Desalination 274 (2011) 91–96

Contents lists available at ScienceDirect

Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

A new apparatus for seawater desalination by gas hydrate process and removal
characteristics of dissolved minerals (Na+, Mg2+, Ca2+, K+, B3+)
Kyeong-nam Park a, Sang Yeon Hong a, Jin Woo Lee a, Kyung Chan Kang a, Young Cheol Lee a,
Myung-Gyu Ha b, Ju Dong Lee a,⁎
a
Korea Institute of Industrial Technology, 421 Daun-dong, Jung-gu, Ulsan 681–802, Republic of Korea
b
High-Technology Component & Material Research Center, Korea Basic Science Institute, 30 Jangjeondong, Geumjeong-gu, Pusan 618–230, Republic of Korea

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

Article history: Potential application of gas hydrate-based desalination was suggested with a novel apparatus design. The
Received 13 November 2010 equipment continuously produces and pelletizes CO2 hydrates by a squeezing operation of a dual cylinder
Received in revised form 28 January 2011 unit, which is able to extract hydrate pellets from the reactor containing hydrate slurries. Removal efficiencies
Accepted 28 January 2011
for each dissolved mineral from seawater samples was also tested by Inductively Coupled Plasma Atomic
Available online 23 February 2011
Emission Spectroscopy (ICP-AES) analysis. In a single-stage hydrate process, 72–80% of each dissolved
Keywords:
mineral was removed in the following order: K+ N Na+ N Mg2+ N B3+ N Ca2+. Our results also showed that ion
Seawater desalination rejection by the hydrate process strongly depends on the ionic size and charge. This study illustrates that the
Gas hydrate suggested method and apparatus may solve the separation difficulty between hydrate crystals and
Removal of dissolved minerals concentrated brine solutions, thus it can be applied for more effective desalination processes.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Gas hydrate formation as a step in developing a method to produce

Many countries in the world suffer from a shortage of fresh water,
mainly due to increased population as well as the large expansion in
industrial activities. Over the last several decades, seawater has
become an important source of fresh water because it is one of the
most abundant resources on earth. Traditional desalination plants
based on the multi-stage flash (MSF) distillation and reverse osmosis
(RO) processes have evolved into reliable and established processes.
Although the desalination technologies are mature enough to be a
reliable source for fresh water from the sea, a significant amount of
research and development has been carried out to constantly improve
the technologies and reduce the cost of desalination [1,2]. We
investigated the potential applications of gas hydrate technologies
for more economical desalination processes.
Gas hydrates are nonstoichiometric crystalline inclusion compounds
formed by water and a number of small molecules at suitable
temperature and pressure conditions. These compounds exist in three
distinct structures, structure I (sI), structure II (sII) and structure H (sH),
which contain differently sized and shaped cages [3]. The desalination
process by gas hydrate is based on a liquid to solid phase change coupled
with a physical process to separate the solids from the remaining liquid
phase.
⁎ Corresponding author. Tel.: + 82 51 974 9274; fax: + 82 51 974 9299.
E-mail address: julee@kitech.re.kr (J.D. Lee).
potable water from seawater was proposed in the 1940s and received
considerable attention in the 1960s and 1970s [4]. In the 1960s
Koppers Co. developed a hydrate desalination process based on
propane [5]. Sweet Water Development Co. was another company
which explored the hydrate process. Both companies operated pilot-
plant facilities with support from the Office of Saline Water in the
United States [4]. Barduhn and associates investigated a variety of
hydrate forming compounds and studied kinetics and separations in
continuous flow systems, and also reviewed the developments of the
desalination process by freezing and gas hydrate formation [6–8].
In the 1960s and 1970s, several process configurations were
developed and demonstrated at pilot-plant scale but were never
realized at an industrial scale. This was due to the difficulty of
separating the crystals from the concentrated brine solutions and the
removal of dissolved hydrate former from the recovered water [9–11].
More recently, the Bureau of Reclamation in the US sponsored a
preliminary study [12], followed by a pilot test conducted at the
Natural Energy Laboratory of Hawaii [13]. The test was somewhat
successful, although a wash column was never built and tested as part
of the operation. Estimates of water cost arising from the test were
$0.46–0.52/m3 with favorable public financing and $0.59–0.68/m3
with private financing. Problems with the test including difficulty in
separating the crystals, and materials compatibility led to a follow-on
program which included tasks to determine the filterability of hydrate
crystals, the design and operation of a wash column, and surveying
alternate higher temperature hydrate formers [14]. Ngan and
Englezos (1996) investigated recovery of water from pulp mill

0011-9164/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2011.01.084
92 K. Park et al. / Desalination 274 (2011) 91–96
effluents and 2.5 wt.% NaCl solutions through propane hydrate
formation in an apparatus in which hydrate nucleation, growth,
separation, and melting occur in one vessel [15]. The average reduction
in the salt content of the recovered water from the NaCl solutions was
found to be 31%. Further improvement in the purity could be
accomplished by washing with water.
In the present study, hydrate-based desalination is suggested with
novel apparatus design to easily extract dehydrated high-density gas
hydrates from a reactor containing hydrate slurries. Removal
efficiency for each dissolved mineral was also tested for real seawater
samples by ICP-AES analysis. This study illustrates that the suggested
method and apparatus may solve the separation difficulty between
hydrate crystals and concentrated brine solutions, thus it can be
applied for effective desalination processes.
2. Experimental section
2.1. Apparatus
Fig. 1 shows a schematic of the new apparatus design, which
continuously produces and pelletizes gas hydrates by a squeezing
operation of a dual cylinder unit. The apparatus can be divided into
five parts: hydrate reactor with dual cylinder unit, water and gas feed
line, circulation pump with bubble generator and the hydrate
discharge unit. The main part of the apparatus is the jacket-type
hydrate reactor, which is made of 316 stainless steel and has an
internal volume of about 1800 cm3. In addition the reactor has a dual
cylinder unit, two viewing polycarbonate windows, a water-level
sensor and a drain valve. In order to temperature control, a refrigerant
fluid (water–ethylene glycol solution) is circulated between the
duplex jacket assembly and an external refrigerator (model HD-03A,
Hyundai Eng. Co., Korea). Three pressure transmitters (Trafag, model
8251, Switzerland) and five copper-constantan thermocouples
(Omega, T-type, USA) are employed for the pressure and temperature
measurements of the hydrate reactor, gas tank and water feed tank.
The pressure of the gas and water feed tanks are kept higher than the
hydrate reactor which enables the supply of gas and water to the
hydrate reactor through the control valves with a PID controller.
In this apparatus, a high pressure circulation pump (Samec,
multiple-stage electric pumps, Italy) and century tube type bubble
generator are used to mix the reactor contents. Preliminary experi-
ments showed that the average bubble size was around 10 μm, which
was measured by optical microscopic analysis through the windows.
Fig. 1. Schematic of the experimental apparatus for desalination process by gas hydrate method.
As shown in Fig. 2, the hydrate reactor includes a dual cylinder unit
along with pistons, which is vertically movable in a connection pipe.
The connection pipe has plurality of passing holes having different
sizes and shapes. The bigger sized passing hole (main hole) provides
channels for the hydrate slurries to flow into the connection pipe.
When sufficient amounts of hydrate slurries are drawn into the
connection pipe, the upper piston moves downwards to squeeze the
slurries. Subsequently, the hydrate slurries are compressed and
squeezed by the strokes of the dual cylinder operation, and then
residual waters flow out through the plurality of small passing holes.
The pistons are operated by hydraulic pressure ranging from 50 to
150 kg/cm2. In this study, 50 kg/cm2 of hydraulic pressure was
applied. Such a squeezing stroke is repeated several times to obtain
a sufficient thickness of hydrate pellet. After the process of pelletizing
(or compressing), the upper and lower piston move downward at the
same speed to extract the hydrate pellet. As shown in the Fig. 1, the
gas hydrate pellet is extracted by a discharging operation beneath the
reactor. An actual extracted hydrate pellet sample is shown Fig. 3.
After the gas hydrate pellet has been extracted, the upper and lower
pistons are returned to the initial state to begin a subsequent process.
2.2. Experiments
For the desalination experiments, seawater samples were obtained
from the southeast coast of Korea (35° 5′ 1″ north, 128° 47′ 11″ east)
and were delivered to hydrate formation experiments. Carbon dioxide
(CO2, 99.8%, SEM Co. Korea) was chosen as the hydrate forming gas,
because the dissolved CO2 in drinking water after desalination process
is not harmful. When the whole system reached the desired
temperature, the gas tanks and hydrate reactor were flushed at least
three times with the hydrate forming gas (CO2) to remove any
residual air. Subsequently a volume of 1000 ml of seawater was
injected and the reactor was filled with hydrate forming gas until the
desired pressure was obtained. The experimental pressure and
temperature conditions were 2.9 MPa and 280 K, respectively.
As CO2 gas is consumed during hydrate formation, additional gas
was automatically supplied from the gas tank and a constant pressure
maintained in the reactor with the help of a PID controller and control
valve. A constant water level was also maintained by a water-level
sensor and control valve.
When the squeezed hydrate pellet was extracted from the reactor,
the weight was measured immediately prior to hydrate dissociation.
As shown in Fig. 3, dissociated gas bubbles are seen on the surface of
 K. Park et al. / Desalination 274 (2011) 91–96 93

Fig. 2. Front view and cross section of the high pressure gas hydrate reactor. (a) Front view and (b) cross section with the dual cylinder operation.

the hydrate pellet which was exposed to atmospheric conditions.
After it fully decomposed at atmospheric pressure condition, the
dissociated water was also weighed to check hydrate conversion.
The salt concentration was analyzed by a digital salt-meter (PAL-
ES2, ATAGO Co., LTD. Japan). The detection principle is the
conductivity method, and maximum uncertainty is less than 5%. The
content of the each dissolved mineral such as sodium, magnesium,
calcium, and potassium was analyzed by Inductively Coupled Plasma
Atomic Emission Spectroscopy (ICP-AES). Removal efficiencies for
each dissolved mineral were calculated from the mineral contents of
the initial seawater and the dissociated hydrate sample. Some
samples of hydrate pellets are reserved in liquid nitrogen for further
ex-situ spectroscopic analysis.
A Unilab II probe having a 60 mm working distance was used for the
Raman analysis.
2.4. Inductively coupled plasma spectrometer
In order to evaluate desalination efficiency, each dissolved mineral
(Na+, Mg2+, Ca2+, K+ and B3+) was measured by ICP-AES (ACTIVA, JY
HORIVA). The sample was filtered with a cellulose nitrate membrane
filter (Whatman, 0.22 μm) and it was boiled with 1 ml Nitric acid at
150 °C for 30 min to eliminate organics. After pretreatment, the
concentration of dissolved ions was measured by ICP-AES. The test
result was assured by Korea Basic Science Institute (KBSI).
3. Results and discussion

2.3. Raman spectroscopy analysis
A fiber optic based Raman spectrometer (Sentinel, Bruker,
Germany) was used to identify the structure of the pure CO2 hydrates.
The light source for excitation was an integrated diode laser whose
wavelength and power level were 532 nm and 100 mW, respectively.
For seawater desalination, CO2 hydrates were formed from a
seawater sample and the formation reaction proceeded for about
150 min after nucleation began. During the hydrate experiments for
the desalination test, CO2 hydrate pellets were successfully produced
and extracted from the hydrate reactor. The pelletizing step can be
viewed in the video accompanying this work (Video 1).

Fig. 3. Real sample of the extracted gas hydrate pellets.

94 K. Park et al. / Desalination 274 (2011) 91–96

Table 1
Salinity (dissolved salt content) changes in the liquid and hydrate pellet sample.
(Hydrates were formed at 2.9 MPa and 280 K).

Sampling time from Salinity changes in Salinity in hydrate Salt removal

beginning [min] seawater sample [wt %] pellet sample [wt %] efficiency [%]

0 3.2 – –
150 3.8 0.7 78.1

Initial seawater and extracted pellet samples were analyzed for

salinity (dissolved salt content) changes, measured by a digital salt-
meter. As the hydrate experiments progressed, the salinity of the
seawater in the reactor increased slightly while the salinity of the
hydrate pellet decreased. As shown in Table 1, around 78% of salinity
was removed by gas hydrate process. The removal (or desalination)
efficiency was calculated as follows: Fig. 4. Removal efficiency of each dissolved mineral with its ionic radius.

CA0 −CA
Removal ðDesalinationÞ efficiency ðηÞ = × 100
CA0
where CA0 is the salinity in the feed seawater and CA is the salinity in
the dissociated hydrate pellet.
ICP-AES analysis was also carried out to investigate the reduction
characteristics of each dissolved mineral. As mentioned in the
experimental section, the pellets were fully decomposed after
weighing, and then ICP-AES analysis was performed. In the present
study, we measured the four most abundant metal ions (Na+, Mg2+,
Ca2+ and K+) and boron ion (B3+). In view of the fact that boron can
have a serious impact on the human body and plants [16], the World
Health Organization (WHO) has set a preliminary limit of 0.5 mg/L for
drinking water and the EU is also suggesting a guideline of 1.0 mg/L
[17]. For that reason, we included boron ion (B3+) analysis.
The experimental results with the content of each dissolved
mineral, removal (desalination) efficiencies and water conversion to
hydrate are summarized in Table 2. The conversion of water to
hydrate was calculated as follows
 
Wpellet −Wwater × hydration number
Conversion of water to hydrate ð%Þ =
Wwater
× 100
where Wpellet is the weight of the hydrate pellet and Wwater is the
weight of the melted water from the hydrate pellet. The hydration
number of 6.2 reported from Udachin et al. [18] was used for the
conversion calculation.
As seen in Table 2, the amount of dissolved ions in the seawater
sample was found in the following order: Na+ N Mg2+ N K+ N Ca2+ N B3+.
The concentration of minerals in each hydrate pellet taken at 90, 120,
150 min were quite similar to each other. Therefore, the average value
ð1Þ
was taken for the evaluation of removal efficiency of minerals. As the
hydrate experiments progressed, the dissolved minerals were success-
fully removed in the following order: K+ N Na+ N Mg2+ N B3+ N Ca2+. In
particular, the removal of alkali metals (Na+ and K+) was better than
that of alkaline earth metals (Mg2+ and Ca2+) by the hydrate-based
desalination process.
When comparing mineral removal efficiency and its ionic radius
[19] (Fig. 4), a good linear correlation was obtained. The
corresponding R2 value was also included in this figure to give an
indication of the goodness of fit of the regression. With the exception
of Ca2+, the order of mineral removal efficiency was strongly
proportional to the ionic radius (R2 = 0.994) which means larger
ions are more expelled from hydrate pellet, whereas smaller ions are
less expelled for the period of hydrate formation and palletizing step.
Another correlation between mineral removal efficiency and its ionic
charge was also obtained as shown in Fig. 5. The data showed a
negatively linear correlation (R2 = 0.953), except for Ca2+. This
relationship can be explained by the electrostatic attraction between
hydrate particles and positively charged ions, because most particles
dissolved in water have negative charge [20], thus hydrate particles
(negatively charged) attract stronger positive ions from the solution.
It can be concluded that the mineral removal efficiency depended on
ð2Þ the ionic radius and strength of positive ionic charge. This suggests
that a size effect or electrostatic attraction exists during hydrate-
based desalination process. To clarify the removal behavior of
dissolved minerals, further studies such as hydrate-ion interaction
or surface analysis such as X-ray diffraction would be required.
As shown in Figs. 4 and 5, the calcium ion (Ca2+) did not show the
linear correlation between ion removal and its radius or charge. This is
probably related to the precipitation of calcium carbonate (CaCO3)
caused by the excess use of CO2 as the hydrate forming gas. As carbon
dioxide dissolved in seawater, carbonate ions (CO2− 3 ) are produced

Table 2
Experimental results with the content of the dissolved minerals (Na, Mg, Ca, K, and B), removal (desalination) efficiencies and water conversion to hydrate.

Sample Sampling time Na Mg Ca K B Water conversion

[min] [mg/L] [mg/L] [mg/L] [mg/L] [mg/L] to hydrate a
[%]

Seawater in reactor 0 10003.82 996.92 403.65 432.74 2.91 –

b
Extracted CO2 hydrate pellet 90 2117.52 234.02 111.24 82.38 0.83 60.0
120 2256.55 249.98 114.79 87.99 0.78 49.3
150 2006.66 216.50 113.54 84.67 0.72 65.2
Average 2126.91 233.50 113.19 85.01 0.78 58.2
Removal efficiency [%]c 78.7 ± 1.3 76.6 ± 1.7 72.0 ± 0.5 80.4 ± 0.7 73.3 ± 1.9 –
a
Hydration number of 6.2, reported from Udachin et al. [18], was used for the conversion calculation.
b
Hydrate pellet was extracted from hydrate reactor (at 2.9 MPa and 280 K) and then decomposed for the analysis.
c C −C
Removal efficiency = A0CA0 A × 100:
 K. Park et al. / Desalination 274 (2011) 91–96
Fig. 5. Removal efficiency of each dissolved mineral versus its ionic charge.
and can react with calcium ions that are already in the seawater.
Consequently, the carbonate ions cause the precipitation of calcium
ions in the form of CaCO3 as follows [21]
2− þ
CO2 ðgÞ þ H2 OðlÞ→CO3 ðaqÞ þ 2H ðaqÞ
2þ 2−
Ca ðaqÞ þ CO3 ðaqÞ→CaCO3 ðsÞ
The magnesium ion (Mg 2+) could also compete with CO2− 3 but
MgCO3 is appreciably more soluble than CaCO3 [22], which indicates
that the CaCO3 particles are more abundant in the test sample. Since a
circulation pump was used for the mixing of the reactor contents, the
solid CaCO3 could combine with hydrate particles. This could be the
reason why the removal efficiency of calcium ion (Ca2+) was below
the regression line shown in Figs. 4 and 5.
Extracted hydrate samples were characterized by Raman spec-
troscopy. To compare Raman spectra, two hydrate pellets formed
from pure water and from seawater were investigated, as well as the
CO2 gas. Raman spectra of CO2 gas and CO2 hydrates are represented
in Fig. 6. The Raman peaks of the intramolecular symmetric C O
stretching vibration mode of CO2 were detected in both gas and
hydrate phases and the spectra exhibit the double peaks, which
correspond to the well-known CO2 Fermi-diad peaks [23]. Raman
Fig. 6. Comparison of Raman spectra of CO2 gas and CO2 hydrates.
95
peaks of CO2 gas were observed at 1285 and 1389 cm− 1, while the
spectra of CO2 in the hydrate phase shifted to the lower frequency side
(at 1276 and 1380 cm− 1 ) than that of the pure gas state. It was also
noted that there is no difference between Raman spectra of CO2
hydrate formed from pure water and that formed from seawater. This
indicates that the dissolved minerals in seawater did not affect the
hydrate structure, Raman peak position and intensity.
For the desalination test, it should be pointed out that the desali-
nation process was performed by a single-stage of hydrate formation–
decomposition without any pre- and post-treatment. In addition, the
hydrate pellet was not sufficiently compressed during the palletizing
step, which means unconverted salt water still remained as listed in
Table 2. Nevertheless, 72–80% of each mineral was effectively removed
by the single-stage hydrate process. If an additional stage of the hydrate
process was added, approximately 92–97% each dissolved minerals
could be removed from the seawater, based on the calculation from the
application of same removal efficiency as listed in Table 2. It is also
noteworthy that the earliest RO membranes reject boron to a level of
about 50%, thus the issue of boron removal has come under the scientific
spotlight. Despite the progressive improvement in membrane material
and fabrication, boron rejection by modern seawater RO membranes
remains considerably lower than that of sodium chloride which is the
main inorganic salt in seawater [24]. In some cases even a two-stage RO
process is insufficient to meet WHO guidelines for the boron level
(0.5 mg/L) [25]. However, a two-stage hydrate process could reject 93%
boron, which is sufficient meet to WHO guidelines.
Due to recent developments in membrane technology, the trend in
the desalination industry is to use reverse osmosis (RO) for desalting
seawater [26]. However, the most serious problem in membrane
processes is the complexity of controlling membrane fouling and
scaling. As a consequence, the efficiency of the RO process will
decrease due to the pressure drop leading to decreasing flux and an
increase of operational cost by increasing the energy consumption,
additional chemical use and reduced membrane lifetime [26].
4. Conclusion and further work
This study illustrates that the suggested method and apparatus
may solve the separation difficulty between hydrate crystals and
concentrated brine solutions, and also it can be applied for more
effective desalination processes instead of membrane process, which
can increase operational cost owing to the fouling and scaling
problems. In spite of the advantages of the hydrate-based desalination
process, many challenges still remain. As stated above, the issue of ion
rejection by the hydrate process depending on the ionic size and/or
charge should be clarified to understand the ion rejection mechanism
of dissolved minerals, which can also apply to metal ion recovery from
industrial wastewater effluent and seawater treatment as well.
In order to commercialize this desalination concept, key technol-
ogies such as rapid hydrate conversion and treatment of larger
amounts of water should be developed in conjunction with properly
designed equipment. In addition, further desalination research with a
different hydrate forming gas (such as HFCs, SF6 and C3H8) should be
carried out, since these gasses are known to from hydrates under
relatively mild conditions (i.e., lower pressure and higher tempera-
ture), which can reduce energy consumption during hydrate-based
desalination process. It is our hope that the principles of hydrate
process and methodologies discussed in this paper will contribute to
improving desalination processes in the near future.
Supplementary materials related to this article can be found online
at doi:10.1016/j.desal.2011.01.084.
Acknowledgments
The authors wish to thank Professor Englezos, University of British
Columbia for helpful suggestions. Financial support for this work was
96 K. Park et al. / Desalination 274 (2011) 91–96
provided from Ministry of Knowledge and Economy (MKE) through
“Energy Efficiency & Resources, KETEP Program (2010 T100200399)”
and Ministry of Land, Transport and Maritime Affairs (MLTM) in
Korea.
References
[1] S.A. Kalogirou, Seawater desalination using renewable energy sources, Prog.
Energy Combust. Sci. 31 (2005) 242–281.
[2] A.D. Khawaji, I.K. Kutubkhanah, J.-M. Wie, Advances in seawater desalination
technologies, Desalination 221 (2008) 47–69.
[3] E.D. Sloan Jr., Clathrate Hydrates of Natural Gases, Second EditionRevised and
Expanded, Marcel Dekker, NY, 1998.
[4] A. Parker, Potable water from sea water, Nature 149 (1942) 184.
[5] W.G. Knox, M. Hess, G.E. Jones, H.B. Smith, The hydrate process, Chem. Eng. Prog.
57 (2) (1961) 66–71.
[6] A.J. Barduhn, H.E. Towlson, Y.C. Hu, The properties of some new gas hydrates and
their use in demineralizing sea water, A. I. Ch. E. J. 8 (No. 2) (1962) 176–183.
[7] A.J. Barduhn, Desalination by crystalline processes, Chem. Eng. Prog. V 63 (No.1)
(1967) 98–103.
[8] A.J. Barduhn, The State of the crystallization processes for desalinating saline
waters, Desalination 5 (1968) 173.
[9] R. Rautenbach, A. Seide, technical problems and economics of hydrate-processes,
Proc. 6th intern, Sympos Fresh Water Sea 4 (1978) 43.
[10] B.W. Tleimat, Freezing methods (Chapter 7), Principels of Desalination, 2ndEd.
Pt8, Academic Press Inc, 1980, p. 359.
[11] A.H. Khan, Freezing, desalination processes and multistage flash distillation
practice, Chptr 5 (1986) 55.
[12] R.A. McCormack, R.K. Andersen, Clathrate desalination plant preliminary research
study, U.S. Dept. of the Interior, Bureau of Reclamation, 1995.
[13] R.A. McCormack, N.G. A. Build and operate clathrate desalination pilot plant, U.S.
Dept. of the Interior, Bureau of Reclamation, 1998.
[14] R.A. McCormack, N.G. A., Investigation of high freezing temperature, zero ozone,
and zero global warming potential, clathrate formers for desalination, U.S. Dept. of
the Interior, Bureau of Reclamation, 2000.
[15] Y.T. Ngan, P. Englezos, Concentraton of mechanical pulp mill effluents and NaCl
solutions through propane hydrate formation, Ind. Eng. Chem. Res. 35 (1996)
1894–1900.
[16] Y. Magara, A. Tabata, M. Kohki, M. Kawasaki, M. Hirose, Development of boron
reduction system for sea water desalination, Desalination 118 (1998) 25–33.
[17] M. Turek, P. Dydo, J. Trojanowska, A. Campen, Adsorption/co-precipitation–
reverse osmosis system for boron removal, Desalination 205 (2007) 192–199.
[18] K.A. Udachin, C.I. Ratcliffe, J.A. Ripmeester, Structure, composition, and thermal
expansion of CO2 hydrate from single crystal X-ray diffraction measurements, J.
Phys. Chem. B 105 (2001) 4200–4204.
[19] R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic
distances in halides and chalcogenides, Acta Crystallogr. A 32 (1976) 751–767.
[20] D. Perret, M.E. Newman, J.-C. Nègre, Y. Chen, J. Buffle, Submicron particles in the
rhine river–I, Physico chemical characterization Water Res. 28 (1994) 91–106.
[21] Y.S. Han, G. Hadiko, M. Fuji, M. Takahashi, Effect of flow rate and CO2 content on
the phase and morphology of CaCO3 prepared by bubbling method, J. Cryst.
Growth 276 (2005) 541–548.
[22] A. AJ, M. FT, B. NR, Life on the margin: implications of ocean acidification on Mg-
calcite, high latitude and cold-water marine calcifiers, Mar. Ecol. Prog. Ser. 373
(2008) 265–273.
[23] M.O. Gborigi, D.A. Riestenberg, M.J. Lance, S.D. McCallum, Y. Atallah, C. Tsouris,
Raman spectroscopy of a hydrated CO2/water composite, J. Petrol. Sci. Eng. 56
(2007) 65–74.
[24] K.L. Tu, L.D. Nghiem, A.R. Chivas, Boron removal by reverse osmosis membranes in
seawater desalination applications, Sep. Purif. Technol. 75 (2010) 87–101.
[25] W. Kloppmann, A. Vengosh, C. Guerrot, R. Millot, I. Pankratov, Isotope and ion
selectivity in reverse osmosis desalination: geochemical tracers for man-made
freshwater, Environ. Sci. Technol. 42 (2008) 4723–4731.
[26] W. Arras, N. Ghaffour, A. Hamou, Performance evaluation of BWRO desalination
plant — a case study, Desalination 235 (2009) 170–178.