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Aquacultural Engineering 45 (2011) 103– 108

Aquacultural Engineering 45 (2011) 103– 108 Contents lists available at ScienceDirect Aquacultural Engineering journa l hmonium (NH )–, CO concentration, Correspondin g author. Tel.: +56 32 2274226. E-mail addres s e s : b e a t r i z . c a n c i n o @ u c v . c l ( B . C ancino-Madariaga), felipe.hurtado@ucv.cl (C.F. Hurtado). Tel.: +56 32 2274264; fax: +56 32 2274264. 0144-8609/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi: 10.1016/j.aquaeng.2011.08.002 temperature, pH, and total solid concentration, is necessary. Nitrogenous compounds, such as ammonium and ammonia, rep- resent the main rejected catabolites through gills and feces of fish, as they result in highly toxic for the organism ( Ali et al., 2010; Qin et al., 2005 ). Therefore, they need to be rapidly eliminated from the RAS and especially from closed systems, as they cause dam- age at the cellular level, as well as gas exchange problems at the respiration level in the fish gills ( Breton, 2007 ). The industry has given a solution to this problem by generating biological treatment systems (Biofiltration) that are currently available in the market as a unique technology for aquaculture, becoming one of the most important processes in a RAS ( Timmons et al., 2002; Gutierrez- Wing and Malone, 2006 ). Biofiltration can be highly effective on controlling ammo- nium (which is the main objective of our study), in comparison with water’s gradual changeover process. This process, biofiltra- tion, depends exclusively on two groups of autotrophic bacterium that participate jointly and perform nitrification ( Chen et al., 2006 ). In biofiltration, nitrifying bacterium normally coexist with heterotrophic microorganisms, protozoa and micrometazoa, that biologically metabolize degradable organic compounds ( Davidson et al., 2008 ). Heterotrophic bacterium grows significantly faster than nitrifying bacterium and prevails over them, competing for space and oxygen in biofilters when concentration on dissolved " id="pdf-obj-0-6" src="pdf-obj-0-6.jpg">

Contents lists available at ScienceDirect

Aquacultural Engineering

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Aquacultural Engineering 45 (2011) 103– 108 Contents lists available at ScienceDirect Aquacultural Engineering journa l hmonium (NH )–, CO concentration, Correspondin g author. Tel.: +56 32 2274226. E-mail addres s e s : b e a t r i z . c a n c i n o @ u c v . c l ( B . C ancino-Madariaga), felipe.hurtado@ucv.cl (C.F. Hurtado). Tel.: +56 32 2274264; fax: +56 32 2274264. 0144-8609/$ – see front matter © 2011 Elsevier B.V. All rights reserved. doi: 10.1016/j.aquaeng.2011.08.002 temperature, pH, and total solid concentration, is necessary. Nitrogenous compounds, such as ammonium and ammonia, rep- resent the main rejected catabolites through gills and feces of fish, as they result in highly toxic for the organism ( Ali et al., 2010; Qin et al., 2005 ). Therefore, they need to be rapidly eliminated from the RAS and especially from closed systems, as they cause dam- age at the cellular level, as well as gas exchange problems at the respiration level in the fish gills ( Breton, 2007 ). The industry has given a solution to this problem by generating biological treatment systems (Biofiltration) that are currently available in the market as a unique technology for aquaculture, becoming one of the most important processes in a RAS ( Timmons et al., 2002; Gutierrez- Wing and Malone, 2006 ). Biofiltration can be highly effective on controlling ammo- nium (which is the main objective of our study), in comparison with water’s gradual changeover process. This process, biofiltra- tion, depends exclusively on two groups of autotrophic bacterium that participate jointly and perform nitrification ( Chen et al., 2006 ). In biofiltration, nitrifying bacterium normally coexist with heterotrophic microorganisms, protozoa and micrometazoa, that biologically metabolize degradable organic compounds ( Davidson et al., 2008 ). Heterotrophic bacterium grows significantly faster than nitrifying bacterium and prevails over them, competing for space and oxygen in biofilters when concentration on dissolved " id="pdf-obj-0-17" src="pdf-obj-0-17.jpg">

Effect of pressure and pH in ammonium retention for nanofiltration and reverse osmosis membranes to be used in recirculation aquaculture systems (RAS)

Beatriz Cancino-Madariaga a, , Carlos Felipe Hurtado b,1 , Rene Ruby a

a School of Food Engineering, Pontificia Universidad Catolica de Valparaiso, Waddington 716, Valparaiso, Chile b School of Marine Sciences, Pontificia Universidad Catolica de Valparaiso, Pontificia Universidad Católica de Valparaíso, Av. Altamirano 1480, Valparaíso, Chile

a r t i c

l e

i n f o

Article history:

Received 15 January 2011 Accepted 5 August 2011

Keywords:

Nanofiltration

Aquaculture

Ammonium removal

Reverse osmosis

a b s t r a c t

Recirculation systems are becoming widely used in the aquaculture industry, where ammonium removal results are crucial for a proper performance considering its high toxicity on fish. The objective of this study was to assess the ammonium retention, when the transmembrane pressure (TMP) in nanofiltration (NF)

and reverse osmosis (RO) membranes are changed. Two pH levels were tested: pH 5, where ammonium is as NH 4+ , and pH 7 which is an average of the most common range in aquaculture (pH 6–8). In this study a model solution of ammonium–water and commercial membranes of polyamide supplied by Alfa Laval (DSSHR98PP) and Dow (NF90, NF200 and NF270) were used, with a membrane area of 0.01018 m 2 . A crit- ical TMP was determined, where the repulsive electrochemical forces at the active layer were exceeded by the transmembrane pressure, causing an irreversible decrease of the retention values. The maximum TMP values for NF and RO membranes were 16 bar and 24.5 bar, respectively. Ammonium retention at pH 7 was higher than pH 5 for all assessed membranes before the critical TMP was reached, with average values of 100, 99.7, 98.4 and 87.5% for membranes NF90, DSSHR98PP, NF200 and NF270, respectively. It may be concluded the ammonium retention mechanism in the studied membranes basically corre- sponds to an electrochemical mechanism, where pH and critical TMP influence the retention values of ammonium.

© 2011 Elsevier B.V. All rights reserved.

1. Introduction

Hatchery’s production may be done in open systems as well as in closed systems, these last ones are known as recirculation aqua- culture systems (RAS). RAS recirculate a specific rate of the water that goes in the system and present, among others, the following advantages: lower standards of water consumption, concentration of the residue that is produced in its interior, lower discharges of wastewater into the environment, higher standards in biose- curity and independence on the production unit’s location. It is widely known that production units used to be attached to places where water had high quality according to the needs of each cul- ture (Merino et al., 2009). This is no longer necessary on RAS as the system provides itself with the specific environment requested. To maintain water’s optimum quality according to the require- ments and established uses, control of critical parameters as dissolved oxygen concentration, nitrogenous compounds concen- tration – specially the ammonium (NH 3 )–, CO 2 concentration,

Corresponding author. Tel.: +56 32 2274226. E-mail addresses: beatriz.cancino@ucv.cl (B. Cancino-Madariaga), felipe.hurtado@ucv.cl (C.F. Hurtado).

  • 1 Tel.: +56 32 2274264; fax: +56 32 2274264.

0144-8609/$ – see front matter © 2011 Elsevier B.V. All rights reserved.

doi:10.1016/j.aquaeng.2011.08.002

temperature, pH, and total solid concentration, is necessary. Nitrogenous compounds, such as ammonium and ammonia, rep- resent the main rejected catabolites through gills and feces of fish, as they result in highly toxic for the organism (Ali et al., 2010; Qin et al., 2005). Therefore, they need to be rapidly eliminated from the RAS and especially from closed systems, as they cause dam- age at the cellular level, as well as gas exchange problems at the respiration level in the fish gills (Breton, 2007). The industry has given a solution to this problem by generating biological treatment systems (Biofiltration) that are currently available in the market as a unique technology for aquaculture, becoming one of the most important processes in a RAS (Timmons et al., 2002; Gutierrez- Wing and Malone, 2006). Biofiltration can be highly effective on controlling ammo- nium (which is the main objective of our study), in comparison with water’s gradual changeover process. This process, biofiltra- tion, depends exclusively on two groups of autotrophic bacterium that participate jointly and perform nitrification (Chen et al., 2006). In biofiltration, nitrifying bacterium normally coexist with heterotrophic microorganisms, protozoa and micrometazoa, that biologically metabolize degradable organic compounds (Davidson et al., 2008). Heterotrophic bacterium grows significantly faster than nitrifying bacterium and prevails over them, competing for space and oxygen in biofilters when concentration on dissolved

  • 104 B. Cancino-Madariaga et al. / Aquacultural Engineering 45 (2011) 103– 108

and particulated organic material is high (>40 mg/L). This forces not only to maintain water in biofilters as clean – with the lowest total solid concentration – as possible (Wheaton et al., 1994), but makes the biofilters capacity on removing ammonium decidedly dependent on the total available area for nitrifying bac- terium development. Inevitably, this phenomenon will represent a stronger effort when trying to maintain a maximum efficiency. In order to reach it, the means of support used has to balance a large specific area with a voids ratio in media big enough for an appropriate hydraulic behavior; this explains why biofilters must be carefully designed to avoid limitation by oxygen, excessive solids charge or high biochemical demand on oxygen or ammo- nium (Rusten et al., 1998). Other parameters that affect nitrification capacity are: dissolved oxygen (DO), temperature, pH, ammonium and nitrite concentration, salinity, alkalinity, turbulence levels, organic matter and hydraulic matter rate (Satoh et al., 2000; Chen et al., 2006). The above referenced data, added to legal environmental and production restrictions in increase, have complicated biologi- cal treatment systems; this has promoted the interest for new technological alternatives, such as the membrane processes. Com- pared to other traditional techniques, membrane processes involve advantages like the possibility of combination with other auxil- iary processes for water treatment without affecting the quality, low field and space requirements (Paugam et al., 2000) and a great capacity to integrate technology through automation pro- cesses (Bodzek and Konieczny, 1998). Such characteristics involve a marked difference from the biological filtration processes depend- ing on microorganism such as bacteria, which are unable to respond immediately to changes in the water quality and even more when their behavior and efficiency is strongly affected by the quality of the water, thus showing significant variations in the removal efficiency. Among classic membrane processes used in water’s industry, we can describe four of them according to their higher or lower selectivity rates as: microfiltration, ultrafiltration, nanofiltration and reverse osmosis. In this paper we proposed, by the results of our experimental and evaluative research, the possible alternative use of these last two membrane processes in RAS as a complemen- tary solution to ammonium removal due to the characteristics of their processes, as a “back up” or as a self standing answer. In nanofiltration process (NF), the particle, molecule or ion exclusion is achieved through charge and size exclusion methods (Seidel et al., 2001). The ion charge exclusion depends on the mem- brane charges, the ionic force and the ion valence. Ionic force and ion valence influence the membrane charge density and the isoelec- tric point. The membrane charge is positive under the isoelectric point, and negative above it. NF membranes are usually negative charged for neutral (pH 7) and alkaline conditions, and positively charged for low pH conditions (Tanninen et al., 2004; Bandini, 2005). Therefore, the charge separation or exclusion is mainly based on the charge differences of the species to be separated (Donnan effect), a fact that is characteristic of nanofiltration membranes and dielectric mechanisms. On the other hand, size exclusion depends on the membrane structure: the denser the structure, the lower the permeation (Nilsson et al., 2008). Nanofiltration process, then, becomes a potential technology for aquaculture in terms of ammonium ion removal. However, given the characteristics and exclusion mechanisms that occur in membrane process, the potential exploitation of this technol- ogy seems closer when using fresh water than marine water. Although this mechanism works with both types of water, ammo- nium removal in marine water would be lower in comparison with levels reached under the same process in fresh water, mainly because of its concentration of NaCl. NaCl has a stronger affinity with the membrane and it can generate a charge in its surface due

to simultaneous acid–base dissociation processes of hydrophilic functional groups. The presence of positive and negatively charged groups on the membrane’s surface causes a rise of electrostatic interaction phenomena between the surface and the dissolved ions. This phenomenon is known as “binding site of counter- ions” which can be classified as a type of adsorption in the membrane’s surface mainly related to electrostatic interactions. Furthermore, ionic adsorption may occur in the membrane’s sur- face specifically because of electrostatic interactions. In fact, some authors commonly acknowledge that, due to their low hydration radius, preferential adsorption occurs with higher probabilities in hydrophobic areas (Childress and Elimelech, 1996). Bearing this in mind, the results of our investigation could be satisfactory in RAS, being ammonium a cation, it was drew towards the membrane cre- ating a positively charged layer that allowed the repulsion of the ammonium ion. However, in marine water, with high presence of NaCl, an adsorption by competition between positive and nega- tive ions would occur in the membrane’s functional hydrophobic groups. Few investigations have approached its potential use in aquacul- ture systems. Ali et al. (2005) prepared their own polyethersulfone (PES) membrane to test fish wastewater coming directly from a sand filter. They evaluated both, the retention of total ammonium compounds and phosphorous, obtaining a maximal retention of 85.7% and 96.49% at 4 bar, respectively. In 2010, shear rate was studied in their own prepared PES membrane by Ali with other collaborators (Ali et al., 2010), trying to connect the shear rate with the molecular orientation to produce better membranes for aqua- culture applications. They found that shear rate in the preparation of the membrane influences the behavior of the membrane related with the retention factor of ammonia–nitrogen compounds. Qin et al. (2005) working with the University of Hawaii group, began to study in a pilot unit the recirculation of water and the removal of nitrogen using reverse osmosis membranes (RO). They obtained removal rate between 90% and 97%. Later, Liu et al. (2007) investigated the use of RO system for aquaculture wastewater, removing the ammoniacal compounds, which represented one of the few papers in this area and one of the few prototypes at pilot scale. They treated part of the brine coming from the tank with fish in a close circuit with RO. Permeate was recirculated to the fish tank and the concentrate was sent to the storage tank to be repro- cessed with new wastewater coming from the fish tank. Once the nitrogen concentration in the storage tank exceeded a limit value, the brine discharge was produced. This discharge was treated in a different reactor. The paper shows a promising and successful sys- tem. Further studies in the topic would help to comprehensively understand the complete process. According to the authors’ literature review, there are no investi- gations for removal of ammonium in fresh water aquaculture with an application of nanofiltration membranes, however Bódalo et al. (2005) presented one of the first papers on ammonium removal using RO. Furthermore its been shown, due to the amount of papers lately presented, that the use of nanofiltration to remove other molecules and ions in water treatments has importantly raised and turned into several implementations, such as its application on drinking water production processes, and on swine production treatments, among others. This is possible ever since the nanofil- tration membranes can operate under low pressure and could be more profitable in comparison with RO membranes on certain applications. On the other hand, NF membranes having a pore size smaller than ultrafiltration and bigger than RO, can widely sepa- rate solvents, monovalent salts and small organic compounds from divalent ions to bigger compounds (Van Reis and Zydney, 2007). This study is aimed to assess the performance of nanofil- tration membranes, evaluating the ammonium retention (AR) and permeation flow per membrane area unit (Flux) at different

B. Cancino-Madariaga et al. / Aquacultural Engineering 45 (2011) 103– 108

105

Permeate Con cen trate 3 4 2 3 Feed
Permeate
Con cen trate
3
4
2
3
Feed

polysulfone as support material (Sjömana et al., 2007; Luo et al., 2010; Hilal et al., 2008; Tanninen et al., 2004). DSHR98PP is a

polyamide thin film composite membrane (Bódalo et al., 2009).

Each membrane was washed and conditioned according to a

protocol developed in our lab. The washing protocol included: step

1: cleaning the membrane with pure water (distilled water with conductivity lower than 5 S/cm); step 2: cleaning the membrane

with Ultrasil 10 ® (Henkel, Ecolab) at 0.25% at 3.5 bar with 40 C during 45 min; step 3: washing the membrane at least three times

  • 1 with pure water until the Ultrasil was removed from the circuit. A test using pH and conductivity was then done.

Compaction of membranes: According to the protocol previously

described, each membrane was compacted after the washing. The membrane compaction is important to maintain the flow condi- tions during the normal use of the membranes. The compaction was made at 15 bar during 1 h using pure distilled water with a conductivity below 5 S/cm at 20 C. Membrane resistance: After the membranes were washed and compacted, the membrane resistance was determined through a recirculation of pure water, maintaining the temperature at 15 C at different transmembrane pressures, using Eq. (1) (Cheryan, 1998; Cancino et al., 2009).

J =

P T ˘

(R M + R F +

R CP )

(1)

Fig. 1. Total recirculation system at stationary condition for the different experi- ences. (1) Flat high pressure cell, (2) high pressure pump, (3) manometers and (4) valve.

transmembrane pressures (TMP) and pH in an ammonium–water model solution at a stationary state. The latter will allow the deter- mination of the maximum TMP the system is able to work before a significant decrease of the AR is observed. This will permit to infer the operational parameters from the flow requirements and maximum ammonium levels according to the culture stages and processes of different species.

  • 2. Materials and methods

    • 2.1. Equipment

All experiments were carried out under a total recirculation mode (Fig. 1), using a flat stainless steel high pressure cell, which was developed and designed by the GKSS Research Cen- tre (Geesthacht, Germany), and included some modifications done at the Laboratories of the PUCV (Chile). To impulse the flow, a high pressure Speck GmbH pump (Germany) working between 0 and 140 bar was included, and to control temperature a Chiller, RESUN, model C-1500 was used. Permeate ammonium concentra- tion was measured using a multi-parameter photometer (Hanna Instruments, series HI-83000) with a resolution of 0.01 mg/L and a typical EMC deviation of ±0.02.

  • 2.2. Membranes characteristics and conditioning

Four commercial membranes were used: NF 90, NF 200 and NF 270 from Dow Liquid Separations, USA and DSHR98PP pro- vide by Alfa Laval, Denmark. The main characteristics are shown in Table 1. NF membranes from Dow are membranes with an active polyamide layer. NF 200 and NF 270 have specifically a semi-aromatic piperazine-based polyamide as active layer with

where J is the flux, P T is the transmembrane pressure, R M is the membrane resistance, R F is the fouling resistance, R CP is the concentration–polarization resistance, is the viscosity and is the osmotic pressure. When the solution is pure water, R F and R CP are zero, and only R M exists. In this case, R M can be obtained directly using the slope of the J vs. P T curve, as shown in Eq. (2):

R M =

m

(2)

with m as the slope of the curve J vs. P T , is the viscosity of water at 15 C, that is 0.001 (Pa s).

  • 2.3. Working conditions

All experiments were carried out using an ammonium model solution (Merck, Germany) and distilled water with conductiv- ity lower than 5 S/cm. The temperature remained constant at 15 ± 1 C during all experiments. Two pH were studied, pH 5 and pH 7, because at pH 5 the ammo- nium is as NH 4+ form and because pH 7 is the average of the normal values used in aquaculture systems, (Colt, 2006; Emparanza, 2009).

Table 1

Characteristics of the commercial polyamide membranes used.

Membrane

Cut-off (g/mol)

Contact angle ( )

Zeta potential (mV)

Isoelectric point

% Retention

Reference

NF90

n/i

44.7 ± 1.9

37 a

3.6

94.4 ± 1.5 (NaCl) b

Tang et al. (2009)

200

63.2

n/i

Close to pH 4 e

95 (NaCl)

Bellona and Drewes (2005)

NF200

300

30.3

n/i

Close to pH 4 e

60 (NaCl)

Bellona and Drewes (2005)

NF270

150–200

30

32.6 ± 1.3

41.3 a

<3; 3.3; 3.5; 5.2

> 97% (MgSO 4 ) c 56.9 ± 3.8 (NaCl)

Sjömana et al. (2007), Tang et al. (2009)

n/i

30

6.8; 15.0 d at pH 7

3.3

n/i

Tanninen et al. (2004)

DSHR98PP

n/i

n/i

n/i

n/i

>97.5 (NaCl) b

Bódalo et al. (2009)

n/i, no information. a Executed measurement at pH 9. b Permeability was assessed through MilliQ water and retention was done using a NaCl (10 mM) solution at pH 7. The TMP applied was 1380 kPa.

  • c MgSO 4 2000 mg/L at 4.8 bar.

  • d Measured by streaming potential measurements through pores (first value) and along the surface (second value). e Results obtained during steaming potential experiments. Bellona and Drewes (2005) concluded NF 90 membranes are more negatively charged than the NF 200 at pH greater than 5 in presence of 10 mM NaCl or KCl.

AR%

AR%

AR%

  • 106 B. Cancino-Madariaga et al. / Aquacultural Engineering 45 (2011) 103– 108

Table 2

Membrane resistances.

Membrane

Resistance (m 1 )

NF90

6.51 × 10 13

NF200

5.25 × 10 13

NF270

2.58 × 10 13

DSHR98PP

1.21 × 10 14

  • 2.4. Filtration assessment

The AR percentage was calculated using Eq. (3):

AR = 1 C p × 100

C f
C
f

(3)

where C p and C f represent the ammonium concentrations (mg/L)

in permeate and concentrate, respectively.

  • 3. Results and discussion Table 2 illustrates that the highest membrane resistance (R m )

was reached by DSS-HR98PP (RO) membrane with a value of

1.21 × 10 14 m 1 , while the lowest value was reached by NF270

membrane with a value of 2.58 × 10 13 m 1 . On the other hand, in

Table 3 we can see an inverse tendency where the highest flux’s

flows are present in NF-270 membrane, while the lowest values

were observed in RO membrane.

These results agree with the different phenomena that could

explain the ion retention of the AR. As previously mentioned, NF’s

membrane acts as a result of combination of steric and electrostatic

effects (Ismail and Hassan, 2007). On this matter, Bruni and Bandini

(2009) explained the phenomena through the ADS-AMF model

developed by Bandini (2005). In her model, three mechanisms are

present, depending on the membrane material and also the effect of

the solution over the membrane itself. One is the acid–basic disso-

ciation of the hydrophilic functional sites of the membrane; second,

the counter-ions site binding on dissociated hydrophilic sites and

the third mechanism is the competitive adsorption of anions and

cations on the hydrophobic functional groups of the membrane. In

this work, Bandini’s research functions as a deeper explanation on

membrane’s structure; it is used as an illustration of the process

in a micro level and a validation of our research results, as well as

the mentioning of the following studies, related in some points that

will be explained with our results.

Hilal et al. (2008) calculated the pure water flux (L/m 2 h) for

NF270 and NF 90 membranes without any temperature specifica-

tion. The results for NF 270 were 157.4, 184.2, 211.1, and 236.7 for

6, 7, 8 and 9 bar, respectively, and for NF 90 they were 57.4, 67.2,

76.9, and 86.4 for the same data of transmembrane pressure. Pro-

cessing these values according to Eq. (2), it is possible to obtain the

R M value of the experiments carried out by Hilal et al. (2008). For the

NF 270 membrane R M is 1.43 × 10 13 and for NF 90 R M is 3.33 × 10 13 ,

using 0.001 Pa s for the viscosity. Comparing these R M results with

Table 2, it can be observed that the range of magnitude is the same

and also that the membranes used in this work have higher resis-

tance. Such difference may lie on the fact that temperature used in

Table 3

Flux at different TMP.

TMP (bar)

NF-270

NF-200

NF-90

DSS-HR98PP

Flux(L/m 2 h)

  • 3.5 24.7

56.2

27.6

10.8

  • 6.0 35.6

81.3

42.0

16.7

  • 9.0 50.7

106.6

57.0

23.3

  • 12.0 65.3

146.0

69.8

29.5

  • 16.0 84.8

186.6

92.5

36.7

a

b

100 NF270 , pH7 NF270 , pH5 80 60 40 20 0
100
NF270 , pH7
NF270 , pH5
80
60
40
20
0
0 5 10 15 20 25 30 TMP (bar) DSS HR98PP , pH5 DSS HR98PP ,
0
5
10
15
20
25
30
TMP (bar)
DSS HR98PP , pH5
DSS HR98PP , pH7
100
80
60
40
20
0
0
5
10
15
20
25
30

TMP (bar)

c

NF200,pH5 NF200, pH7 100 80 60 40 20 0
NF200,pH5
NF200, pH7
100
80
60
40
20
0
0 5 10 15 20 25 30 TMP (bar) 100 d 80 60 NF90, pH5 40
0
5
10
15
20
25
30
TMP (bar)
100
d
80
60
NF90, pH5
40
NF90, pH7
20
0
0
5
10
15
20
25
30
AR%

TMP (bar)

Fig. 2. Retention of ammonium at a stationary phase. (a) Membrane NF270; (b) Membrane DSSHR98PP; (c) Membrane NF200 and (d) Membrane NF90. Processing conditions: 15 ± 1 C and 6.5 ± 0.5 mg/L of ammonium.

Hilal et al. (2008) was higher, thus producing an easy flow through

the membrane. Furthermore, the membrane compaction treatment

used in our work is higher compared to the 9 bar used by Hilal et al.

(2008), causing a denser membrane compared to a low pressure

treatment.

B. Cancino-Madariaga et al. / Aquacultural Engineering 45 (2011) 103– 108

107

1,0E-0 4 8,0E-0 5 6,0E-0 5 NF90, pH5 DSSHR 98PP, pH7 DSSHR 98PP, pH5 NF90, pH7
1,0E-0
4
8,0E-0
5
6,0E-0
5
NF90, pH5
DSSHR 98PP, pH7
DSSHR 98PP, pH5
NF90, pH7
NF200, pH7
NF200, pH5
NF270, pH7
NF270, pH5
4,0E-0
5
2,0E-0
5
0,0E+00
0
5
10
15
20
25
30
35
Flux (m 3 /m 2 *s)

TMP (bar)

Fig. 3. Permeation flux at the stationary stage for the membranes with TMP and pH variation. Processing conditions: 15 ± 1 C and 6.5 ± 0.5 mg/L of ammonium.

Ali et al. (2005) prepared their own PES membrane to be used as

a low pressure membrane in an aquacultural system. Consequently,

they obtained a lower membrane resistance (4.86 × 10 12 m 1 ) as

we did in our work. When the data supplied by Ali et al. (2005) is

used according to Eq. (2), once again the difference can be attributed

to the difference in the membrane compaction and also to the fact

that Ali et al. (2005) prepared a special thin membrane to produce

high flux.

Bellona and Drewes (2005) determined the pure water perme-

ability for NF 200 in 1.2 L/(m 2 day kPa at) 25 C. Using Eq. (2) with a

viscosity of 8.937 × 10 4 Pa s at 25 C, the R M is 8.06 × 10 13 m 1 .

Comparing this result with Table 2, the membrane resistance

obtained in our experiments resulted slightly lower.

Fig. 2 shows the ammonium retention for all the studied

membranes at pH 5 and 7. Significant differences (p 0.05) in

ammonium retention were observed in the studied membranes

at these pHs. All membranes showed a higher AR at pH 7. This

behavior can be explained because the furthest they were from

their isoelectric point, which is approximately between 3.0 and 4.3,

the higher the charge was, thus helping the ammonium ion reten-

tion (NH 4+ ) in the areas of the negatively charged active layer. Such

explanation totally coincides with the principle of electroneutral-

ity described by Schaep and Vandecasteele (2001), and Chellam and

Taylor (2001).

The coupling of ammonium ions to the active layer of the mem-

brane forms a positively charged superficial layer, those charged

functional groups attract ions of the opposite charge (Chellam and

Taylor, 2001), which managed the repulsion of other ammonium

ions and exceeded for all cases a 76.8% of AR. This explanation

becomes the reason, added to the relevance of pH factor over the

efficiency in AR and its application potential in RAS, why its indis-

pensable to maintain pH variable in a value close to 7. RAS can

manage the above without problem; the system integrates moni-

toring of pH methods.

To follow the interpretation, the positively charged layer cre-

ates an incremental rejection due to increased pressure caused

by solute (NH 4+ ) retained by superficial forces of the membrane

active layer. As shown in Fig. 2b, these rejection forces are inde-

pendent from pressure as long as, the latter keeps below a limit

value, named critical TMP. Whenever the pressure reaches the crit-

ical TMP or higher values, the various electrochemical forces are

surpassed by pressure forces, offsetting their rejection effect and

allowing the ion ammonia to go through the membrane (Pontalier

et al., 1999; Paugam et al., 2004). Thus, this process allows the

reduction of the chemical potential of the ammonium ions (Debye-

Hückel Theory). The critical TMP value was determined for all the

membranes involved in this study with values of 16 bar for the

nanofiltration membranes (NF90, NF200 and NF270) and 24.5 bar

for the reverse osmosis membrane (DSSHR98PP). RO membrane

presents a thicker active layer with diffusion areas smaller than

the hydrated ammonium, thus generating a lower diffusion coeffi-

cient with respect to the rest of the studied membranes (Bellona

et al., 2004), thus explaining the difference in the critical TMP.

Membranes NF90, DSSHR98PP, NF200 and NF270 showed values

of AR 100, 99.7, 98.4 and 76.8%, respectively, near the critical TMP

and pH 7.

According to the AR value of 85.7% at 4 bar obtained by Ali et al.

(2005), NF 90, NF 200 and RO membranes presented higher AR,

especially at pH 5. The same happens in the work of Qin et al.

(2005). This effect may be due to the previously mentioned com-

paction procedure. A higher compaction as the treatment done for

NF and RO membranes, produce a more dense membrane, lower

flux, higher R M and a higher AR.

Fig. 3 shows the influence at the flux when the TMP varied. No

significant differences (p 0.05) were observed in the permeation

flow of the studied membranes between pH 5 and 7. Membranes

DSSHR98PP, NF200 and NF90 showed a higher permeation at pH

7; this behavior coincides with Mänttäri et al. (2006), who estab-

lished that as pH increases, the membrane pore grows allowing an

increment in the permeation flow.

The flux reported by the experiences of Qin et al. (2005) was

between 8.516 E-6 (m 3 /m 2 s) and 1.228 E-5 (m 3 /m 2 s), with approx-

imately 96% of AR with the RO module. Observing Fig. 3, the value

obtained by NF 90 is within this range. At 20 bar with pH 7, for

example the flux is 1.65 E-5 (m 3 /m 2 s) with a 100% of AR.

These results agree with the different phenomena that could

explain the ion retention or the AR. As previously mentioned,

NF’s membranes act as a result of a combination of steric and

electrostatic effects (Ismail and Hassan, 2007). Bruni and Bandini

(2009) explain the phenomena through the ADS-AMF model devel-

oped by Bandini (2005). In this model, three mechanisms are

present, depending on the membrane material and also the effect

of the solution over the membrane itself. One is the acid/basic

dissociation of the hydrophilic functional sites of the membrane;

second, the counter-ions site binding on dissociated hydrophilic

sites and the third mechanism is the competitive adsorption of

anions and cations on the hydrophobic functional groups of the

membrane.

  • 108 B. Cancino-Madariaga et al. / Aquacultural Engineering 45 (2011) 103– 108

4. Conclusions

There is a critical TMP for all the studied membranes, since the

AR decreases, with a value of 6 bar for membranes NF90, NF200 and

NF270, and 24.5 bar for the membrane DSSHR98PP. Ammonium

retention remains stable before the critical TMP is reached in all

membranes, with average values at pH 7 of 100, 99.7, 98.4 and 87.5

for membranes NF90, DSSHR98PP, NF200 and NF270, respectively.

The AR in all membranes was higher when the pH of the solution

was 7. For equal TMP, membrane NF270 exhibited the higher flow,

which was twice the flow of the membrane NF200 and four times

higher than membrane NF90.

Finally, it may be concluded that the selectivity in the ammo-

nium retention results from an electrochemical process, where the

pH and critical TMP influence the retention values of ammonium.

Taking these conclusions and other future works in this area, it is

possible to think in a future where membranes could be incorpo-

rated in the RAS systems to help control ammonium concentration.

Acknowledgements

The authors would like to thank Dr. Frank Lipnizki for supplying

the membranes of Alfa Laval used during this study, and specials

thanks to Dr. Nicolás Cifuentes Araya, for his contributions to the

first experiences with membranes.

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