Journal of Cleaner Production 207 (2019) 85e96

Contents lists available at ScienceDirect

Journal of Cleaner Production

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

A technical-economical approach to promote the water treatment &

reuse processes
M. Capocelli a, *, M. Prisciandaro b, V. Piemonte a, D. Barba a
a
Faculty of Engineering, University Campus Bio-Medico, Via Alvaro del Portillo, 21, 00128 Roma, Italy
b
Department of Industrial Engineering and Information and of Economics, University of L'Aquila, Viale Giovanni Gronchi 18, 67100 L'Aquila, Italy

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

Article history: Despite the emergency of water scarcity, the man's choices have always been directed towards the
Received 8 March 2018 mismanagement of this vital resource; drinking water is far from being a right for everyone and is rather
Received in revised form scarce and poorly distributed in many areas of the world. The aim of this work is to set up a water cost
12 September 2018
evaluation methodology based on the energetic equivalence among all the possible treatment strategies,
Accepted 15 September 2018
Available online 26 September 2018
water sources and water end-uses. An economic incentive is proposed on the basis of the thermody-
namic and process analysis of a Wastewater Treatment & Reuse (WWTR) Plant. The analysis extends our
^ as de
Handling Editor: Cecilia Maria Villas Bo previous approach to the whole panorama of the water-cycle related technologies. The energy use in-
Almeida tensity of different (in-series) process of a water reuse project has been addressed: from the COD and
nutrient removal, to the energy harvesting and to the separation of dissolved ions. The incentive is able
Keywords: to reward the processes having the goal of low energy consumption and low carbon emissions. The
Energy efficiency methodology has been applied to WWTR projects at different scales. The results showed that it is
Reuse cost possible to obtain an acceptable Return of Investment (ROI), even for a low plant productivity (around
Economic incentive
200 m3/day). Moreover, based on the profitability of the WWTR Project, the calculation of the “true
Biosolids
value” of the “water source” has been presented. An acceptable price of waster (as a commodity) is
Micropollutants
evaluated for both wastewater and seawater by varying the potentiality of the water reclamation plant.
This calculation could be implemented to evaluate the economic benefit of public investment as well as
to reduce the use of water from non-renewable sources.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction projects the demographic and economic trends to 2050: global

Two third of world population will be facing the shortage of
freshwater by 2025 and, by 2050, the global water demand will
exceed the supply by 50% due to the population increase and the
current changing of the global climate equilibrium (UNESCO, 2015;
OECD, 2012). The consequent growing demand for energy and
natural resources is visible in the discomforting statistic reported
by the World Bank that shows the annual availability of renewable
water decreasing from 13000 m3/person in 60's to the actual value
below 6000 m3/person (World Bank's population estimates). The
impacts of no action (in the whole sector of water management)
has been assessed by The OECD Environmental Outlook that
* Corresponding author. Chemical Engineering for the Sustainable Development,
University Campus Bio-Medico di Roma, Via Alvaro del Portillo, 21, 00128, Roma,
Italy.
E-mail address: m.capocelli@unicampus.it (M. Capocelli).
water demand is projected to increase due to growing demand
from manufacturing (þ400%), electricity generation (þ140%) and
domestic use (þ130%); it is also estimated that, by 2050, the agri-
culture will need to double the food production in developing
countries (OECD, 2012). In many parts of the world, the water
quality continues to decline, groundwater basins are overexploited,
and the water availability is characterized by the alternation be-
tween floods and droughts; these issues also exacerbate the con-
flicts and the poverty (UNESCO, 2015; OECD, 2012).
In this context of uncertainty, wastewater can be considered a
“misplaced resource”, suitable for the recovery of energy, valuable
materials and obviously clean water (Gao et al., 2014; Plappally and
Lienhard V, 2012; Water Reuse, 2012; Vourch et al., 2008; El-
Abbassi et al., 2013). The reuse of treated wastewater is a valuable
but under-used means to alleviate the pressure on over-exploited
resources (Water Reuse, 2012; Vourch et al., 2008; El-Abbassi
et al., 2013). The industries promoted the “zero liquid discharge”
in different sectors, mainly to reduce the demand of freshwater as

https://doi.org/10.1016/j.jclepro.2018.09.135
0959-6526/© 2018 Elsevier Ltd. All rights reserved.
86 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
raw materials and to reduce the environmental impacts (Vourch
et al., 2008; El-Abbassi et al., 2013; Piemonte et al., 2015, 2017;
Abdullah Alkhudhiri et al., 2013; Mickley, 2008). The “ground-wa-
ter replacement” as well as the “direct potable reuse” are rapidly
increasing, starting from some virtuous examples in Namibia,
Singapore, Israel and United States (Asano, 1998; Wilf, 2010;
Lazarova et al., 2001).
Based on some recently published works (Gao et al., 2014;
Plappally and Lienhard V, 2012; Prisciandaro et al., 2016), Fig. 1
reports the concept of circular economy in the water sector (here
adopted) consisting in a network of both natural and artificial in-
frastructures and technologies. Water is seen both as a resource and
as a carrier of pollutants, minerals as well as a non-negligible
“energy content” (Gao et al., 2014; Plappally and Lienhard V,
2012; Drioli et al., 2015). It undergoes innumerable processes and
is transported back to a receiving body, with a degraded quality.
Therefore, looking at the treatment stage, it is possible to recovery
water, energy and precious resources in order to reduce the impact
to the receiving body and the withdrawal from non-renewable
sources. This comprehensive view includes the reuse of water of
different quality for different end uses (municipal; industrial;
agriculture, etc …).
Within this continuous cycle, the role of technologies is to
intervene with different reaction-separation steps to purify water
and, at the same time, to recover precious resources.
The main examples of recovery are the integration of membrane
separation and crystallization for mineral recovery in the desali-
nation sector (Drioli et al., 2015; Xuheng et al., 2015; Giwa et al.,
2017) and the nutrient recovery from the wastewater (Kim et al.,
2016). Furthermore, in the desalination sector, R&D efforts are
facing the issue to address the water-energy-resource nexus by
investigating the feasibility of salinity gradient energy and the zero-
discharge desalination systems (Cipollina and Micale, 2016; Chung
et al., 2017).
On the other hand, the water sector presents very low return of
investments and the costs and the economic benefit of the water
reuse are difficult to monetize. Except for bottled drinking water,
the economic value per cubic meter verges to be very low, placing
the water among the “bulky” commodities (Young and Loomis,
2014), i.e. its weight-to-value ratio is very high. The principal
paradox in the water sector is that capital and energy costs for
Fig. 1. Overall Process Scheme of the water “artificial” life-cycle including Water Reuse, Resource and Energy harvesting following the approach of the Circular Economy.
transportation and storage are very high relative to the final eco-
nomic value at the point of use (Plappally and Lienhard V, 2012).
Lastly, the water is distinguished from most other resources by
some peculiarities that pose significant challenges to the quantifi-
cation of costs and benefits of water-related strategies: its natural
mobility, its social role and its peculiar way of utilization. In fact,
water is utilized and partially rejected to the environment in a
“degraded form” therefore the net consumption typically tends to
be a small fraction of water withdrawals (Young and Loomis, 2014;
Kalavrouziotis et al., 2013; Abramson et al., 2010).
The Dublin Statement on Water and Sustainable Development
says that water has an economic value and that its management as
an economic good is fundamental to achieve an equitable use and
to efficiently protect it (The Dublin Statement on Water and
Sustainable Development Adopted, 1992). Moreover, past failure
to recognize the economic value of water has led to wasteful and
environmentally damaging uses (Abramson et al., 2010). Because of
these and other reasons, the water is posed to be the good of the
21st century and considering it as a quantifiable economic asset is
the only way to promote initiatives for its preservation (Abramson
et al., 2010; The Dublin Statement on Water and Sustainable
Development Adopted, 1992; Adar et al., 2015). Although the idea
appears to be controversial, this concept has been endorsed by
many scientists, politicians and stakeholders (Young and Loomis,
2014; Abramson et al., 2010; The Dublin Statement on Water and
Sustainable Development Adopted, 1992; Adar et al., 2015;
Molinos-Senantea et al., 2011; Winpenny, 1997). Winpenny, in
fact, suggested that “mankind gets water too cheaply” and fair ac-
cess to water does not imply it has to be free but that it has to be
equal fair to everyone (Winpenny, 1997).
In this framework, an “energy based” incentive for water reuse
projects in the context of the circular economy is described and
applied to some case-studies in this work. The incentive is based on
the process and thermodynamic analysis of the reference techno-
logical solutions in this field and the comparison between theo-
retical and actual consumption. A recently published paper by the
same research group (Prisciandaro et al., 2016) analysed the
membrane desalination in water reuse and evaluated a possible
strategy of incentives to accelerate the shifting towards a closed-
cycle water management. In this paper, the integration with the
waste-water treatment and its potentiality to recovery energy and
 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
precious materials is added for a more complete approach.
In more details, the proposed methodology is applied to a
conventional municipal wastewater treatment coupled to energy
harvesting from biosolids and a membrane-based reuse technology
(Reverse Osmosis, RO). The thermodynamic analysis of the inte-
grated physical/biological processes enabled the individuation of
the minimum work required and the realization of the energy
balances. The incentive provides a universal methodology, capable
to promote innovative and “low-carbon” solutions and to improve
the profitability of integrated Treatment & Reuse Project in the
water sector. Furthermore and differently from most of the in-
centives in the public sector, this policy rewards integrated solu-
tions and promotes the research in this field, with the aim to reduce
the energy requirements and the CO2 emissions of the overall
system.
The calculation of the incentive has been implemented to the
business plan of three case studies at different scales. For each
configuration, the basic design and the evaluation of economic
feasibility (including investment, fixed and operating costs) are
introduced to evaluate the cost of water production and the return
of the investment (ROI). The effect of the incentive on the project
profitability has been addressed though a sensitivity analysis.
Moreover, based on the profitability of the Water Treatment and
Reuse Project, the calculation of the “water source” cost is pro-
posed. This calculation could be implemented to evaluate the “true
value of water”, to estimate the economic benefits of public in-
vestments in this sector as well as to rationalize the use of water
from “non-renewable sources”.
2. Methodology
In our previous work (Prisciandaro et al., 2016), an economic
incentive to reward water reuse projects was presented. Its calcu-
lation was focused on the desalination process implementing, as
feed, the treated effluent from a conventional WWTP. This
approach is now extended to the whole cycle of water treatment
(including wastewater treatment, sludge treatment and disposal)
and successive water reclamation. The incentive I (V/m3 in Eq. (1))
is proportional to the ratio of the actual and the reference energy
efficiency, respectively e and eref, of the processes:
. dynamic and reference values, as the sum of the energy use in-
I ¼ ðP0 =PÞa $cE $E$e eref
where cE is the cost of electricity [V/kWh], E is the electrical energy
consumption [kWh/m3]. The actual process efficiency e, is calcu-
lated from the ratio of the specific energy demand E over the least
“thermodynamic” work Et by fixing the fundamental process vari-
ables (e.g. water composition, flowrate of the “purified” product P,
recovery fraction r). Whereas the reference efficiency eref, the ratio
of the minimum thermodynamic work Et and the Eref of the
representative process, is evaluated on the basis of the best avail-
able technology at the state-of-the-art. This incentive rewards the
most efficient technology and can be seen as the avoided cost of
fresh water production (e.g. through desalination). To consider the
effect of the plant potentiality on the energy footprint, the
correction factor (P0/P) addressing the scale-law of these plants is
included, where P and P0 (product flow rate in m3/day) are the
potentialities of the actual and the reference plants. This factor is
found to be 12.5 P-0.28 for this kind of process in our previous work
(Prisciandaro et al., 2016) if P is expressed in m3/h.
In addition to the costs, the promotion of water reuse involves
several legal and cultural barriers, with significant territorial dif-
ferences (Gao et al., 2014; Plappally and Lienhard V, 2012; Young
and Loomis, 2014; Adar et al., 2015; Molinos-Senantea et al.,
87
2011; Winpenny, 1997; http://ec.europa.eu/envir). The Waste water
is a mixture rich in water (~99% in mass) and many other com-
pounds (~1% in mass). Conventionally, it is assumed that in WWTP,
this mixture is transformed into minerals, carbon dioxide, biosolids
(the biologically generated volatile suspended solids) and inerts
(Garrido et al., 2013). The national and local normatives regulate
the concentration of several compounds in the effluents. The EU
Commission is taking important actions to promote the wastewater
reuse including the setting of minimum requirements for irrigation
and the co-financing in innovation project through the Horizon
2020. At the same time, the European Commission proposed new
rules to facilitate water reuse in the EU for agricultural irrigation.
Useful reports and links related to the EU policy development can
be found in the references (http://ec.europa.eu/envir). A compre-
hensive review, including wastewater reuse standards and related
treatment strategies, research in progress, regulations, economics
and public acceptance issues as well as the assessment of risks and
benefits is given by Kalavrouziotis et al. (2013). Generally, the level
of treatment depends on the regulatory framework and the desti-
nation of reclaimed water. From the industrial point of view, the
water quality is controlled by the technology utilizing the
reclaimed water. From the agricultural point of view, differences of
requirements can lead to inequalities for producers entering the
global market with goods irrigated by reclaimed water treated to
different standards in different countries (http://ec.europa.eu/
envir; Garrido et al., 2013). The Water quality benchmarks in-
cludes water uses, treatment processes, achievable contaminant
reductions and water quality objectives are stated by EU water
standards (http://ec.europa.eu/envir; EU-level instruments on wa-
ter reuse, 2016). In the case of aquifers recharging, the reclaimed
water quality underlies the Drinking Water Directive, also including
the micropollutants (heavy metals, pesticides, polycyclic aromatic
hydrocarbons, etc.) potentially dangerous to human health (EU-
level instruments on water reuse, 2016).
The mass and energy balance for each physical, chemical and
biological unit composing the overall WWTR are addressed in the
following. For the sake of clarity, the treatment stages and the
estimation of E values are discussed separately in different sections:
3.1 COD and Nutrient removal, 3.2 Solid Management, 3.3 Removal
of micropollutants, 3.4 Removal of dissolved ions. The energy
consumption is calculated, both in the case of minimum thermo-
(1) tensity of each individual process taking part of the whole system
(Eq. (2)).
WWT AOP RO S
Et;ref ¼ Et;ref þ Et;ref þ Et;ref ±Et;ref (2)
The procedure is independent from the process/technology,
rewards the solutions with the lowest carbon footprint and can be
at the forefront of the most recent developments through the
continuous updating of Eref.
3. Calculation of the energy footprint
3.1. COD and nutrient removal
The estimated values of the electrical use intensity for the
wastewater treatment is in the range 0.30e0.60 kWh/m3 (Garrido
et al., 2013; Wan et al., 2016). Similarly, Sherson & Criddle located
this range at 0.4e0.65 kWh/m3 of which about a half is required for
the oxygen delivery (Scherson and Criddle, 2014). According to
their calculations, the energy stored in the form of chemical bonds
(of the compounds, both dissolved and suspended in the waste-
water) can be of the same order of magnitude (and even higher)
and can be recovered by different routes, such as the anaerobic
88 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96

digestion as well as the thermochemical valorisation of biosolids
(Zhou et al., 2013; Shizas, 2004; Tchobanoglous et al., 2004). This
aspect will be discussed in the following section. The process
scheme, analysed to estimate the reference Energy consumption
Eref, is based on the conventional treatment plant with the anoxic-
aerobic unit operations of nitrification and denitrification,
described by Tchobanoglous et al. (Fytili and Zabaniotou, 2008). The
overall stoichiometry R is given by combining the half reaction for
oxidation of the donor (Rd) with the weighted half reactions for
synthesis (Rs) and energy (Ra). The reactions are catalyzed by en-
zymes present within the cell and produce the energy necessary to
support bacterial growth. The electrons fraction used for cell syn-
thesis is fs and the remaining fraction fe is transferred to the ter-
minal electron acceptor. Only one part of the energy produced
(40e80%) is caught by bacteria, the rest is dissipated as heat
(Scherson and Criddle, 2014; Tchobanoglous et al., 2004). Main
reactions for nitrification and denitrification processes are reported
in the book of Tchobanoglous et al. (2004) and in the cited work of
Sherson and Criddle (Scherson and Criddle, 2014).
R ¼ fe Ra þ fs Rcs  Rd
The thermodynamic limit of the net energy demand (kWh/m3)
has been calculated for each configuration showing a minimum
energy required for oxygen transfer Et ¼ 0.1 kWh/m3 (500 mgCOD/
L, averaged on different process configurations) according to the
work of Scherson and Criddle (2014).
To estimate the electrical energy demand for the reference case,
the specific energy consumption for aeration ECO2 (assuming that
1 kWhr of electrical energy is used to deliver 1 kg of oxygen) should
be multiplied by the actual oxygen demand (Eq. (4)). The oxygen
demand cO2 is estimated through Eq (5) according to the energetic
and kinetic correlation stated by the process analysis of the con-
ventional nitrification-denitrification process (Tchobanoglous et al.,
2004).
WWT
Eref ¼ ECO2 $cO2 þ ECb
 
Y f $k $Y$SRT
cO2 ¼ 1  1:42 þ d d
1 þ kd $SRT 1 þ kd $SRT
 
NOx Yn
þ $ 4:33 
ðS0  SÞ 1 þ kdn SRT
where the description of the kinetic and thermodynamic constants
and the selected parameters for Eq. (5) are reported in Table 1. For
all configurations, the baseline energy required for plant operation
(pumping, screening, settling and disinfection) is fixed at
ECb ¼ 0.23 kWh/m3 according to the literature estimation
(Scherson and Criddle, 2014; Zhou et al., 2013).
3.2. Solids management
In a typical configuration, the biosolids removed during primary
treatment (particulate bCOD) and secondary settling (biomass) are
mixed, thickened, and subjected to methane fermentation in an
anaerobic digester. The thermodynamic energy content of the
biosolids per m3 of treated wastewater has been estimated in
relation to the COD content, EtBS ¼ 11e15 kJ/gCOD (Giwa et al., 2017;
Wan et al., 2016; Scherson and Criddle, 2014). It is important to
notice that this theoretical value does not represent an energy
consumption but an energy content and therefore, if considered in
this estimation of energy requirements, it should be taken as a
negative number. This value is close to the energy content esti-
mated from the stoichiometric reaction of equivalent-CH4, around
14 kJ/gCOD or 3.88 kWh/kgCOD (Garrido et al., 2013). In wastewater
(3)
streams this is equivalent to 1.9 kWh/m3 for a COD concentration of
500 mg/L as confirmed by the potential energy estimation in me-
dium strength U.S. wastewater of 1.96 kWh/m3 (Shizas, 2004) and
the postulation of sewage energy content of 1.7 kWh/m3 in sewage
(Garrido et al., 2013).
On the other hand, the energy consumption in conventional
process is around 3.2 kJ/gCOD. It is nearly 4-fold lower than the free
energy content of COD. These numbers potentially suggest that
WWTPs may be energy self-sufficient so long as 20% of the total
energy in wastewater could be completely converted. At a com-
mercial level, only a small portion of this energy can be recovered
from the anaerobic digestion (of either wastewater or sludge) in the
form of biogas or from the direct thermal valorisation of the
digested biosolids (in the form of thermal energy) (Wan et al., 2016;
Scherson and Criddle, 2014; Zhou et al., 2013; Shizas, 2004;
Tchobanoglous et al., 2004). A schematic representation of these
(4)
concepts regarding the energy flow distribution is reported in
Fig. 2.
Sludge is a mixture of microorganisms, suspended and dissolved
organic matter as well as minerals (dissolved ions) in a dilute
(5)
mixture (up to 99% of water); the solid concentration is about
0.10 kg/m3 (as order of magnitude) of solids in municipal and
“light” industrial wastewater (treated), depending on the kind of
sludge. Anaerobic digestion stabilizes biosolids and minimizes the
volume for transport and disposal. Electrical energy and heat is

Table 1
Process Parameters for the evaluation of the EWWT.

Process variable value unit


T, temperature 15 C
pressure 95.6 kPa
SRT, Sludge retention time 12 day
kd, Endogenous decay coefficient 0.12 g SSV/gSSV d
SF, TKN peak/TKN 1.50 e
fd, fraction of biomass that remains at cell debris 0.15 g/m3
MLSS, concentration of microorganisms 3000 g/m3
OD, dissolved oxygen concentration 0.50 g/m3
mmax, maximum specific growth rate 6.00 gSSV/gSSV d
Ks, half-velocity constant 20.00 gN-NH4/m3
Y, Synthesis yield coefficient 0.40 g SSV/gNNH4
Kd, Endogenous decay coefficient 0.12 g SSV/gSSV d
m, specific bacterial growth rate 0.75 gSSV/gSSV d
kn maximum specific substrate utilization rate 0.74 gN-NH4/m3
Yn nitrifying biomass yield coefficient 0.12 g SSV/gNNH4
kdn endogenous decay coefficient for nitrifying organisms 0.08 g SSV/gSSV d
K0 oxygen inhibition coefficient 0.50 g/m3
 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
Fig. 2. Energy flow distribution considered for the evaluation of the minimum thermodynamic work in the biological degradation of waste water, extended from the literature
(Scherson and Criddle, 2014).
recovered by the production of biogas followed by its oxidation
with combined heat and power: the conventional 35:65 split
assumed between electricity and heat production with a relevant
portion of this latter lost into the environment (Gao et al., 2014;
Scherson and Criddle, 2014). Some heat is lost into the environ-
ment (thermal losses up to 10%), another portion is then used to
heat up the water (for anaerobic digestion) and for drying of solids.
The sludge is typically dewatered mechanically from the 4e5% to
the 20% of dry solids to be transported to a landfill or sent to a
thermal valorisation process (thermochemical conversion block in
the flow diagram of Fig. 2) (Scherson and Criddle, 2014). Histori-
cally, the land disposal of biosolids (treated sewage sludge) is the
most frequently implemented option for sludge management and
contributes to the nutrient recovery (Fytili and Zabaniotou, 2008).
On the other hand, the disposal has become less attractive because
of the land availability, the transport cost and the always more
stringent regulations on the pollutants detected in the recycled
materials.
The thermal conversion processes become fundamental in the
integrated management of wastes to reduce the volume whereas
recovering the energy content from unrecyclable materials. In the
Waste-to-energy (WtE) sector, the direct power generation by
means of combustion is of great interest from the thermodynamic
point of view in spite of the issues related with the pollutant
emissions (Barba et al., 2015). Although associated with lower po-
wer production and higher complexity, the gasification of solid
wastes is a valid alternative in this framework enabling the
reduction of waste amount to disposal and the enabling strategies
for the syngas utilization (Barba et al., 2011, 2016). The sludge
gasification can be performed in steam, air or CO2/O2 to producing
syngas or biofuel with different configurations and source of
thermal energy and has been well demonstrated at pilot and in-
dustrial scales (Fytili and Zabaniotou, 2008; Barba et al., 2011, 2015,
2016; Lumley et al., 2014; Shatir et al., 2017; He et al., 2013). The
fundamentals of the three main routes of sewage sludge thermo-
chemical conversion (pyrolysis, gasification and combustion) have
been reviewed in the cited literature (Shatir et al., 2017). Further-
more, hydrothermal carbonization (HTC) is considered a viable
conversion process for treating and stabilizing waste streams
(including sludge/biosolids) while producing residual solid with
high energy content (hydrochar) (He et al., 2013).
From the analysis of the integrated cycle with energy recovery
from biosolids (represented in Fig. 2), the reference value of the
energy recovery can be estimated through the following equation:
BS
Eref ¼ EAD þ ETV  EWE
By assuming a conventional fraction of the total COD form primary
89
and secondary settling converted into methane (multiply the
fraction fe by input bCOD) in the ratio 0.25 g methane per g COD and
by assuming that only about the 35% of the chemical energy of
methane (0.015 kWh per g whit O2 as oxidant) can be converted to
electricity through combustion in gas engine, the net electrical
energy output is 1.6 kJ/gCOD.
As aforementioned, this simple calculation implies that the
practical recovery limit for WWT is around the 10% of the total
potential free energy (Ets ¼ 11e15 kJ/gCOD) in typical domestic
wastewaters. The portion of the energy content implemented for
the drying of biosolids has been accounted by subtracting the water
evaporation energy EWE. To evaluate the reference value of the
energy recovered by thermochemical valorisation process ETV , it is
possible to implement our algorithm, based on the calculation of
the Gibbs free Energy gradient and validated on experimental tests
obtained in rotary kiln and downdraft gasifiers for different kind of
wastes ½40; 41. The gasification starts to present a positive energy
balance below the 15% of water content in the stabilized solids in
agreement with the literature (Scherson and Criddle, 2014). On the
other hand, practically speaking, only a small portion (below the
10%) of the energy content in the influent can be recovered through
gasification of the digested and dried sludge. To eliminate the un-
certainties that still lie in the technical-economical evaluation of
these solutions, this contribution will not be considered in the
calculations that follow. Moreover, at the moment there is not a
clear thermodynamic methodology to account for the positive
contribution of producing soil-improvers and/or nutrient recovered
from the digestate (both solid and liquid streams).
3.3. Removal of micropollutants
In parallel to biochemical oxidation, the disinfection and the
oxidative control of organic micropollutants as well as inorganic
contaminants and “aesthetic parameters” (such as iron(II) and
Mn(II), color, taste and odor) may occur in WWTPs (von Gunten,
2018). Synthetic organic compounds (micropollutants) cause spe-
cial attention due to their widespread detection in drinking water
sources (also thanks to the development of analytical techniques)
(von Gunten, 2018). Contaminants of emerging concern at very low
concentration (mg/L), including bacteria, pesticides, biocides,
pharmaceuticals and personal care products, are recently detected
and quantified in the effluents of WWTPs (Belgiorno et al., 2007).
Many chemical compounds can be toxic, carcinogenic or can act as
endocrine disruptors; therefore, they are causing an emerging
concern regarding the impact on aquatic life and human health
(6) (von Gunten, 2018; Belgiorno et al., 2007; Capocelli et al., 2013).
The elimination of micropollutants, often bio-refractory, in
WWTP has been among the main water-related research topics in
90 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
the last years (Capocelli et al., 2012, 2013, 2014; Lofrano, 2010;
Virkutyte et al., 2010; Bourgin et al., 2017a, 2017b; Bolton et al.,
2001; Chonga et al., 2012). The treatment principles beside
micropollutant abatement in the clarified effluent rely on physical,
oxidative, adsorptive and biological processes. Several studies point
out the prominent role of advanced oxidation processes (AOP),
tested for a wide range of biorefractory contaminants and operating
near ambient temperature and pressure through the release of
highly oxidative species, $OH radicals (Belgiorno et al., 2007;
Capocelli et al., 2013).
The most consolidated solutions implement the use of hybrid
techniques based on H2O2, UV, O3 and Fenton chemistry (von
Gunten, 2018; Belgiorno et al., 2007). In the framework of direct
potable reuse in California, all of the suggested treatment trains
include an ozonation and/or UV/H 2O2 process (combined with
reverse osmosis) for disinfection and the abatement of micro-
pollutants (von Gunten, 2018).
Capocelli et al. tested the cavitation, both ultrasonic (Capocelli
et al., 2012) and hydrodynamic (Capocelli et al., 2014) for the
degradation of priority pollutants and pharmaceuticals. Different
solutions of AOPs supported by sunlight are described in the cited
literature (Lofrano, 2010). This final abatement step can be also
realized though biologically active filter with activated carbon
(BAF), adsorption by activated carbon (GAC, PAC) with or without
ultrafiltration (UF) and can be followed by an additional biological
degradation treatment, since the oxygen-rich by-products, after an
AOP, are often easily biodegradable (Bourgin et al., 2017a, 2017b).
These processes can be realized into different combinations; a
simplified process scheme is represented in Fig. 3.
Clearly, both for ozone and UF technology, the operation of this
additional treatment causes an increased energy use. Also for
adsorption-related technologies (PAC, GAC, BAF), the production
and regeneration of activated carbon requires non-negligible
amounts of energy. Including these additional treatment to
remove micropollutants, the climate impacts of different configu-
ration in different scenarios for a WWTP varies from 10 to 40 CO2
eq/m3 of water (Virkutyte et al., 2010).
Due to the chemical stability of these compounds, the large
variability in concentration, chemical structures and by-products
and due to the differences in the $OH formation pathways of each
removal technology, many difficulties arise in the evaluation of
electrical energy consumption related to the removal of these kind
of pollutants. Bolton et al. (2001) proposed the use of the electrical
energy per order EEO and gave a first comprehensive review of the
methodologies for the estimation of the theoretical energy con-
sumption in the case of AOP.
AOP Pel
EEO ¼
Q logðci =co Þ
Fig. 3. Simplified process scheme of post-biodegradation treatment and micropollutant abatement extracted from (von Gunten, 2018; Virkutyte et al., 2010; Bourgin et al., 2017a).
As example, the theoretical limit for EEO in the UV/H2O2 degra-
dation of trichloroethene (TCE) 100 mg/L (2.94 mM) (1-kW lamp
with 25% UV power efficiency in the 200e300 nm region) is
0.034 kWh/m3 (Bolton et al., 2001). The actual EEO for industrial
processes can differ by one or two orders of magnitude. Depending
on several factors such as temperature, materials, purity of oxygen
supplied, as well as construction details of ozone generator, the
energy demand for ozone generation can be more than 2 kWh/m3
(Bolton et al., 2001; Chonga et al., 2012; Sievers). Chong et al.
estimated specific energy for wastewater treatment in the case of
ozonation at 11.93 kWh/m3, O3/UV at 6.15 kWh/m3, H2O2/UV at
0.23 kWh, photocatalysis at 7.09 kWh/m3 (Chonga et al., 2012;
Sievers). According to von Gunten the UV/H2O2 process has a EEO
of 0.17e2.3 kWh/m3 and the O3/H2O2 process a EEO in the range
0.04e0.25 kWh/m3 (von Gunten, 2018). Capocelli et al., reported an
EEO of 80 kWh/m3 for the degradation of PNP by pure hydrody-
namic cavitation; this value can be decreased by an order of
magnitude by the application of hybrid techniques including cavi-
tation and H2O2 or O3 (Capocelli et al., 2014; Sievers, 2011).
For simplicity, most studies on pollutant oxidation are focused
on the disappearance of target compounds and are carried out in
ultrapure water (von Gunten, 2018; Belgiorno et al., 2007; Capocelli
et al., 2013; Capocelli et al., 2012; Capocelli et al., 2014; Lofrano;
Virkutyte et al., 2010; Bolton et al., 2001; Chonga et al., 2012;
Sievers, 2011). However, under realistic conditions, the largest
fraction of chemical oxidants is consumed by dissolved organic
matter (DOM) (von Gunten, 2018; Bourgin et al., 2017b). Therefore,
the oxidation does not yield full mineralization of target com-
pounds but generates transformation by-products (bromate and
oxygen-rich compounds such as aldehydes, ketones and carboxylic
acids) (von Gunten, 2018; Bourgin et al., 2017a; Bourgin et al.,
2017b). For the scope of this procedure, the reference consump-
tion has been linked to the most consolidate process (ozonation) by
Eq. (8).
AOP
Eref ¼ EO3 $DO3 $½DOM (8)
where the energy required for an ozone exposure is calculated by
multiplying the ozone generation EO3, in the
range 0.018e0.026 kWh g1 in a model reactor (Rosenfeldt et al.,
2006), by the ozone dose, obtained by multiplying the specific
dose DO3 (gO3/gDOM) times the DOM concentration (mg/L). These
values have been estimated both theoretically and experimentally
in the literature (Bourgin et al., 2017a; Bourgin et al., 2017b; Bolton
et al., 2001; Chonga et al., 2012; Sievers).
As aforementioned, the oxidation processes are not selective to
specific target compounds and the actual efficiency eref falls below
(7) the 2e3% (von Gunten, 2018). Eq. (9) defines the reference effi-
ciency by considering the scavenging of produced OH radicals by a
 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96 91

generic substrate S. 4. Results and discussion

kOH;M ½M 4.1. Process analysis of the water reuse process

eref ¼ P (9)
kOH;M ½M þ kOH;S ½S
S The basic design of the treatment and reuse plant with the in-
vestment and operating costs are presented to discuss the cost of
Where S is the scavenger concentration (e.g. DOM, alkalinity, ni-
water for different plant size. Following the proposed procedure,
trate …). An extensive work focusing on the $OH generation and
the incentive has been analysed by applying the algorithm at
availability for oxidation (in O3/H2O2 and UV/H2O2) is presented by
different scales (relative to 8000e160000 inhabitants). As above-
(Rosenfeldt et al., 2006).
mentioned, in order to perform a first “conventional” case study
and for sake of clarity, the overall system does not include the
3.4. Removal of dissolved ions advanced oxidation of micropollutants and the thermal valorisation
of the biosolids. Further considerations regarding this assumption
In our previous paper (Prisciandaro et al., 2016) the calculation have been addressed in section 4.4.
of the minimum “thermodynamic” work, required to separate the Table 2 shows the main parameters of the wastewater influent
water from the saline solution through a reversible process, is to the WWT plant. This latter is based on the process described in
defined from the Gibbs energy difference DG between the saline the previous sections and depicted in Fig. 5. The process is thought
and the desalted water (Eq. (10)). On the other hand, the techno- to remove COD and nitrogen by the anoxic-aerobic unit operations
RO has been estimated assuming the reverse osmosis
logical work Eref of nitrification and denitrification (Tchobanoglous et al., 2004). The
treatments include a screening stage to separate the coarse parti-
(RO) process as the reference technology. Accordingly, the actual
cles, the nitrate reduction stage with contemporary oxidation of the
energy required to separate the water from the solute is defined by
organic content as well as two settler stages. The final nitrate
Eq. (11).
concentration is controlled by the recirculation from the Nitro-
nð2 Denitro outlet. The effluent is eventually sent to the secondary
EtRO ¼ DG ¼ RT$ ln aw dn (10) settler to separate the treated water from the secondary flocs and
biosolids (sludge). This latter is sent (after a thickening process) to
n1
the anaerobic digestion reactor (followed by the conditioning and
  mechanical dewatering) to stabilize and dehydrate the sludge. The
1 J
RO
Eref ¼ $ D þ Dp (11) treated water separated from the sludge treatment is sent to the
36:7rh K main WWT line. As aforementioned, the CH4 recovery from the
sludge has not been considered in the calculations of the global
where the minimum thermodynamic work Et practically represents energy flows. The disinfection is realized by hypochlorite. Because
the value that Eq. (11) assumes with an infinite-surface membrane of the cited uncertainties, at the present no micropollutants (and
(JD ¼ 0). Further details can be found in our previous paper related treatments) have been considered in this procedure
(Prisciandaro et al., 2016) as well as in the cited literature (Plappally (further considerations regarding AOP implementation can be
and Lienhard V, 2012). The trend of the minimum work Et, required found in Section 4.4). The RO plant is realized with two stage
to separate n moles of water in a way independent from the used modules (low pressure brackish RO, Low fouling RO membrane)
technology is reported Fig. 4 as a function of salinity (at T ¼ 25  C). with two pre-treatment units, multimedia and cartridge filters,
high-pressure pump units, dosing units to adjust pH, alkalinity,
hardness and antiscaling potential as well as membrane flushing
2.5
and cleaning unit, as depicted in our previous work (Prisciandaro
et al., 2016). The procedure has been implemented with the com-
mercial software Hydranautics IMSDesign™. The effluent and
2 concentrate salinity specification are reported in Table 3.
Table 4 reports the results of the energy footprint and related
efficiencies. The process efficiency in the WWT is higher because
the thermochemical conversion of the biosolids (producing a
1.5 negative energy consumption EC) has not been considered in this
Et, kWh/m3

preliminary conservative calculation. The efficiency of the RO

reclamation plant is in agreement with our previous work
(Prisciandaro et al., 2016).
1

0.5
Table 2
Average characteristics of the waste water.

Process variable value Unit

0 T 15 
C
0 20 40 60 80 100 COD 400.00 mg/L
recovery raƟo, ρ bCOD 300.00 mg/L
sbCOD 140.00 mg/L
sCOD 140.00 mg/L
200 ppm 1000 ppm 35000 ppm
iCOD 100.00 mg/L
TKN 25.00 mg/L
Fig. 4. Least “thermodynamic” work as a function of recovery ratio r and salinity
EtRO
N-NO3 15.00 mg/L
expressed as NaCl concentration [ppm] at T ¼ 25  C.
92 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96

recycle Secondary Settler

Influent Primary settler

Effluent to
disinfection

Nitro-Denitro

Air

Return Sludge
Biogas

Recovered Sludge Anaerobic digestion

Concentrate

Fig. 5. Schematic of the biological WWT process here considered as state-of-the-art technology.

Table 3 Table 5
Average characteristics of the Feed, Permeate and Concentrate of the RO Reclama- Business Plan evaluation of the Water Reclamation Plants at different installed ca-
tion Plants assumed in this work. pacity. Cost of electricity CE ¼ 0.08 V/kWh, sludge disposal at 55 V/ton; depuration
fee (income) at 0.69 V/m3.
ions Feed (ppm) Concentrate (ppm) Permeate (ppm)
kV/yr 100 m3/h 500 m3/h 2000 m3/h
Ca2þ 75.0 373.3 0.33
Mg2þ 3.30 14.90 0.01 Revenues from Depuration 604 3022 12,089
Naþ 33.2 162.3 0.69 Ancillary Revenues from Water Reuse 221 618 1691
Kþ 4.00 19.60 0.10 Total Revenues 825 3640 13,779
NHþ 4 8.00 39.20 0.21 Electrical energy WWT (44) (219) (1052)
Ba2þ 0.00 0.00 0.00 Electrical energy Reuse (122) (367) (832)
2þ
Sr 0.00 0.00 0.00 Spare parts (membrane replacement) (7) (35) (139)
CO2-3 0.10 0.40 0.00 Chemicals (45) (222) (999)
HCO 3 111.9 554.5 1.38 Personnel Costs (120) (450) (900)
SO2-4 42.30 209.7 0.07 Fixed O&M Costs (52) (175) (524)
Cl 98.20 492.3 0.68 Sludge Disposal (60) (298) (1190)
F 3.30 14.80 0.04 Other Cost & Overhead (39) (194) (778)
NO 3 20.4 96.00 1.00 Total cost (548) (2178) (6886)
SiO2 1.30 5.00 0.01 EBITDA no incentive 57 845 5203
EBITDA with incentive 366 1826 7870
NOPAT (with incentive) 292.0 1750.5 8570.8

Table 4
Results of the process analysis including both WWT and RO and evaluation of the
thermodynamic limit and related efficiencies. previous work (Prisciandaro et al., 2016), the cost of investment has
Et Eref eref E e been calculated and reported in Fig. 6 (capex estimation) for the
WWTP, the RO and the Integrated Reclamation Plant.
WWT 0.10 0.37 27% 0.54 19%
RO 0.01 0.66 1% 0.83 1% Globally, the return of investment (ROI) is satisfactory even at
tot 0.11 1.03 11% 1.37 8% lower installed capacity (considering the overall context of water
technologies). The ROI for the smallest installed capacity is 8% and
increases up to 27% for the biggest size investigated. On the other
4.2. Business plan of the water reuse process hand, despite the incentive, the plant with the lowest installed
capacity shows a balanced budget (very low net profit), such as not
The water cost calculation and the business plan that includes to be attractive to a private investor, if not encouraged or forced by
the proposed incentive (“ancillary revenues”) is reported in Table 5. external factors. In addition to any obligations imposed by gov-
The Earnings Before Interest, Taxes, Depreciation and Amortization ernment agencies, some external factor forcing the reuse at very
(EBITDA) and the Net Operating Profit After Taxes (NOPAT) are re- low scales may be the lack of a receiving water body and/or a
ported (at the bottom) to evaluate the profit generated by the sewage system as well as the company's environmental policies.
WWTR Plant. Nonetheless, the incentive is higher at lower potentiality and try to
The economic incentive goes from 0.19 V/m3 to 0.44 V/m3 reward small projects for decentralized WWTR. Furthermore, the
respectively for the plant potentiality of 2000 m3/h and 100 m3/h higher the cost of electricity, the lower the water production cost
increasing the profitability of smaller plants where the final overall after incentives. These peculiarities are intrinsically linked to the
cost of water reclamation is higher. This cost assumes the values of proposed calculation methodology, which tends to reward energy
0.491, 0.621, 0.782 V/m3 respectively for 100, 500, 2000 m3/h of saving solutions.
installed capacity. From the basic design, also discussed in our
 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96 93

35000 4.4. Water “price” calculation

Eventually and with a different (“market-driven”) approach, the

30000
estimation of a possible “acceptable price” of the water source is
proposed. This method is based on the profitability of the WWTR
25000 projects, hence a fixed return of investment (ROI) is assumed to
Investment Cost [k€]

start the calculation. The same economic procedure implemented

20000
15000
10000
5000
0 stored, and delivered by a (municipal) water supply systems, it
500 1000
Installed capacity [m /h]
Fig. 6. Investment cost vs. Installed capacity for RO, WWT and Integrated WWTR
Plants.
4.3. Sensitivity analysis
Fig. 7 summarizes the aforementioned features of the incentive.
The economic results have been repeated for different energy pri-
ces and water depuration fees (sensitivity analysis). The results
summarize the cost of water by considering the variation of fees
and incentive (by varying the independent variable “cost of elec-
tricity”, V/kWh) in the range under consideration: the upper limit
of each sector refers to a null incentive, while the lower limit to the
maximum cost of electricity (0,15 V/kWh). Compared to our first
implementation of this approach (Prisciandaro et al., 2016) the
novel incentive has a stronger size-effect. The calculate cost of
produced water is below the reference values of seawater desali-
nation with the additional environmental benefit of avoided
emissions (discharge of the WWT effluent as well as brine from
desalination).
to study the effect of the incentive, is applied to estimate the price
of water considered “acceptable” to produce a fixed return of the
investment. In other words, what is the highest possible cost the
water-source should have to make the project economical feasible.
With this approach, considering water as a commodity, it is
possible to compare different kind of “sources” and different kind of
projects able to obtain the same product. The comparative analysis
includes both the wastewater and the saline water as the sources.
RO The freshwater is the product, with a fixed price of 1 V/m3.
WWT Water pricing in different countries can be fixed by a “full recovery
Integrated cost” method and/or as a consequence of public resources to
finance the water sector. After being captured, filtered, treated,
1500 2000
typically costs less than US 0.50 $/t (Kalavrouziotis et al., 2013). This
3 value can vary by an order of magnitude (from 0.1 to 1 V/m3)
depending on the local policies, electricity cost and water afford-
ability. Veolia, starting from the consideration that the 70% of the
world's GDP will be produced in water-scarce regions by 2050,
proposed the calculation of the “true cost of water” to help com-
panies mitigate production risks whilst optimising environmental
impacts (Adar et al., 2015). The value of 1 V/m3 here adopted is an
arbitrary choice “of common sense” to establish an economic re-
turn from the production of reused water and clearly depends on
the characteristics and the type of use of the produced water.
The results in Fig. 8 could represent a first tentative to propose a
technical-based calculation method. The reference conditions have
been fixed according to the previous calculation including medium
strength wastewater (WASTEWATER I). The second stream is
SEAWATER (@ 35000 ppm) that undergoes pre-treatment and
Reverse Osmosis Desalination. An additional case (WASTEWATER
II), including medium strength wastewater with residual concen-
tration of 500 mg/L of micropollutants, has been considered to
include the impact of AOP on the energy consumption. For this
stream, the process investigated by Bourgin et al. (2017a), recom-
mending a specific ozone dose of 0.55 gO3/g DOC to ensure an

1.2 1.2
a) no incentive b) no incentive
cE = 0.04 €/kWh cE = 0.04 €/kWh
1.0
cE = 0.08 €/kWh cE = 0.08 €/kWh 1.0
water appreciation €/m 3
water appreciation €/m 3

cE = 0.12 €/kWh cE = 0.12 €/kWh

0.8
cE = 0.16 €/kWh cE = 0.16 €/kWh
0.8

0.6

0.6
0.4

0.4
0.2

0.0 0.2
0 500 1000 1500 2000 0 500 1000 1500 2000

Flow rate of produced water [m3/h] Flow rate of produced water [m3/h]

Fig. 7. Cost of reclaimed water versus Plant potentiality (m3/h) at different incentive (varying the electrical energy price) and two values of the treatment fee: a) 0.20 V/m3; b) 0.40
V/m3.
94 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
1.0
0.8
0.6
water price [€ m ] 0.4
-3
0.2
0.0
-0.2
-0.4
-0.6
-0.8
-1.0
500
Plant capacity [m3 h-1]
Fig. 8. True value of water vs. water withdrawal (as plant capacity).
average 80% abatement of the twelve selected substances in a Swiss
WWTPs, has been implemented. Two ROI levels have been
considered: 5% and 10%. Results are reported in Fig. 8.
The seawater has a higher economical value than wastewater if
the depuration fee is not included in the business plan. Moreover,
the wastewater containing micropollutants (WASTEWATER II) has a
lower economic value than the medium strength wastewater
described in Table 1. For potentiality below 750 m3/h, no cost of the
water source can be addressed in order to avoid a “very poor” in-
vestment in Water Reuse Projects. In other world, the feed water
should have no economic value to make the investment profitable.
At this potentiality, the incentive to reuse it is even more necessary.
On the other hand, the Water Desalination and Reclamation ini-
tiatives at higher installed capacity are able to pay a small amount
for the water source: (around 0.4 V/m3 for seawater and around 0.7
V/m3 for medium strength wastewater).
By considering different water composition and different use of
the “water-as-product” a continuous graph could be realized: the
higher the salinity the lower the value of water; similarly the higher
the “strength of wastewater” and contents of micropollutants, the
lower the acceptable value of water.
5. Conclusions
Despite the emergency of water scarcity, the man's choices have
always been directed towards the disequilibrium of this vital
resource; drinking water is far from being a right for everyone and
is rather scarce and poorly distributed in many areas of the world.
In this work, a water cost evaluation based on the energetic
equivalence among all the possible treatment strategies, water
sources and water end-uses, has been proposed for evaluating in-
vestment strategies in the water cycle with a cross-cutting
approach.
An economic incentive is proposed on the basis of the ther-
modynamic and process analysis of a Wastewater Treatment &
Reuse (WWTR) Plant. The methodology considers the global water
cycle with a water-energy integrated approach, practically
Wastewater I (5% ROI)
Wastewater I (10% ROI)
Wastewater II (5% ROI)
Wastewater II (10% ROI)
Seawater (5% ROI)
Seawater (10% ROI)
1000 1500 2000
extending our previous work (that addressed only desalination
processes) to the thermodynamics of the WWT for small, medium
and large municipalities in order to define the economic incentive
and to evaluate the effect of the main economic drivers on the
business plan.
By calculating the energy footprint of processes in-series and by
comparing it to the maximum “thermodynamic” efficiency (with
the goal to reward the decarbonization pathway in the water
sector), the proposed approach does not depend on the chosen
technology and can be also implemented to address the “true value
of water”.
Globally, the water reuse projects can be considered attractive
thanks to the proposed incentive for installed capacity >200 m3/h;
smaller plants suffers of the economy of scale. The estimation of the
“true value of water” in a future water trading system is done by
addressing the acceptable cost of “water-as-a-commodity” in a
reclamation plant (in relation to the plant size, water characteris-
tics, depuration fees, cost of electricity).
According to the presented results, the Desalination and Recla-
mation initiatives at the medium-high installed capacity are able to
pay a small amount for the water source: (around 0.4 V/m3 for
seawater and around 0.7 V/m3 for wastewater including depu-
ration fee).
It should be noted that also for the final product (freshwater)
different quality specifications can be implemented depending on
the intended use.
To understand the economic value of water is not in contrast
with the social view of public water but is important (for policy-
makers, users as well as managers) to efficiently allocate this
precious source and to promote R&D for its safeguard and to
decarbonize the water sector. As a matter of fact, the water, as a
commodity, generates an economic value. The World Bank reported
the yearly water productivity at around 20 US$ GDP per cubic meter
of the withdrawn freshwater from a very lower value, around 3
$/m3, assumed in the 60's. The proposed approach promotes small-
scale and decentralized solution of water treatment & reuse
because:
 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96 95

 the smaller the plant, the higher the incentive per m3 of water Yn Synthesis yield coefficient for denitrification, gVSS/
 the lower the energy footprint of the process, the higher the gbsCOD
incentives per m3 of water
 the higher the electricity cost, the higher the incentives per m3 Greek letters
of water h pump efficiency, dimensionless
 the approach rewards solutions that reduce discharges and r recovery rate, dimensionless
related environmental impacts. p osmotic pressure, Pa

Some innovations in this field to obtain a positive energy bal-

Subscripts
ance in the integrated process are the side-stream treatment to
ref Reference value
upgrade the nitrogen removal as the CANON process, well
t Minimum thermodynamic value
described in the cited literature. The limit of profitability at very
Superscripts
low scales should be addressed by including the energy recovery
AOP Relative to the Advanced Oxidation Process
from the WWT. Further works are needed to include and validate
AD Relative to the Anaerobic digestion Process
this economic incentive in the case of “energetic” valorisation of
RO Relative to the reverse osmosis process
solids in the WWT. The thermodynamic evaluation of the value can
S Relative to the solid management
promote the: i) decreasing of water losses; ii) transnational and
TV Relative to the thermal valorisation process
transboundary cooperation on water project; iii) protection of
WE Relative to the water evaporation process
natural reservoirs of high-quality water; iv) attraction of venture
Acronyms & Abbreviations
capitals in this sector; v) revenues from wastewaters and conse-
AOP Advanced Oxidation Process
quently the promotion of waste water treatment (independently
WWT Waste Water Treatment
from any directive). Moreover, to “technically address the true
WWTR Waste Water Treatment & Reuse
value of water” is fundamental to: i) charge rich countries the real
RO Relative to the Reverse Osmosis Process
price of financing water technologies and infrastructure, ii) adopt
S Relative to the Solid Management Process
strategies to preserve the water consumption and to equally
distribute it iii) exploring the most feasible technology first (from
both the economic and environmental point of view). References

Abdullah Alkhudhiri, A., Darwish, N., Hilal, N., 2013. Produced water treatment:
application of air gap membrane distillation. Desalination 309, 46e51.
Abramson, A., Tal, A., Becker, N., El-Khateeb, N., Asaf, L., Assi, A., Adar, E., 2010.
Nomenclature Stream restoration as a basis for IsraeliePalestinian cooperation: a comparative
analysis of two transboundary streams. Int. J. River Basin Manag. 8, 39e53.
Adar, E.M., 2015. In: Margolis, Liat, Chaouni, Aziza (Eds.), Bridging the Gap between
aw activity coefficient Available Water and Water Demand: Water Technologies for Agricultural Pro-
cE cost of electricity, V/kWh duction in Israel. Chapter in the Book Out of Water - Design Solutions for Arid
Regions. Birkh€ auser, p. 208.
Ci Inlet concentration, mg/l Asano, T., 1998. Wastewater Reclamation and Reuse: Water Quality Management
Co Outlet concentration, mg/l Library, vol, 10. CRC Press, p. 1528. CRC Press.
cO2 Specific oxygen consumption, g/m3 Barba, D., Prisciandaro, M., Salladini, A., Mazziotti di Celso, G., 2011. The Gibbs free
energy gradient method for RDF gasification modelling. Fuel 90, 1402e1407.
DO3 Ozone dose, g/g
Barba, D., Brandani, F., Capocelli, M., Luberti, M., Zizza, A., 2015. Process analysis of
E specific energy demand, kWhel/m3 an industrial waste-to-energy plant: theory and experiments. Process Saf. En-
ECO2 Oxidation energy consumption, kWh/kgO2 viron. Protect. 96, 61e73.
Barba, D., Capocelli, M., Cornacchia, G., Matera, D.A., 2016. Theoretical and experi-
ECb Baseline energy consumption, kWh/m3
mental procedure for scaling-up RDF gasifiers: the Gibbs Gradient Method. Fuel
e energy efficiency of the actual process, dimensionless 179, 60e70.
fe Moles of e for substrate oxidation per mol e-substrate Belgiorno, V., Rizzo, L., Fatta, D., Della Rocca, C., Lofrano, G., Nikolaou, A., Naddeo, V.,
fs Moles of e for cell synthesis per mol e substrate Meric, S., 2007. Review on endocrine disrupting-emerging compounds in urban
wastewater: occurrence and removal by photocatalysis and ultrasonic irradia-
fd Moles of e for energy production per mol e of tion for wastewater reuse. Desalination 215, 166e176.
substrate Bolton, J.R., Bircher, K.G., Tumas, W., Tolman, C.A., 2001. Figures-of-merit for the
G Gibbs free energy, kJ/kg technical development and application of advanced oxidation technologies for
both electric- and solar-driven systems (IUPAC Technical Report) Pure Appl.
JD permeate flux, m3/m2 h Chem 73, 627e637.
k correction factor, dimensionless Bourgin, M., Beck, B., Boehler, M., Borowska, E., Fleiner, J., Salhi, E., Teichler, R., von
kd Endogenous decay coefficient, gVSS/sVSS day Gunten, U., Siegrist, H., McArdell, C.S., 2017. Evaluation of a full-scale waste-
water treatment plant upgraded with ozonation and biological post-
knd Endogenous decay coefficient, gVSS/sVSS day treatments: abatement of micropollutants, formation of transformation prod-
K membrane permeability, m3/m2 h Pa ucts and oxidation by-products. Water Res. https://doi.org/10.1016/
n moles of water j.watres.2017.10.036.
Bourgin, M., Borowska, E., Helbing, J., Hollender, J., Kaiser, H.-P., Kienle, C.,
NOx Effluent NOx concentration, mg/L McArdell, C.S., Simon, E., von Gunten, U., 2017. Effect of operational and water
P Reclaimed water production, m3/h quality parameters on conventional ozonation and the advanced oxidation
Pel Electrical power, kWh process O3/H2O2: kinetics of micropollutant abatement, transformation prod-
uct and bromate formation in a surface water. Water Res. https://doi.org/10.
Q Water flowrate, m3/h 1016/j.watres.2017.05.018.
Ra Half reaction for electron acceptor Capocelli, M., Joyce, E., Lancia, A., Mason, T.J., Musmarra, D., Prisciandaro, M., 2012.
Rcs Half reaction for cell synthesis Sonochemical degradation of estradiols: incidence of ultrasonic frequency.
Chem. Eng. J. 210, 9e17.
Rd Half reaction for electron donor
Capocelli, M., Prisciandaro, M., Lancia, A., Musmarra, D., 2013. Modeling of cavita-
S0 Influent organic substrate, mg/l tion as an advanced wastewater treatment. Desalin. Water Treat. 51, 1609e1614.
S Effluent organic substrate, mg/l Capocelli, M., Prisciandaro, M., Lancia, A., Musmarra, D., 2014. Hydrodynamic
SRT Sludge Retention Time cavitation of p-nitrophenol: a theoretical and experimental insight. Chem. Eng.
J. 254, 1e8.
T temperature, K Chonga, M.N., Sharma, A.K., Burn, S., Saint, C.P., 2012. Feasibility study on the
Y Synthesis yield coefficient, gVSS/gbsCOD application of advanced oxidation technologies for decentralised wastewater
96 M. Capocelli et al. / Journal of Cleaner Production 207 (2019) 85e96
treatment. J. Clean. Prod. 35, 230e238.
Chung, H.W., Nayar, K.G., Swaminathan, J., Chehayeb, K.M., Lienhard, J.H., 2017.
Thermodynamic analysis of brine management methods: zero-discharge
desalination and salinity-gradient power production. Desalination 404,
291e303.
Cipollina, A., Micale, G., 2016. Sustainable Energy from Salinity Gradients Edited by:
Andrea Cipollina and Giorgio Micale. Elsevier, ISBN 978-0-08-100312-1.
Drioli, E., Ali, A., Macedonio, F., Quist-Jensen, C.A., 2015. Minerals, energy and water
from the sea: a new strategy for zero liquid discharge in desalination. JSM
Environ. Sci. Ecol. 3, 1018.
El-Abbassi, A., Hafidi, A., Khayet, M., García-Payo, M.C., 2013. Integrated direct
contact membrane distillation for olive mill wastewater treatment. Desalina-
tion 323, 31e38.
EU-level instruments on water reuse, 2016. Final Report to Support the Commis-
sion's Impact Assessment. Prepared by:. Amec Foster Wheeler Environment &
Infrastructure UK Ltd, IEEP, ACTeon, IMDEA and NTUA.
Fytili, D., Zabaniotou, A., 2008. Utilization of sewage sludge in EU application of old
and new methodsda review. Renew. Sustain. Energy Rev. 12, 116e140.
Gao, H., Scherson, Y.D., Wells, G.F., 2014. Towards energy neutral wastewater
treatment: methodology and state of the art. Environ. Sci. Process. Impacts 16,
1223e1246, 2014 May.
Garrido, J.M., Fdz-Polanco, M., Fdz-Polanco, F., 2013. Working with energy and mass
balances: a conceptual framework to understand the limits of municipal
wastewater treatment. Water Sci. Technol. 67, 2294e2301.
Giwa, A., Dufour, V., Al Marzooqi, F., Al Kaabi, M., Hasan, S.W., 2017. Brine man-
agement methods: recent innovations and current status. Desalination 407,
1e23.
He, C., Giannis, A., Wang, J.-Y., 2013. Conversion of sewage sludge to clean solid fuel
using hydrothermal carbonization: hydrochar fuel characteristics and com-
bustion behaviour. Appl. Energy 111, 257e266.
http://ec.europa.eu/environment/water/reuse.htm.
Kalavrouziotis, I.K., Kokkinos, P., Oron, G., Fatone, F., Bolzonella, D., Vatyliotou, M.,
Fatta-Kassinos, D., Koukoulakis, P.H., Varnavas, S.P., 2013. Current status in
wastewater treatment, reuse and research in some mediterranean countries.
Desalin. Water Treat. https://doi.org/10.1080/19443994.2013.860632.
Kim, J., Hwang, M.J., Lee, S.J., Noh, W., Kwon, J.M., Choi, J.S., Kang, C.M., 2016. Effi-
cient recovery of nitrate and phosphate from wastewater by an amine-grafted
adsorbent for cyanobacterial biomass production. Bioresour. Technol. 205,
269e273.
Lazarova, V., Levine, B., Sack, J., Cirelli, G., Jeffrey, P., Muntau, H., Salgot, M.,
Brissaud, F., May 2001. Role of water reuse for enhancing integrated water
management in Europe and Mediterranean countries. Water Sci. Technol. 43
(10), 25e33.
Lofrano, G., 2010. Emerging compounds removal from wastewater natural and solar
based treatments. In: Lofrano (Ed.), Giusy SpringerBriefs in Green Chemistry for
Sustainability. ISBN 978-94-007-3916-1.
Lumley, N.P.G., Ramey, D.F., Prieto, A.L., Braun, R.J., Cath, T.Y., Porter, J.M., 2014.
Techno-economic analysis of wastewater sludge gasification: a decentralized
urban perspective. Bioresour. Technol. 161, 385e394.
Mickley, M., 2008. Survey of High-recovery and Zero Liquid Discharge Technologies
for Water Utilities. Water Reuse Foundation, Alexandria, VA, US.
Molinos-Senantea, M., Herna ndez-Sancho, F., Sala-Garrido, R., 2011. Cost benefit
analysis of water-reuse projects for environmental purposes: a case study for
Spanish wastewater treatment plants. J. Environ. Manag. 92, 3091e3097.
OECD, 2012. OECD Environmental Outlook to 2050: the Consequences of Inaction.
ISBN 978-92-64-122161 ©.
Piemonte, V., Prisciandaro, M., Mascis, L., Di Paola, L., Barba, D., 2015. Reverse
osmosis membranes for treatment of produced water: a process analysis.
Desalin. Water Treat. 55, 565e574.
Piemonte, V., Losito, G., Di Paola, L., De Falco, M., Capocelli, M., Prisciandaro, M.,
2017. Produced water treatment technologies: how to compare by LCA meth-
odology. Desalin. Water Treat. 73, 323e329.
Plappally, A.K., Lienhard V, J.H., 2012. Energy requirements for water production,
treatment, end use, reclamation, and disposal. Renew. Sustain. Energy Rev. 16,
4818e4848.
Prisciandaro, M., Capocelli, M., Piemonte, V., Barba, D., 2016. Process analysis
applied to water reuse for a “closed water cycle” approach. Chem. Eng. J. 304,
602e608.
Rosenfeldt, E.J., Linden, K.G., Canonica, S., von Gunten, U., 2006. Comparison of the
efficiency of OH radical formation during ozonation and the advanced oxidation
processes O3/H2O2and UV/H2O2. Water Res. 40, 3695e3704.
Scherson, Y.D., Criddle, C.S., 2014. Recovery of freshwater from wastewater:
upgrading process configurations to maximize energy recovery and minimize.
Resid. Environ. Sci. Technol. 48, 8420e8432.
Shatir, S., Syed-Hassan, A., Wang, Yi, Hu, Song, Su, Sheng, Xiang, Jun, 2017. Ther-
mochemical processing of sewage sludge to energy and fuel: fundamentals,
challenges and considerations. Renew. Sustain. Energy Rev. 80, 888e913.
Shizas, Bagley, 2004. Experimental Determination of energy content of unknown
organics in municipal wastewater streams. J. Energy Eng. 130, 45e53.
Sievers, Michael, 2011. Advanced oxidation processes. Treatise Water Sci. 4,
377e408. https://doi.org/10.1016/B978-0-444-53199-5.00093-2.
Tchobanoglous, G., Burton, F.L., Stensel, H.D., 2004. Wastewater Engineering -
Treatment and Reuse, fourth ed. Metcalf & Eddy, Inc.
The Dublin Statement on Water and Sustainable Development Adopted, January 31,
1992. In: Dublin, Ireland. International Conference on Water and the
Environment.
UNESCO, 2015. Water Reuse: Potential for Expanding the Nation's Water Supply
through Reuse of Municipal Wastewater. The National Academies Press, 500 5th
Street, NW Washington DC 20001.
Virkutyte, J., Varma, R.S., Jegatheesan, V., 2010. Treatment of Micropollutants in
Water and Wastewater IWA. Publishing, p. 520. ISBN13: 9781843393160.
von Gunten, U., 2018. Oxidation processes in water treatment: are we on track?
Environ. Sci. Technol. 52 (9), 5062e5075.
Vourch, M., Balannec, B., Chaufer, B., Dorange, G., 2008. Treatment of dairy industry
wastewater by reverse osmosis for water reuse. Desalination 219, 190e202.
Wan, J., Gu, J., Zhao, Q., Liu, Y., 2016. COD capture: a feasible option towards energy
self-sufficient domestic wastewater treatment. Sci. Rep. 6, 25054.
Water Reuse, 2012. Potential for Expanding the Nation's Water Supply through
Reuse of Municipal Wastewater. The National Academies Press, Fifth Street, NW
Washington, DC 20001.
Wilf, M., 2010. The Guidebook to Membrane Technology for Wastewater Recla-
mation. Balaban Desalination Publications, Hopkinton, USA.
Winpenny, J.T., 1997. Managing Water Scarcity for Water Security. A Discussion
Paper Prepared for the First FAO E-mail Conference on Managing Water
Scarcity.
World Bank's population estimates. World Development Indicators ata.worldbank.
org/data-catalog.
Xuheng, L., Xingyu, C., Lihua, H., Zhongwei, Z., 2015. Study on extraction of lithium
from salt lake brine by membrane electrolysis. Desalination 376, 35e40.
Young, R.A., Loomis, J.B., 2014. Determining the Economic Value of Water: Concepts
and Methods, second ed. Routledge.
Zhou, Y., Zhang, D.Q., Minh Tuyet, L., Puah, A.N., Ng, W.J., 2013. Energy utilization in
sewage treatment - a review with comparisons. J. Water Clim. Change 4, 1e10.