwongrungson et al., 2007). In Wood-Ljungdahl pathway, an
ATP breakeven situation is formed after 2 mol of CO2 being reduced
to acetate, as one ATP is consumed in the activation of formate and
could be latterly regained via substrate-level phosphorylation. On
the other hand, the reduction of CO2 to CO in the carbonyl
branch may also consume energy (estimated as 1/3 ATP
equivalent) (Drake, 1994), resulting in the overall homoacetogenic

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focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx 7

Table 3
Comparison of VFAs production by different promoting strategies.

Strategies Specific methods Optimal condition VFAs production Possible metabolic Reference
pathways
Improve hydrolysis Pretreatment 60 min thermal, 0.1%(v/v) 6.6 g COD/L NA Kim et al.
enzyme (2005)
Improve hydrolysis; inhibit the Acidic condition 30 C, pH 6 0.918 g/g VSS removal Eqs. (1), (3), (11), Wang et al.
activity of methanoges (12) (2014)
Improve hydrolysis; promote pH 35 C, pH 7 36 g/L Eqs. (1)(3), (9) Zhang et al.
acidogenesis process (12) (2005)
Promote acidogenesis process; Co-fermentation of WAS and pH 8, C/N ratio 22, 37 C, 6d 692.4 mg COD/g VS Eqs. (1)(3), (912) Chen et al.
enhance methaogenesis kitchen waste (2013c)
Promote acidogenesis process Temperature, pH, ORL 35 C, pH6,OLR 11 g/L 39.46 g/L; 0.316 g/g VSfed Eqs. (1)(3), (9) Jiang et al.
(12) (2013)
Promote acidogenesis process Temperature, pH, HRT, ORL 35 C, pH6, HRT 8 days, ORL 9 g/L 25 g/L Eqs. (1)(3), (9) Lim et al.
d (12) (2008)
Promote acidogenesis process Acetobacterium woodii co- 37 C, pH7, A.woodii + heat- Enhance the acetate in Eqs. (1), (8), (12), Yan et al.
culture treated sludge products (16) (2014b)
Promote acidogenesis process Propionibacterium 30 C,pH7, two stage Enhance the propionic Eqs. (9), (10) Chen et al.
acidipropionici as inoculum acid production (2013b)
2
Remove products Electrodialysis with bipolar Effective surface area of 100 cm NA Eqs. (1), (3), (11), Arslan et al.
membranes with 5 cell trios (12) (2016)

NA-Not available.

fermentation as endergonic process under normal condition. How-
ever, in some special situations, such as acidic environments
(Phelps and Zeikus, 1984), lower temperature (Conrad and Klose,
1999), or higher hydrogen partial pressure (Siriwongrungson
et al., 2007), homoacetogens can out-compete other acidogens
under adverse condition and would take over the hydrogen oxidiz-
ing function due to their tolerance to a wide range of environmen-
tal conditions.
Homoacetogens are the most metabolically diverse group of
obligate anaerobes, which are known to be present in mesophilic
digester with 105107 CFU/ml (Zhang and Noike, 1994), taking
approximately 311% of total bacteria in anaerobic sludge. Hence,
the role played by homoacetogenic type metabolic pathway in aci-
dogenic fermentation cannot be ignored. Operational factors that
influence the performance of this pathway are pH, temperature,
headspace pressure, etc. (Kotsyurbenko et al., 2001). Demler and
Weuster-Botz (2011) carried out a study on hydrogenotrophic pro-
duction of acetate by homoacetogens. With pH controlled at 7.0,
the production of acetate by Acetobacterium woodii increased with
the increase of hydrogen partial pressures and the maximum value
was achieved at a hydrogen pressure of 1.7 bar (Demler and
Weuster-Botz, 2011).
4. Strategies to enhance VFAs production
Based on phased stages of AD, strategies for enhancing VFAs
production are generally classified into (Fig. 3): 1) improving
hydrolysis rate to produce more soluble substrates for further fer-
mentation, 2) promoting the acidogenic process, and 3) removing
the inhibiting factors (Table 3).
Besides the augmentation of total VFAs yield, it is more attrac-
tive to enhance the proportion of high-value added fatty acids dur-
ing the acidogenic fermentation of FW. As it is discussed above, the
values of propionic acid and butyric acid are higher than that of
acetic acid, hence the accumulation of propionate or butyrate is
more economic favorable.
4.1. Improving the hydrolysis rate
acidogenic fermentation of FW (Kim et al., 2005). It is believed that
the improvement of hydrolysis could increase the readily available
substrate-carbon for subsequent conversion to VFAs, which would
certainly enhance the production of VFAs. The methods to enhance
the hydrolysis include optimization of key operational factors such
as pH, temperature and pretreatment of FW before fermentation.
In order to improve the overall product recovery efficiency, when
choosing the operational conditions for hydrolysis, the subsequent
acidogenesis should be considered as a whole. Pretreatment of
substrates could enhance the generation of soluble chemical oxy-
gen demand (sCOD) from hydrolysis (Fdez.-Gelfo et al., 2011).
In the anaerobic digesting metabolic pathway, sCOD as the impor-
tant intermediates linking hydrolysis and acidogenesis could influ-
ence the yield of VFAs. Hence, pretreatment of FW is considered as
a favorable way to enhance VFAs production from acidogenic fer-
mentation of FW. Chemical (acid and alkaline), physical (thermal,
microwave and ultrasound) and biological (enzymes) methods
can be used in the pretreatment of FW. Kim et al. (2005) studied
the effect of thermal, enzymatic, and combined thermal-
enzymatic pretreatment on acidogenic fermentation of food waste.
Results showed that all the three pretreatments could enhance
sCOD generation and VFAs production, and combined thermal-
enzymatic treatment lead to the maximum VFAs production.
Hydrolysis also influenced the composition of VFAs. The find-
ings from Chen et al. (2013b) showed that after pre-fermenting
the food waste mixture with sludge, production of propionate
was enhanced in the second stage, which might be attributed to
the domination of lactate in the pre-fermenting stage. As the pre-
cursor for propionate production, abundant lactate in reactor
enhanced the propionate-type metabolic pathway in the second
stage (Chen et al., 2013b).
4.2. Promoting the acidogenesis process
Critical factors that determining the efficiency of VFAs produc-
tion and quality of VFAs such as characteristics of the substrate,
inoculum, pH, temperature, HRT, OLR and headspace gas (Lee
et al., 2014) will be reviewed in this part.

Generally, the degradation of complex polymers such as ligno- 4.2.1. Substrate

cellulosic materials, lipids and proteins in food waste to smaller The characteristic of substrate is one of the most important
molecules takes the most time during AD process (Marin et al., factors affecting the VFAs production and product composition.
2010). Hence, hydrolysis is regarded as the rate-limiting step in Previous research showed that substrate with higher total kjeldahl

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focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
8 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx
nitrogen (TKN) increased the yield of propionate up to 78% of total
VFAs (Min et al., 2005), whereas in the other research, substrate
with too rich protein content (C/N 7.1) limited the production of
propionate (Feng et al., 2009). This may be relevant to the micro-
bial community and functional enzymes during acidogenic fer-
mentation. For example, supplementation of carbohydrate to
high-protein substrate and appropriate pH could promote propi-
onate production via propionate-type metabolic pathway with
the dominated species of Clostridia, b-Proteobacteria, and Bac-
teroidetes (Feng et al., 2009). In many cases, the lack of some nec-
essary nutrients and elements in food waste could reduce the yield
of products. Co-digestion of different wastes is helpful to solve this
problem, which could supplement nutrient and make the carbon-
nitrogen ratio of substrates more suitable for anaerobic digestion.
In addition, potential toxic compounds in one substrate could be
diluted by adding another substrate (Zhu et al., 2008). Previous
research showed that the co-digestion of FW and sewage sludge
lead to higher carboxylate production compared to single-
substrate fermentation (Kim et al., 2004).
4.2.2. Inoculum
The degradation of organic wastes requires well working mixed
microorganisms, therefore the inoculum is the fundamental dri-
vers to accelerate the process. Hydrolytic bacteria, acidogenic bac-
teria, acetogens and methanogens are the main microbes during
AD. To improve the production of VFAs, methanogens in inoculum
must be inhibited to reduce the consumption of VFAs. To date, sev-
eral methods have been used to inhibit the activities of methano-
gens, such as heat-pretreatment, pH control and addition of
inhibitor. Researchers heated their inoculum at 100 C or over
100 C before experiments in order to inactivate the non-pore
forming methanogens to improve the production of VFAs (Yan
et al., 2014b). The pH in the digester can also be adjusted to pre-
vent the activities of methanogens because the preferred operating
pH range for methanogens is 7.88.2 (Chaganti et al., 2011).
Researches showed that too low or too high of the pH could inhibit
the methanogenesis and lead to the accumulation of VFAs (Wang
et al., 2014; Yuan et al., 2006). Besides, the addition of inhibitors
is another method to avoid methanogenesis and prompt the accu-
mulation of VFAs (Yu et al., 2014). There are two kinds of methano-
genesis inhibitor: specific and nonspecific inhibitors. The specific
group inhibits the enzymes only existing in methanogens and
the nonspecific group can inhibit the activity of both methanogens
and non-methanogens (Liu et al., 2011). In addition, the variation
of inoculum will lead to the change of metabolic pathway of VFAs
production in acidogenic process. Hence, the production of one
particular acid can be enhanced by using some specific inoculum.
Yan et al. (2014b) investigated the acetate production by homoace-
togen Acetobacterium woodii in co-culture with common acetogens.
Results showed that the addition of A. woodii induced homoaceto-
genic fermentation during the first 3 days and lead to acetate as
dominant product (Yan et al., 2014b). Chen et al. (2013b) got a high
propionate content in products by using Propionibacterium
acidipropionici as inoculum (Chen et al., 2013b).
4.2.3. pH
pH is always the critical factor that controlling the production
of VFAs during acidogenic fermentation. pH in the system affects
the activity of microorganisms because most of the enzymes can-
not tolerate the hostile acidic (pH < 3) or alkaline (pH > 12) envi-
ronments (Liu et al., 2012). During acidogenic fermentation of
FW, pH could influence not only hydrolysis but also acidogenic
process (Neyens et al., 2004). Thus, the optimal pH for VFAs pro-
duction should be favorable for both hydrolysis and acidogenic
process. Zhang et al. (2005) found that pH of 7.0 was the most suit-
able for hydrolysis and acidogenesis of kitchen waste as it led to
Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
the highest VFAs concentration in comparison with other pH val-
ues (Zhang et al., 2005). This may be because that under neutral
condition, most of the protein in substrate was degraded into
ammonia nitrogen which can be used as the additional buffer of
acidified fermentative solution. However, different result was
achieved by co-fermenting sludge and food waste, which showed
that production of VFAs was significantly improved and remained
stable when the fermentation condition was at pH 9.0 (Chen et al.,
2013a). These results might be related to more soluble protein and
carbohydrate produced in hydrolysis step while the acidogens was
not inhibited under pH 9.0.
In addition, many studies suggested that pH could change the
metabolic pathway in acidogenic fermentation and affect the dis-
tribution of products. For instance, increase of NADH/NAD+ ratio
at low pH makes the consumption of NADH more favorable
(Temudo et al., 2007). In butyrate-producing process, NADH was
consumed to reduce acetoacetyl-CoA to 3-hydroxybutyryl-CoA
and crotonyl-CoA to butyryl-CoA. Hence, the butyrate-type meta-
bolic pathway would be enhanced under acidic condition to
decrease the NADH/NAD+ ratio in the fermenter. However, there
is no consistent conclusion of the influence of pH on the composi-
tion of products. By investigating anaerobic digestion of FW under
different acidic conditions for VFAs production, Wang et al. (2014)
found that butyrate was the primary product under pH 5.0 with
the percentage of butyrate above 80% (Wang et al., 2014). Jiang
et al. (2013) found that when the pH was at 5.0 or uncontrolled,
acetate was the dominant product, followed by butyrate, propi-
onate, and valerate; and when the pH was at 6.0 and 7.0, butyrate
became the main product (Jiang et al., 2013). Kim et al. (2011)
found that the production of butyrate was highest at pH 8.0 com-
paring with other pH at 5.0, 6.0, 7.0 and 9.0 (Kim et al., 2011). Min
et al. (2005) found that the maximum propionate fraction (80%)
was observed at pH 6.5 in a continuous reactor (Min et al., 2005).
The inconsistent research findings suggest that the composition
of products and production of specific VFA are dependent on vari-
ous factors.
4.2.4. Temperature
Temperature affects the growth of microorganisms, the activi-
ties of enzymes and the hydrolysis of particulate organic matters
to soluble substances (Kim et al., 2003). The mesophilic (35C) con-
dition is considered as the most efficient and economical favorable
temperature for VFAs production as the VFAs yield was highest at
this temperature or similar with that in higher temperatures (Jiang
et al., 2013). But when the composition of VFAs was considered,
the optimal temperature was different. Acetate and propionate
were the most prevalent acids generated at 35 C and 45 C during
the fermentation of FW, whereas butyrate was the main product
accounting for 81% of all products when the temperature increased
to 55 C, followed by acetate and propionate (Jiang et al., 2013).
Similar results were found by investigating the effect of three dif-
ferent temperatures on the hydrolysis and acidification of FW, in
which the production of butyric acid was higher at 55 C than that
at 70 C and 35 C (He et al., 2012).
4.2.5. HRT and OLR
Theoretically, longer HRT has advantages to the production of
VFAs from acidogenic fermentation as the microorganisms have
more time to react with the substrate (Bengtsson et al., 2008).
However, when HRT increases to some extent, the VFAs yield will
keep stable due to the limitation of substrates. Lim et al. (2008)
showed that the yield of VFAs from acidogenic fermentation of
FW increased with the HRT increasing from 4 days to 8 days, but
no significant enhancement was observed between those at HRT
of 8 and 12 days (Lim et al., 2008). Another research demonstrated
that the concentration of VFAs after co-digestion of mixed waste
 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx
increased when HRT increased from 1 day to 2 days; however,
when the HRT further increased to 3 and 4 days, there was no sig-
nificant improvement on the VFAs concentration (Dinsdale et al.,
2000). As for specific acid production, the dominating microbial
population could be selected by regulating HRT, because of the
slower growing organisms being washed out at short HRT. When
acidogenic fermentation of whey, the production of propionic acid
was enhanced as the HRT increases from 20 h to 95 h, but the for-
mation of butyric acid was suppressed (Bengtsson et al., 2008).
While in the co-fermentation of waste active sludge and fruit/veg-
etable waste, the proportion of VFAs did not change too much with
a HRT range from 1 to 4 days (Dinsdale et al., 2000). It is suggested
that HRT should not be the only factor that determines the selec-
tive production of VFA, other operational parameters could also
take their roles for building up the selectivity.
The production of VFAs also increases with the rising of OLR due
to the increasing availability of substrate. For example, the produc-
tion of VFAs from FW increased with OLR increasing from 5 to 13 g/
(L d); however, the broth became very viscous at high organic load-
ing, which resulted in the unstable operation (Lim et al., 2008).
Research about the influence of OLR on the composition of VFAs
showed that low OLR was helpful for the production of propionate
and butyrate while the percentage of acetate and valerate
increased with elevated OLR (Jiang et al., 2013).
4.2.6. Headspace gas pressure
The operational parameters mentioned above such as pH, tem-
perature, OLR and HRT are adequately addressed by researchers
except the headspace gas pressure in the digester. Under most cir-
cumstances, H2 is formed along with the acidogenic fermentation.
The accumulation of H2 in the headspace of reactors may alter the
electron flow in the metabolic pathway of microorganisms
(Valdez-Vazquez et al., 2006) and influence the corresponding pro-
duction of VFAs. Changing metabolic pathways towards production
of reduced compounds such as lactate, ethanol and propionate,
which are commonly accompanied with less H2 production is the
microbial response to the increase of H2 concentration in the
environment.
It is known that maintaining a low level of headspace H2 pres-
sure is essential for sustainable production of VFAs, especially
those associated with the generation of H2. Strategies reported to
reduce the headspace H2 pressure including reuse of H2 through
coupling a homoacetogenic reactor for converting H2 & CO2 to acet-
ate (Nie et al., 2007) and establishment a syntrophism in the acido-
genic reactor which enables the utilization of H2 generated in the
acidogenic reactor itself while maintaining efficient acidogenesis
(Yan et al., 2014b), resulting in the high yield of VFAs, especially
acetate. In addition, the composition of products would be influ-
enced by the headspace environment. Butyrate was the dominant
VFA in reactor when the headspace full of CO2, which was relevant
to the inhibitory effect on acetogens and lactate-producing bacte-
ria under high CO2 partial pressure (Kim et al., 2006).
4.3. Removing inhibitors
Previous researches showed that the concentration of VFAs
could not be increased continuously because of the products inhi-
bition (Jiang et al., 2013). It is known that undissociated VFAs
which can permeate the cell membrane freely could lower the
activities of microorganisms (Zoetemeyer et al., 1982). And accu-
mulation of VFAs may cause the acidogenic reactions thermody-
namically unfavourable, resulting in the shift of metabolic
pathway to produce other products (Pind et al., 2003). Hence, there
is a limitation of total yield of VFAs and production of specific acid.
Such limitation can be overcome if the products were removed
from system continuously. Various techniques have been applied
Please cite this article in press as: Zhou, M., et al. Enhanced volatile fatty acids production from anaerobic fermentation of food waste: A mini-review
focusing on acidogenic metabolic pathways. Bioresour. Technol. (2017), http://dx.doi.org/10.1016/j.biortech.2017.06.121
9
for the recovery of organic acids including precipitation, extraction,
crystallization and distillation. These traditional techniques are
unfavorable due to their disadvantages such as solid pollution,
high costs for chemical use, low yield and high energy-
consumption (Wang et al., 2006). Methods with more economic
and environmental advantages are needed for the downstream
processing of VFAs. Electrodialysis technique has been proving
their advance in the fields of separation and purification of organic
acids due to its technological symbiosis, low pollution, high effi-
ciency (Jones et al., 2015) and supplement of H+ and OH ions by
configuring bipolar membrane without salt introduction (Huang
et al., 2007). For now, some researchers have used electrodialysis
to separate VFAs from fermentation broth to reduce the products
inhibition and enhance the conversion of substrates. Redwood
et al. (2012) recovered 5070% of a carboxylate mixture from an
E. coli continuous fermentation experiment by coupling electro-
dialysis with bipolar membranes and maintained the pH for 30
days (Redwood et al., 2012). Jones et al. (2015) removed 99% of
VFAs from fermentation broths within 60 min by conventional
electrodialysis (Jones et al., 2015). In-situ recovery of products by
electrodialysis not only reduces the inhibition of products, but also
could control the pH which can help select the microbial commu-
nity for different purposes. However, it is still a challenge to
recover one specific acid form the mixed VFAs during anaerobic
fermentation. Arslan et al. (2017) used a novel electrodialysis with
bipolar membranes stack to remove carboxylates in-situly from
broth and allow direct pH control. The results showed that total
production of carboxylates increased, especially, productivities of
acetate and propionate were selectively doubled, possibly because
they were selectively removed from the reactor (Arslan et al.,
2017). This research suggested that if one of the products could
be removed continuously from the reactor, it would change the
metabolic pathway in acidogenic process to produce specific acid.
5. Perspectives
FW is considered to be one of the most promising sources for
recycling energy or producing chemicals as it is taking 3060% of
municipal solid waste. AD treatment is specifically suitable for
FW due to its easily biodegradable nature, rich nutrient availability
and high moisture content. VFAs are the products of the first-two
stages of AD, and are widely applied in chemical industry recent
years. Since the concentration and distribution of VFAs are the
result of acidogenic metabolic pathways, a clear elucidation of
the pathways of VFAs production can give guidance for optimiza-
tion of the acidogenic products recovery and selective production
of specific product. The products are mixed after the acidogenesis
process because of the complex substrates and mixed culture.
For getting high-value product, concentration, separation, and
purification are necessary downstream steps for anaerobic diges-
tion of FW. For date, there are many techniques studied for the
recovery of VFAs. However, in-situ recovery of pure acids from
anaerobic fermentation broth still has difficulty due to the similar
characteristics of VFAs. In the future, measures of separating and
purification of waste derived VFAs are still needed to be investi-
gated in order to increase values of products and expand the range
of applications.
6. Conclusions
Recovery of VFAs from acidogenic fermentation of FW is attract-
ing growing attention due to the high added value of VFAs and
their potential market. This review summarizes major acidogenic
metabolic pathways in fermentation of FW, including acetate-
ethanol type, propionate-type, butyrate-type, mixed-acid type,
10 M. Zhou et al. / Bioresource Technology xxx (2017) xxxxxx
lactate-type and homoacetogenic metabolic pathway. Regulating
strategies for enhancing VFAs production during acidogenic fer-
mentation of FW are also discussed. Based on metabolic pathways,
improvement of hydrolysis, promoting acidogenesis process, and
removal of inhibiting factors are the main aspects should be con-
sidered for VFAs generation. Methods for separation and purifica-
tion of waste-derived VFAs need to be investigated in the future.
Acknowledgements
The authors would like to appreciate the financial support of
the Shandong Provincial Natural Science Foundation (ZR2016b-
b06), 100 Talents Program of Chinese Academy of Sciences
(CAS) and the National Basic Research Program of China
(2013CB733500).
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