Journal of Membrane Science 375 (2011) 172181

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Journal of Membrane Science
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A novel low energy fertilizer driven forward osmosis desalination for direct
fertigation: Evaluating the performance of fertilizer draw solutions
Sherub Phuntsho
a
, Ho Kyong Shon
a,
, Seungkwan Hong
b
, Sangyoup Lee
b
, Saravanamuthu Vigneswaran
a
a
School of Civil and Environmental Engineering, University of Technology, Sydney (UTS), Post Box 129, Broadway, 2007, NSW, Australia
b
School of Civil, Environmental & Architectural Engineering, Korea University, 1, 5-ka, Anam-Dong, Sungbuk-Gu, Seoul 136-713, Republic of Korea
a r t i c l e i n f o
Article history:
Received 25 November 2010
Received in revised form 21 January 2011
Accepted 19 March 2011
Available online 29 March 2011
Keywords:
Forward osmosis
Desalination
Draw solution
Fertilizer
Fertigation
a b s t r a c t
Forward osmosis (FO) is a novel and emerging low energy technology for desalination. It will be particu-
larly more attractive, if the drawsolution separation and recovery are not necessary after FOprocess. The
application of this newconcept is briey described here in this paper for the desalination of saline water
for irrigation, using fertilizer as a draw agent. Instead of separating the draw solution from desalinated
water, the diluted fertilizer drawsolution can be directly applied for fertigation. We report the results on
the commonly used chemical fertilizers as FO draw solution. Based on the currently available FO tech-
nology, about nine different commonly used fertilizers were nally screened from a comprehensive list
of fertilizers and, their performances were assessed in terms of pure water ux and reverse draw solute
ux. These results indicate that, most soluble fertilizers can generate osmotic potential much higher than
the sea water. The draw solutions of KCl, NaNO
3
and KNO
3
performed best in terms of water ux while
NH
4
H
2
PO
4
, (NH
4
)
2
HPO
4
, Ca(NO
3
)
2
and (NH
4
)
2
SO
4
had the lowest reverse solute ux. Initial estimation
indicates that, 1kg of fertilizer can extract water ranging from 11 to 29L from sea water.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The world population is growing rapidly while the problems
associated with a lack of fresh water is becoming a known
fact affecting drinking water supplies, energy, food production,
industrial output, and the quality of our environment ultimately
underminingthe economies of the worldat large [1,2]. Water is also
essential for improvingthe productivityof agricultural landtomeet
the worlds increasing food demand; however, fresh water scarcity
is a serious issue in many parts of the world. Water shortages are
further exacerbated by the impact of climate change resulting in
frequent drought and unpredictable rainfall events [35].
Nowadays, researches are being focussed on tackling water
issues fortunately offering options in terms of advanced tech-
nologies, using alternative and unlimited water sources such as
impaired water and sea water [1]. Desalination is one of the
advanced technologies, where people have relied for augmenting
the limited fresh water resources. The over searching goal for the
future desalination is to increase the fresh water supply via desali-
nation of sea water and saline aquifers [1].

Corresponding author. Tel.: +61 2 9514 2629; fax: +61 2 9514 2633.
E-mail address: hkshon@eng.uts.edu.au (H.K. Shon).
Although, desalination for drinking water supplies is becoming
common these days, desalination for irrigation is rare. Desalination
using currently available technologies such as thermal distillation
and reverse osmosis (RO) is still energy intensive [69] and there-
fore cannot be considered a cost effective option for large scale
irrigation although signicant improvements have been made in
the last few decades especially in membrane technology. When
water, energy and the environmental issues are all interrelated
[8,9], a desalination technology that consumes much lower energy
is essential especially for large scale irrigation. Addressing of global
water scarcity problems therefore calls for anextensive investment
on research to identify robust and newmethods of purifying water
at lower energy and cost [1]. If low cost desalination technolo-
gies are made available, its impact on the agriculture sector would
be signicant for drought stricken countries like Australia where
saline water is abundant in the form of sea water along the coastal
areas and brackish groundwater in the inland areas.
Forward osmosis (FO) technology is an emerging and a novel
technology for desalination, which has edge over reverse osmosis
(RO) process in terms of energy consumption and fouling resis-
tance [8,1014]. Unlike RO process, where high hydraulic pressure
is required, FO process simply uses the intrinsic osmotic pres-
sure differential between the two solutions of different osmotic
potential (highlyconcentrateddrawsolutionandsaline feedwater)
separated by a semi-permeable membrane to desalinate water.
0376-7388/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2011.03.038
S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181 173
Althoughliteratures onFOmembrane fouling are still scarce, recent
studies indicate that, membrane fouling may not be a signicant
issue for FO process, which is another signicant advantage for FO
over RO process. In the absence of hydraulic pressure, membrane
fouling during FO process is reported to be physically reversible
indicating that chemical cleaning may not be essential for FO pro-
cess like in RO process [1417].
Althoughthenovel concept of FOwas developedas earlyas 1968
[18], it has not been able to advance mainly due to lack of suit-
able FO membranes and lack of suitable drawsolution. The current
asymmetrical membranes used for pressure based ltration result
inconcentrationpolarization(CP) effects that severely decrease the
net osmotic pressure between the two solutions and hence lower
the water ux across the membrane [11,1921]. While external CP
(ECP) that occurs on the membrane surface can be mitigated using
crossow, similar to pressure based membrane ltration system
such as RO, internal CP (ICP) occurs within the porous support layer
of the asymmetrical membranes and therefore cannot be mitigated
[20]. ICP is exclusive to FO process and is said to be mainly respon-
sible for much lower water ux achieved in FO process than the
expected or theoretical water ux [19]. A comprehensive model
to predict the water ux, taking into consideration CP effects is
describedelsewhere[11,2123]. Several signicant researchbreak-
throughs havebeenhowever reportedrecentlyintheFOmembrane
fabrication particularly with thin lm composites and also carbon
nanotube membranes that may provide lower CP effects [2427].
Challenges now still remain related to separation and recov-
ery of the draw solution from desalinated water. The success of
FO desalination in the future especially for drinking purposes, will
rely mainly on how easily and efciently the draw solution can be
separatedandrecoveredfromthe desalinatedwater [28]. However,
where the fate of the drawsolutionafter desalinationby FOprocess
is irrelevant, FO offers a signicant advantage over RO desalina-
tion. For this reason, FO process has been already commercialized
on smaller scale such as in the case of nutrient rich drinks used
for life saving equipments in the boats or during the emergency
such as natural calamities [20]. The same advantage can be capi-
talized if the end use of the FO desalinated water is for agricultural
purpose such as for fertigation or fertilized irrigation. Fertigation
is a method where the crop nutrients/fertilizer in dissolved form
are supplied to the crops through an irrigation network system.
Fertilizers are anyway extensively used in the agricultural produc-
tion and, their use will continue to rise to feed the growing world
population [29,30]. In such a situation, fertilizer can be used as a
draw agent for FO process because the diluted draw solution can
be directly appliedfor fertigation. This concept offers several novel-
ties: rstlythe cost of desalinatedwater remains verylow, secondly
draw solution need not undergo an additional separation process
and thirdly the process provides nutrient rich water for irrigation
of plants and crops. Besides, FOdesalination has high recovery rate
and high salt rejection rate [20,31], which will be an additional
advantage for the irrigation application.
The concept of fertilizer driven FO desalination was initially
studied by Moody [32] part of which was reported in his article
[33], since then, there has been no detailed study related to this
particular eld. The objective of this study is therefore to carry out
an initial assessment on the feasibility of some commonly used
fertilizers as osmotic draw solute for FO desalination. The assess-
ment is performed considering the initial FO desalination process
design concept based on the best currently available technology.
Therefore, this study aims to evaluate the potential of FO process
indesalinationfor irrigationrst byscreening, assessingandidenti-
fying suitable drawsolutions froma comprehensive list of chemical
fertilizers considering their various physical and chemical proper-
ties compatible to the currently available FOtechnology. The study
includes preliminary assessment of the osmotic potential of differ-
ent fertilizer solutions and carrying out basic FOexperimental tests
to evaluate their performance in terms of water ux and reverse
draw solute ux of the fertilizer draw solutions. The assessment
also includes the estimation of the theoretical amount of water per
kilogram of each fertilizer, which can be extracted from sea water
or brackish groundwater.
2. The design concept of fertilizer driven FO desalination
for direct fertigation
A conceptual layout of the fertilizer driven FO desalination pro-
cess for fertigationis showninFig. 1. The process is not signicantly
different fromthe conventional FOdesalinationprocess except that
it excludes draw solution recovery process. The process consists of
FO membrane unit with one face connected to the feed water and
the other face connected to the draw solution. The draw solution
in this particular case consists of only soluble fertilizer which after
extractionof water canbe useddirectly for fertigationwithor with-
out the need of further dilution. Water is extracted from the saline
feed water due to high osmotic gradient between the concentrated
fertilizer drawsolution and the feed solution. The only energy used
in this process is for running two pumps which does not exert any
hydraulic pressure.
The FO desalination using fertilizer draw solution does not
intend to encourage the use of fertilizers rather the concept is
based on the belief that the chemical fertilizers are anyway used
for the production of crops. Besides making irrigation water avail-
able at lower energy cost, FO desalination is more advantageous
for those farms adopting fertigation as a means of applying fertil-
izers with irrigation system and therefore can be easily integrated
within their existing fertigation system. The uses of conventional,
broadcast application of fertilizers are not effective and fertigation
thus provides an effective and cost-efcient way to supply water
and nutrients to crops [34,35]. In general, fertigation gives a better
crop response than either banded or broadcast applications. Fer-
tigation can also be advantageous for application in mixture with
other micronutrients and fungicides in a dust free environment,
eliminating separate applications of those chemicals [36] which
can also provide osmotic pressure.
However, few limitations are envisaged with this concept. The
fertilizer solution can extract water only up to the concentration
where its osmotic potential equals that of the brackish feed water
and, the nal fertilizer concentration may require further dilution
using potable water fromother sources to bring down the fertilizer
concentrations to the acceptable limit. This could be a signicant
impediment where other sources of potable water for irrigation do
not exist. In such situations RO desalination may need to be inte-
gratedto augment the additional water requirements. The quantity
of additional fresh water required to further lower the nutrient
concentration of the diluted draw solution before fertigation may
depend on many factors such as types of crops to be irrigated, crop-
ping seasons, and soil nutrient conditions [37,38]. A novel hybrid
process using FO and RO using impaired water source such as
wastewater efuent from the treatment plant or the storm water
as proposed by Cath et al. [39,40] may also provide an additional
source of water for dilution and concentrate management.
3. Materials and methods
3.1. Chemicals and reagents
All chemicals used were reagent grade supplied by Samchun
Chemicals Co. Ltd., South Korea and they were used as received
without any further treatment. Table 1 provides detail of the chem-
174 S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181
Fig. 1. Initial design concept of the fertilizer drawn forward osmosis desalination for direct fertigation.
icals used. Draw solutions were prepared by dissolving fertilizer
compounds in deionized water (DI).
3.2. Forward osmosis experimental set up
A bench-scale FO set up similar to the one explained elsewhere
was adopted for conducting the FO experiments [31]. The cross-
ow membrane unit consisted of an FO cell with channels (2.6cm
width7.7cm length0.3cm depth) on both sides of the mem-
brane to allow feed water to ow on active side of membrane and
drawsolution on the support side of membrane. FOmembrane was
obtained from the Hydro well lter modules (Hydration Technolo-
gies Inc.) and it is considered made up of cellulose acetate (CA)
membrane embedded in a polyester woven mesh [11,20,41]. Zeta
potential of the membrane was analyzed using streaming potential
and streaming current analyzer (SurPASS Electrokinetic Analyzer,
Anton Paar).
3.3. Performance measurements
For FOperformance test, fertilizer with 2.0Mconcentration was
used as draw solution with DI as feed water. It must be mentioned
here that, DI water was used as feed water for comparative study
only. The water uxes may be signicantly lower if saline water
is used as feed water for FO process. The ow adopted was co-
current mode in order to minimize strain on the suspended FO
membrane [15]. The feed water and drawsolutions were both sup-
plied at crossow velocities of 8.5cm/s using two variable speed
peristaltic pumps. The temperature of the feed and draw solutions
in all cases was maintained at 25

C using temperature water bath

controlledbyheater/chiller. Water uxwas measuredcontinuously
by connecting draw solution to a digital mass scale connected to a
computer.
Reverse draw solute ux for all experiments were monitored
by electrical conductivity (EC) online using a multimeter (CP-500L,
ISTEK) withseparate probes attachedand, connectedto a computer
for data logging.
3.4. Calculation of fertilizer osmotic pressure and speciation
The speciation and the osmotic potential of the fertilizer draw
solutions were predicted using OLI Stream Analyzer 3.1 (OLI
Systems Inc., Morris Plains, NJ, USA). This software uses ther-
modynamic modeling based on published experimental data to
predict properties of solutions over a wide range of concentrations
and temperature [31]. Osmolality of the fertilizer draw solutions
was measured using cryoscopic osmometer (OSMOMAT 030-D,
Genotec), based on the freezing point depression method and had
measurement range of 02.5osmoles/kg. Osmometer calibration
was performed using NaCl standards of 2osmoles/kg, as received
from the same supplier.
Table 1
Details of the chemical fertilizers used for the draw solution assessment.
Name of fertilizers Chemical formula MW Purity (%) Supplier
Ammonium nitrate NH
4
NO
3
80.04 98.5
All chemicals
supplied by
Samchun Chemicals
Co. Ltd., South Korea
Ammonium sulfate (NH
4
)
2
SO
4
132.1 99.0
Ammonium chloride NH
4
Cl 53.5 98.5
Calcium nitrate Ca(NO
3
)
2
164.1 98.5
Sodium nitrate NaNO
3
85.0 98.0
Potassium chloride KCl 74.6 99.0
Mono-ammonium phosphate NH
4
H
2
PO
4
115.0 98.0
Diammonium hydrogen phosphate (NH
4
)
2
HPO
4
132.1 98.5
Potassium nitrate KNO
3
101.1 99.0
S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181 175
3.5. Determination of FO membrane transport parameters
The pure water permeability coefcient A of FOmembrane was
evaluated using laboratory-scale crossowROunit having aneffec-
tive membrane area similar to the FO unit described in the earlier
section. The pure water (DI) ux was measured at a constant tem-
perature (25

C) and pressure for a minimum duration of 10h. The

membrane permeability coefcient was determined separately for
each pressure at 50, 100, 150, 200, 250 and 300psi. The permeabil-
ity coefcients obtained at these pressures were averaged to get
the nal permeability coefcient A of the membrane.
4. Results and discussion
4.1. Screening of fertilizer draw solutions
A comprehensive list of chemical fertilizers (synthetic and min-
eral fertilizers) was initially considered for selection. The initial
screening was based on their basic properties such as solubility
in water, pH, osmotic potential, and their popularity of use as
crop nutrients. Regardless of the nal application, any draw solute
should ideally be inert, neutral or near neutral pH and non-toxic
[42]. It should also have high osmotic potential, much higher than
the osmotic potential of the target saline water. For example, sea
water has an osmotic pressure of about 26atm while for brack-
ish water, the osmotic pressure is usually lower depending on the
salinity of the water. The drawsolution should not react chemically
withthe feedsolutes toformundesirable products that couldeither
hamper osmotic process or the ultimate use of the product water.
The selection was also considered keeping in mind that the current
commercial CA FO membrane has pH range between pH 4.0 and
8.0 [43,44]. However, pH may not be a limiting factor in the future,
when new generation of thin lm composite FO membranes are
made available in the market [24,25].
Based on the preliminary screening, a total of nine different
fertilizers were nally selected for further study (Table 2). These
fertilizers are the most commonly used fertilizers around the
world as crop nutrients and they are not foreseen to have any
immediate potential problem when used as draw solution for FO
desalination. The list contains both single and double/complex
fertilizers. Although complete fertilizers (Nitrogen Phosphorous
PotassiumNPK) are also available commercially, they are usu-
ally mixed or blended fertilizers and their chemical compositions
remain proprietary and therefore excluded in our assessment. The
selected list does not include ammonia solution, ammonium car-
bamate and ammonium bicarbonate fertilizers as they have been
widely used as draw solutions [20,31,41,45]. Moreover, ammonia
carbamate and ammonia bicarbonate solutions are volatile and
therefore can be a potential problem while handling the draw
solution. However, volatility couldbe anadvantage only if thermal-
based regeneration is needed. The assessment also excludes urea
which is one of the most popular chemical fertilizers in the world.
Although urea has low molecular weight and is highly soluble in
water, it does not dissociate in water or form charged species and
therefore was found to have very low osmotic potential and high
reverse solute ux (data not shown).
4.2. Predicted osmotic pressure of fertilizer draw solutions
Table 2 provides the types of species formed for each fertilizer
and the osmotic pressure at 2.0M solution based on OLI Stream
Analyzer. Most selected fertilizers generate charged species except
for NH
4
NO
3
, NaNO
3
, KCl and NH
4
H
2
PO
4
where very small quan-
tities of uncharged species are expected to be formed at higher
concentrations. The osmotic pressure is a colligative property of the
Fig. 2. Calculated osmotic potential of selected fertilizer draw solutions at 25

C
using OLI Stream Analyzer.
solution and therefore depends on the number of species formed
and not on the type and nature of species. Fig. 2 shows the osmotic
pressure of fertilizer draw solutions at different concentrations
at 25

C. Ca(NO
3
)
2
has the highest osmotic pressure at 2M con-
centration followed by (NH
4
)
2
SO
4
, NH
4
Cl, and KCl. KNO
3
showed
the lowest solubility and osmotic pressure amongst the selected
fertilizers. These results indicate that, all the selected fertilizers
can generate osmotic potential much higher than the sea water
(28atm) or brackish water for use as osmotic draw agent.
4.3. Water ux generated by fertilizer draw solutions
Theexperimental purewater uxof eachfertilizer drawsolution
as a function of its molar concentration is presented in Fig. 3. The
water ux increased at higher molar concentrations of the fertilizer
drawsolutions however, the correlationbetweenmolar concentra-
tionandwater uxes was nonlinear unlike osmotic pressure where
the correlation was observed fairly linear (Fig. 2). Water uxes are
usually reported to have logarithmic correlation with the pressure
[46,47]. KCl showed the highest pure water ux (6.337m/s) fol-
lowed by NaNO
3
, NH
4
Cl and (NH
4
)
2
SO
4
. KCl is also reported to
have much higher ux than other inorganic draw solutions [10].
Fig. 3. Pure water ux of the fertilizer draw solutions as a function of molar con-
centrations. Feed: DI water, crossow rate: 8.5cm/s.
176 S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181
Table 2
List of selected fertilizers for FO draw solution testing with their physical and chemical properties.
Name of fertilizers Chemical formula MW pH
a
at 2M Max. solubility Species formed in 2.0M solution at
25

C and 1.0atm pressure

Ammonium nitrate NH
4
NO
3
80.04 4.87 84.0M NH
4
+
: 0.85M, NO
3

: 0.85M, NH
4
NO
3
:
aq. 1.15M
Ammonium sulfate (NH
4
)
2
SO
4
132.1 5.46 5.7M NH
4
+
: 3.07M, SO
4
2
: 1.07M, NH
4
SO
4

:
0.93M
Ammonium chloride NH
4
Cl 53.5 4.76 7.4M NH
4
+
: 2M Cl

: 2M
Calcium nitrate Ca(NO
3
)
2
164.1 4.68 7.9M NO
3

: 3.47M, Ca
2+
: 1.47M, CaNO
3

:
0.53M, total =5.47
Sodium nitrate NaNO
3
85.0 5.98 10.5M Na
+
: 1.92M, NO
3

: 1.92M, NaNO
3
(aq.
0.08M at 2M)
Potassium chloride KCl 74.6 6.80 4.6M K
+
: 1.99M, Cl

: 1.99M, KCl (aq.):

0.01M at 2M
Mono-ammonium phosphate NH
4
H
2
PO
4
115.0 3.93 3.7M NH
4

: 2.0M, H
2
PO
4

: 1.76M,
H
2
P
2
O7(ion): 0.10M, H
3
PO
4
(aq.):
0.02M, HP
2
O7(ion): 0.004M
Diammonium hydrogen
phosphate
(NH
4
)
2
HPO
4
132.1 8.12 6.5M NH
4
+
: 3.94M, HPO
4
(ion): 1.79M,
P
2
O7(ion): 0.07M, H
2
PO
4
(ion): 0.02M,
HP
2
O7(ion): 0.02M.
Potassium nitrate KNO
3
101.1 5.99 3.3M K
+
: 2.0M, NO
3

: 2.0M
a
pH values as measured at 2.0M. Solubility and speciation data were adapted from OLI Stream Analyzer speciation results.
(NH
4
)
2
HPO
4
and NH
4
H
2
PO
4
have the lowest water ux amongst
all the selected fertilizer draw solutions.
4.4. Comparison of measured and predicted water uxes based
on bulk osmotic pressure
In ideal case, the water ux through FO membrane due to
osmotic gradient between the two solutions is given by the fol-
lowing equation [31,48]:
J
w
= A (
ds

fs
) (1)
where J
w
is the water ux, A is the membrane permeability coef-
cient, is the reection coefcient,
ds
and
fs
are the bulk osmotic
pressure of drawsolution and feed solution respectively. In our cal-
culations, the value of has been assumed to be unity (complete
rejection of solute) although practically FO membranes have salt
rejection above 95% [31].
Table 3 shows that the experimental ux is much lower than
the estimated or predicted ux which is mainly attributed to CP
effects especially dilutive ICP as reported by many earlier stud-
ies [10,11,19,4951]. The theoretical ux was calculated based on
the bulk osmotic pressure (predicted using OLI StreamAnalyzer) at
2.0M concentrations using Eq. (1). The permeability coefcient of
the membrane was found to be A=0.430.03m/s atm at 25

C.
The performance ratio of each fertilizer solution was calculated as
a percentage ratio of actual ux to the estimated theoretical ux
and the results are shown in the same table. This ratio indicates the
percentage of the effective bulk osmotic pressure difference that
is effectively generating water ux across FO membrane [31]. KCl
and NaNO
3
showed the highest performance ratio closely followed
by KNO
3
, NH
4
NO
3
and NH
4
Cl. (NH
4
)
2
HPO
4
however showed the
lowest water ux performance followed by Ca(NO
3
)
2
, NH
4
H
2
PO
4
and (NH
4
)
2
SO
4
.
4.5. Comparing experimental water ux and bulk osmotic
pressure of different fertilizers
The results in Table 3 indicate that, some of the fertilizer draw
solutions with higher bulk osmotic pressure have much lower
experimental ux than the expected ux. For example, Ca(NO
3
)
2
has the highest bulk osmotic pressure amongst all the selected fer-
tilizers however, its actual ux is lower than draw solution such as
KCl, NaNO
3
, NH
4
Cl and (NH
4
)
2
SO
4
. In addition to water ux perfor-
mance ratio, we have tried to observe the correlation between the
experimental ux and the theoretical osmotic pressure of different
fertilizer draw solutions comparatively. The osmotic pressure and
the experimental water ux of the drawsolutions were taken from
Table 3 and their correlation plotted in Fig. 4. The experimental ux
of the ve fertilizer draw solutions (NH
4
Cl, NaNO
3
, KNO
3
, KCl and
NH
4
NO
3
) has a fairly linear correlation with the predicted osmotic
pressure, while the other four fertilizers (NH
4
H
2
PO
4
, (NH
4
)
2
HPO
4
,
Ca(NO
3
)
2
and (NH
4
)
2
SO
4
) showed very poor correlation. Several
explanations were explored for this anomaly.
Firstly, the osmotic pressure is calculatedusing proprietary soft-
ware(OLI StreamAnalyzer) andwelackedtheunderstandingonthe
actual osmotic pressure prediction models used by this software.
Calculation of theoretical osmotic pressure is not easy although
data for fewcommonly usedcompounds are available anddetermi-
nation of actual osmotic pressure is even more difcult because of
the lack of ideal membrane [52]. Since osmotic pressure is a colliga-
tive property, the osmolality of a solution is directly related to the
osmotic coefcient and therefore osmolality is the practical way of
measuring the contribution of the various active solutes present in
solution[53,54]. We usedthe osmolalityas anindicator tostudythe
osmotic trend comparatively since, comparative method has some
advantage as it enables sets of osmotic coefcients to be compared

F
(atm) of different fertilizers
60 70 80 90 100 110
E
x
p
e
r
i
m
e
n
t
a
l

w
a
t
e
r

f
l
u
x

(

m
/
s
)
3.5
4.0
4.5
5.0
5.5
6.0
6.5
Ca(NO
3
)
2

3
a
3
NH
4
H
2
PO
4
NH
4
Cl
KCl
(NH
4
)SO
4
(NH
4
)
2
HPO
4
Fig. 4. Experimental water ux of each fertilizer draw solutions as a function of
predicted osmotic potential at 2.0M.
S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181 177
Table 3
Performance ratio calculated using estimated theoretical ux and experimental ux. Membrane permeability coefcient A=0.430.03m/s atm. Osmotic pressure and the
water ux are based on the 2M concentration of fertilizer draw solutions.
Fertilizers Osmotic pressure
a
(atm) Actual Jw (m/s) Estimated Jw (m/s) Performance ratio (%)
KCl 89.3 6.337 38.445 16.48%
NaNO
3
81.1 5.706 34.915 16.34%
KNO
3
64.9 4.429 27.940 15.85%
NH
4
NO
3
64.9 4.177 27.940 14.95%
NH
4
Cl 87.7 5.348 37.756 14.16%
(NH
4
)
2
SO
4
92.1 5.391 39.650 13.60%
NH
4
H
2
PO
4
86.3 4.349 37.153 11.71%
Ca(NO
3
)
2
108.5 5.022 46.711 10.75%
(NH
4
)
2
HPO
4
95.0 3.892 40.899 9.52%
a
Osmotic pressure of the fertilizer draw solutions at 2.0M concentrations was adapted as predicted by OLI Stream Analyzer.
directly and it can examine consistencies between various sets of
values. Since the osmometer used had measurement range only up
to 2.5osmoles/kg, we could not determine the osmolality of the
draw solutions at 2M concentration. However, the osmolality at
1.0Mconcentrations was measured and their corresponding water
ux and osmotic pressure were used for comparison. The osmolal-
ity of the fertilizer drawsolutions indicated linear correlation with
the molar concentrations up to 1.0M and the results are shown in
Fig. 5.
First we compared the measured osmolality of the draw solu-
tion with the osmotic pressure predicted by OLI Stream Analyzer
for 1.0M concentrations as shown in Fig. 6. The osmolality of the
selected fertilizer draw solutions indicated a fairly linear correla-
tion with the osmotic pressure data from OLI software except for
NH
4
H
2
PO
4
, (NH
4
)
2
HPO
4
and NH
4
NO
3
draw solutions. However,
the results in Fig. 7 still show poor correlation between the mea-
sured osmolality and the experimental ux similar to results in
Figs. 4 and 7. Although osmolality is a measure of the active solute
that contributes to osmotic pressure, the non-linearity with the
actual ux and the measured osmolality indicates that, the actual
ux is inuenced by factors other than the bulk osmotic pressure
differences as explained in the next paragraph.
The anomaly between the bulk osmotic pressure of fertilizer
draw solutions and the actual water ux indicates that, the nature
of the species has signicant inuence on the severity of CP in the
FO process. Since, experiments were conducted in FO mode (draw
solution on the porous support layer side of FO membrane), ICP
might be the main factor responsible for lowering pure water ux.
Fig. 5. Osmolality of the draw fertilizer solutions at various molar concentrations
determined using OSMOAT.
ICP reduces the effective osmotic pressure difference across the
membrane layer thereby lowering the water ux [10,11,21,23,51].
The results in Fig. 4 also indicate that the severity of ICP depends
on the type of draw solution. ICP is modeled by considering the
resistance to diffusion of solute molecules within the porous sup-
port layer [21,23]. Ca(NO
3
)
2
with the highest molecular weight
amongst the selected fertilizer draw solution is probably affected
more severely by ICP. The rate of diffusion is inversely proportional
to molecular mass [55,56]. For the same osmotic pressure, draw
solution with higher diffusion coefcient results in higher water
ux [10,22].
4.6. Reverse fertilizer draw solute ux
No semi-permeable membranes are ideal or perfect barrier and
therefore reverse salt permeation is inevitable [57]. Reverse salt
movement can be a signicant disadvantage for FO because it can
complicate the feed water concentrate management and also is
likely to decrease the net osmotic potential or driving force [47,57]
and fouling potential of the feed solution [47,58]. Reverse solute
ux(RSF) couldbe particularly signicant especially whennitrogen
and phosphorus containing draw solutions are used as these com-
pounds are known to cause eutrophication in the receiving water
environment. Therefore it is essential to assess the performance of
fertilizer draw solution in terms of RSF.
The fundamentals and models to describe reverse draw solute
permeation through the semi-permeable membrane are described
elsewhere[11,47,57,59]. Our initial investigationindicatedthat, the
reversesoluteconcentrationat thefeedsidewas signicantlylower
than the drawsolution concentration used initially. For dilute solu-
(NH
4
)
2
HPO
4
Osmolality of draw solution at 1.0 M (osmoles/kg)
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
O
s
m
o
t
i
c

p
r
e
s
s
u
r
e

(
a
t
m
)
30
35
40
45
50
55
NH
4
Cl
NH
4
NO
3
Ca(NO
3
)
2
KCl
NH
4
H
2
PO
4
NaNO
3
KNO
3
(NH
4
)
2
SO
4
Fig. 6. Theoretical osmotic pressure of the fertilizer draw solutions as determined
by OLI StreamAnalyzer as a function of measured osmolality at 1.0Mconcentration.
178 S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181
Ca(NO
3
)
2
Osmolality of draw solution at 1.0 M (osmoles/kg)
1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
E
x
p
e
r
i
m
e
n
t
a
l

w
a
t
e
r

f
l
u
x

(

m
/
s
)
2.5
3.0
3.5
4.0
4.5
5.0
5.5
NaNO
3
KCl
(NH
4
)
2
HPO
4
NH
4
H
2
PO
4
NH
4
NO
3
KNO
3
(NH
4
)
2
SO
4
NH
4
Cl
Fig. 7. Experimental water ux of each fertilizer draw solutions as a function of osmolality of the 1.0M fertilizer draw solution measured by osmometer.
tion, the molar concentrations indicated a very good correlation
with the electrical conductivity (EC) for all the selected draw solu-
tions (data not shown) and therefore, RSF was monitored online
using EC as an indicator.
The performance of fertilizer drawsolutions in terms of RSF var-
ied widely depending on the type of fertilizers used as shown in
Table 4. (NH
4
)
2
SO
4
showed the lowest RSF amongst the selected
fertilizers while NH
4
NO
3
draw solution had the highest RSF value.
In general, the ammonium compounds of sulfate and phosphate,
and Ca(NO
3
)
2
containing monovalent elements performed well in
terms of RSF since lower RSF is preferred for any FOprocess. Table 4
also includes specic RSF, whichis dened as the ratio betweenRSF
andwater ux [47,60]. Specic RSF actually indicates the amount of
drawsolutelost throughdiffusionor permeationthroughthemem-
brane towards the feed water during the FO process. For example,
0.00103M of NH
4
SO
4
DS diffuses towards the feed water for every
litreof water extractedwhilefor NH
4
NO
3
DS, it amounts to0.189M.
(NH
4
)
2
SO
4
, Ca(NO
3
)
2
, (NH
4
)
2
HPO
4
and NH
4
H
2
PO
4
have ionic
species with hydrated diameter of SO
4
2
, PO
4
2
and Ca
2+
compar-
Fig. 8. Variation of pH of a DI feed during the FO process using different fertilizer
draw solutions. The gradual increase in pH with time may be due to decrease in
the feed water volume (initial volume of 2.0L) with time as it was a closed loop
experiment where the feed water was recycled recirculated in a closed loop.
atively much higher than the hydrated diameter of other fertilizer
species (NH
4
+
, Cl

, NO
3

, K
+
and Na
+
) [10] and therefore could be
one of the reasons for lower RSF. Ca
2+
as divalent ions, also has
much lower reverse permeation rate than monovalent ions [47]. In
addition, (NH
4
)
2
HPO
4
draw solution has a weakly alkaline pH at
2M concentration and at this pH, FO membrane remains slightly
negative charged (data not shown). This negative charge could
repel phosphate containing anions, which are usually made up of
higher hydrated diameter with greater force. Achilli et al. [10] also
reported lower RSF for draw solutions containing SO
4
2
and Ca
2+
species.
The other possible explanation is due to ion-pairing. Associ-
ation of ions occurs as a result of purely electrostatic attraction
between oppositely charged ions, a common behavior for divalent
metal sulfates [52] andcalciumnitrate [61] inaqueous solution. KCl
and NH
4
Cl electrolytes are of the non-associated type, therefore
do not form ion pair [62]. Although, NH
4
H
2
PO
4
and (NH
4
)
2
HPO
4
contain NH
4
+
with much smaller hydrated ion which can easily dif-
fuse through the membrane, nevertheless their net diffusion will
be lowsince these compounds have anions made up of much larger
hydrated diameter (PO
4
2
and HPO
4

) which cannot pass through

the membrane and, in order to maintain electrical neutrality across
the membrane, the smaller cations will naturally diffuse back to the
draw solution.
NH
4
NO
3
has obviously the highest RSF rstly because NH
4
+
and NO
3

have much lower hydrated diameter. Secondly, ammo-

Table 4
Reverse solute ux of the fertilizer draw solutions.
Fertilizers Actual Jw
(m/s)
RSF Js
(mmoles/m
2
s)
a
Js/Jv
(mmoles/L)
NH
4
NO
3
4.177 0.790876 189.34
KNO
3
4.429 0.485625 109.65
NH
4
Cl 5.348 0.333000 62.27
NaNO
3
5.706 0.277500 48.63
KCl 6.337 0.222000 35.03
NH
4
H
2
PO
4
4.349 0.069375 15.95
(NH
4
)
2
HPO
4
3.892 0.009713 2.50
Ca(NO
3
)
2
4H
2
O 5.022 0.009019 1.80
(NH
4
)
2
SO
4
5.391 0.005550 1.03
a
RSF calculated for 10h of FO operation for all cases.
S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181 179
Table 5
Estimated quantity of water a kilogram of fertilizer can extract from sea water (SW) and brackish water (BW). Osmotic potential assumed for SW is 28atm and BW 14atm.
Fertilizers MW Con. at 14atm (M) Vol. from BW (L) Con. at 28atm (M) Vol. from SW (L)
NH
4
Cl 53.5 0.318 58.779 0.643 29.069
KCl 74.6 0.316 42.420 0.638 21.011
NaNO
3
85.0 0.338 34.807 0.665 17.691
NH
4
NO
3
80.04 0.386 32.367 0.820 15.236
KNO
3
101.1 0.324 30.528 0.722 13.700
(NH
4
)
2
HPO
4
132.1 0.251 30.159 0.526 14.392
NH
4
H
2
PO
4
115.0 0.315 27.605 0.636 13.672
(NH4)
2
SO
4
132.1 0.288 26.285 0.598 12.659
Ca(NO
3
)
2
164.1 0.257 23.711 0.530 11.498
nium nitrate does not dissociate fully in water. OLI speciation
indicates that, at 2MNH
4
NO
3
concentration in water, about 1.15M
of NH
4
NO
3
remains in non-dissociated form. Uncharged species
have higher RSF than the charged species [47].
The pH of the DI feed water changed signicantly during
the course of the FO process. For the NH
4
H
2
PO
4
, (NH
4
)
2
HPO
4
,
Ca(NO
3
)
2
, NH
4
NO
3,
and NH
4
Cl draw solutions, the pH of the DI
feed water initially increased, and then decreased showing a peak,
nallyreachingalmost aconstant pHafter certaintime. Fig. 8shows
the variation of DI feed water pH. It is not explained at this time
however, one interesting point to be noted is that, although the pH
of these ve draw solutions are acidic except for (NH
4
)
2
HPO
4
, the
pHof their correspondingDI feedwater remainedat aroundneutral
pH throughout the experiment.
Ammonium phosphate fertilizers are the important group of
the most concentrated soluble fertilizer materials containing both
Nand P, essential fertilizer elements needed by the plants [63] and
can be either alone as fertilizer or is compatible to be used as mixed
fertilizer with a number of other fertilizers [64,65]. Although, their
water ux is lower than the other draw solutions, their low
RSF makes them a promising candidate for FO desalination for
fertigation.
4.7. Estimating water extraction capacity of fertilizer draw
solutions
Sea water has osmotic potential of about 28atm while the
osmotic potential of brackish groundwater can vary depending on
its total dissolved solids. Water transfer from saline feed water to
draw solution by natural osmotic process will occur as long as the
osmotic potential of the drawsolutionremains higher thanthe feed
water. Assuming that the volume of the saline feed water remains
unlimited, the water transfer will continuously dilute the draw
solution during the FOprocess until a point where net water move-
ment will cease. This occurs at a point when osmotic equilibriumis
reached(zeroosmotic gradient). Basedonthe mass balance, Table 5
shows that the theoretical amount of water per kilogram of fertil-
izer can extract from brackish water (0.3M NaCl 14atm) and sea
water (0.6M NaCl 28atm) by FO process. Assuming ideal mem-
brane and similar effect of CP for all fertilizers, different fertilizers
will achieve osmotic equilibriumat different molar concentrations
and this depends largely on the molecular weight of the drawsolu-
tion. Based on the theoretical calculations, all soluble fertilizers can
extract water frombrackishwater as longas it cangenerateosmotic
potential higher than the saline feed water. NH
4
Cl with the lowest
molecular weight can extract the maximum volume of water from
the saline water followed by KCl and NaNO
3
while Ca(NO
3
)
2
with
largest MW amongst the selected fertilizers can extract the lowest
volume of water per mass of fertilizer.
In reality however, the ux may be extremely slow as the draw
solution is further diluted and the feed solution further concen-
trated (since feed source is actually not unlimited) and the ux may
not be economically viable for FOto continue operating. Therefore,
engineering and process optimization could also play a signicant
role in the economics of the FO desalination.
5. Conclusions
A novel low energy desalination concept using fertilizer drawn
FO has been developed wherein desalinated water can be directly
used for fertigation. This process avoids the need for an additional
process for separating desalinated water and drawsolution, which
is one of the major challenges of FO technology. Based on this
concept, about nine chemical fertilizers have been selected from
a comprehensive list of chemical fertilizers and properties thor-
oughlyassessedfor their applicationas FOdrawsolution. Following
conclusions have been drawn from this particular study:

All soluble fertilizers can generate osmotic pressure however,

based on the currently available FOmembrane technology, about
nine different fertilizers were found most suitable candidates for
drawsolutionandtheir performance was assessedinmore detail.

Different fertilizers resultedintodifferent solutionproperties and

therefore showed different osmotic potentials. Ca(NO
3
)
2
showed
the highest osmotic pressure while KNO
3
had the lowest osmotic
pressure amongst the selected fertilizers.

Although the experimental pure water ux increased with the

increase in fertilizer concentrations however, their correlation
was observed quite poor. KCl showed the highest pure water ux
while NH
4
H
2
PO
4
and (NH
4
)
2
HPO
4
showed the lowest pure water
ux amongst the selected fertilizers.

The experimental pure water ux was much lower than the pre-
dicted ux which is mainly attributed to CP effects. In terms of
performance ratio, KCl and NaNO
3
performed much better than
all the other selected fertilizers.

A poor correlation between experimental pure water ux and

the bulk osmotic pressure of all the selected fertilizer draw solu-
tions was observed. This anomaly indicates that, the nature of
the species has signicant inuence on the CP in the FO process
although it does not affect the osmotic potential of the solution.

The performance of fertilizer draw solutions in terms of RSF

varied widely depending on the type of fertilizers used. The
ammonium compounds of sulfate and phosphate, and Ca(NO3)2
containing divalent anions had very lowRSF which is very signif-
icant for any FO process.

Based on the volumetric mass balance and the osmotic equi-

librium, all fertilizer draw solutions are shown to extract water
from saline feed water as long as the fertilizer draw solution can
generate osmotic potential much higher than the feed water.
Acknowledgements
This study was funded by National Centre for Excellence in
Desalination (NCED). This research was also supported by World
180 S. Phuntsho et al. / Journal of Membrane Science 375 (2011) 172181
Class University (WCU) program (Case III) through the National
Research Foundation of Korea funded by the Ministry of Educa-
tion, Science and Technology (R33-10046). The authors appreciate
HydrationTechnologies Inc. for their kindsupport throughthe sup-
ply of FO membranes used in this study.
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