Accepted Manuscript

Fish canning industry wastewater treatment for water reuse – a case study

Raquel O. Cristóvão, Cidália M. Botelho, Ramiro J.E. Martins, José M. Loureiro, Rui
A.R. Boaventura

PII: S0959-6526(14)01119-6
DOI: 10.1016/j.jclepro.2014.10.076
Reference: JCLP 4865

To appear in: Journal of Cleaner Production

Received Date: 27 June 2014

Revised Date: 20 October 2014
Accepted Date: 27 October 2014

Please cite this article as: Cristóvão RO, Botelho CM, Martins RJE, Loureiro JM, Boaventura RAR, Fish
canning industry wastewater treatment for water reuse – a case study, Journal of Cleaner Production
(2014), doi: 10.1016/j.jclepro.2014.10.076.

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1 Fish canning industry wastewater treatment for water reuse – a case

2 study
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4 Raquel O. Cristóvão1*, Cidália M. Botelho1, Ramiro J. E. Martins1,2, José M. Loureiro1,

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5 Rui A.R. Boaventura1

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8 Laboratory of Separation and Reaction Engineering (LSRE), Associate Laboratory LSRE/LCM,
9 Departamento de Engenharia Química, Faculdade de Engenharia, Universidade do Porto, Rua do Dr.
10 Roberto Frias, 4200-465, Porto, Portugal

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Department of Chemical and Biological Technology, Superior School of Technology, Polytechnic
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12 Institute of Bragança, Campus de Santa Apolónia, 5301-857 Bragança, Portugal

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16 *Corresponding author:

17 Tel: +351 22 508 2263; Fax: +351 22 508 1674

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18 E-mail: raquel.cristovao@fe.up.pt
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1 Abstract

2 The valorization of wastewaters from the fish canning industry is of great

3 concern, not only because of the high quantities generated, but also economic and

4 environmental benefits may result from a proper treatment approach of the waste

5 generated while reducing costs related to wastewater discharge.

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6 A limiting factor for the reuse and recycling of treated fish canning wastewater

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7 into the an industrial plant and also for other uses is the high salt content, which persists

8 even after conventional treatment. So, the reuse of fish canning industry industrial

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9 wastewater was assessed by combining conventional treatments, such as sedimentation,

10 chemical coagulation-flocculation and aerobic biological degradation by (activated

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sludge process) followed by a polishing step using by reverse osmosis (RO) and
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12 ultraviolet (UV) disinfection.
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13 In this investigation all these treatment processes were optimized in order to

14 remove essentially the effluent suspended particles (primary treatment), the organic
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15 matter content in a the biological aerated reactor by activated sludge (secondary

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16 treatment) and, finally, the remaining salts and microorganisms (tertiary treatment).

17 The overall removal efficiencies obtained were: 99.9% for dissolved organic
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18 carbon (DOC), 99.8% for oil and grease (O&G), 98.4% for total suspended solids

19 (TSS), above 96% for anions and cations and 100% for heterotrophic bacteria expressed
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20 as colony-forming units (CFU). The final clarified effluent was found to have the

21 quality requirements to be recycled or reused in the industrial unitplant, allowing the

22 reduction of the effluent to be discharged, the water use and the costs of tap water for

23 industrial use.

24 As regards the operating energy and chemicals costs, the unit cost to obtain a

25 treated effluent to be reused in the process is costs 0.85 €/m3. This value can be reduced

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1 by about 60% if the goal is only to meet the legislated standards for the effluent

2 discharge into water bodies. Tap water for the industrial plant costs about 2.1 €/m3.

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6 Keywords: Fish canning wastewater; wastewater reuse; reverse osmosis; UV

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7 disinfection; coagulation-flocculation; biological treatment

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9 1. Introduction

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10 Water consumption in fish processing industry and the production of high
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11 strength wastewaters are of great concern worldwide (Chowdhury et al., 2010). In fact,

12 in this type of industries a huge amount of water is used throughout all steps, including
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13 cleaning, cooking, cooling, sanitization and floor washing. Fish canning wastewaters
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14 are known to contain organic contaminants in soluble, colloidal and particulate form
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15 (Chowdhury et al., 2010). The biodegradable organic matter is mainly in the form of

16 proteins and lipids. The concentration and volume of wastewater from fish processing
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17 varies widely, depending on the composition of the fish to be processed, the additives

18 used (e.g. brine, oil, tomato sauce), the unit processes involved and the source of the
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19 water (Palenzuela, 1999), among other factors. There is a need, for both economic and
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20 environmental sustainability reasons, to consider the wastewater treatment in order to

21 obtain water with the quality requirements established by the European Directive

22 98/83/EC (Table 1), which allows its reuse into the industrial process.

23 Fish processing wastewaters are generally treated using physical-chemical

24 methods (Fahim et al., 2001), biological methods (Palenzuela, 1999), or a combination

25 of both. In integrated treatment systems, sedimentation, dissolved air flotation and pH

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1 adjustment are usually employed as primary treatment steps (Zufía and Aurrekoetxea,

2 2002) and the biological processes (aerobic and anaerobic) are known to be the more

3 appropriate for organics removal as a secondary treatment (Alexandre et al., 2011;

4 Chowdhury et al., 2010). However, fish canning wastewaters also have high salinity.

5 The elimination of salts is usually expensive and, on the other hand, the high salinity

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6 and the seasonal variation of the effluent characteristics make difficult to remove the

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7 organic matter through by a biological treatment process (Zufía and Aurrekoetxea,

8 2002). Nevertheless, for water reuse, a polishing step to remove the effluent salinity is

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9 necessary. Recent studies revealed that membrane separations may help in solving the

10 problem of attaining a quality of water that allows being recycled back to the process

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(Mavrov and Bélières, 2000). Membrane separation allows the removal of
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12 contaminants, the recovery of dissolved or suspended high added value components
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13 constituents (proteins, pigments, enzymes, etc.) (Martin et al., 1995) and even the water

14 reuse for certain applications (Rautenbach and Linn, 1996). Kuca and Szaniawska
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15 (2009) studied the application of microfiltration using ceramic membranes for treatment
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16 of salted aqueous effluents from fish processing and Pérez-Gálvez et al. (2011)

17 investigated the performance of three ceramic membranes in the treatment of the press
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18 liquor resulting from the compaction of sardine by-products. However, reverse osmosis

19 is based on a lower pore size (around 0.001 micron), which allows the retention of
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20 smaller particles, including most ions present in the water. Reverse osmosis has been

21 shown to be able to separate the salt content out of wastewater, retaining small ions

22 such as Na+ or Cl- (Rautenbach and Mellis, 1995).

23 Although conventional treatment processes remove up to 95–99% of some

24 microorganisms, the characteristics of the treated wastewater render it inappropriate for

25 direct reuse, mainly due to the presence of a high concentration of pathogenic pathogens

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1 microorganismsrender the water inappropriate for direct reuse. The safe operation reuse

2 of water reuse systems therefore depends on wastewater disinfection (Gómez et al.,

3 2006). Requirements for wastewater reuse are based principally on biological quality

4 considerations. However, due to wide fluctuations in industrial effluent quality, this

5 becomes more challenging. Chlorination is the most widely used method to inactivate

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6 pathogenic microorganisms in water and wastewater. However, questions have been

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7 raised regarding the formation of disinfection by-products (DBPs), known as

8 carcinogens (Liberti et al., 2003), the erosion of water pipes and unsafe operation (Guo

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9 et al., 2011). In recent years, UV light was has been increasingly used as a disinfectant,

10 to inactivate bacteria without the formation of toxic by-products (Hijnen et al., 2006). In

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addition, the photoreactor design and lamp technology have improved considerably
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12 (Cassano et al., 1995). These facts led to the recognition by US Environmental
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13 Protection Agency (USEPA) that UV disinfection is the best current disinfection

14 technology (Hijnen et al., 2006). UV light, emitted by mercury arc-lamps (low or

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15 medium pressure), is effective against a variety of pathogenic pathogens

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16 microorganisms including viruses, bacteria and protozoan cysts (Hallmich and Gehr,

17 2010). Essentially, the inactivating effects of UV rays are due to DNA changes (e.g.,
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18 strand breaks, formation of thymine dimers) that result in inhibition of replication and,

19 in case of lethal doses, in a loss of reproducibility. A disadvantage of this method is the

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20 possible reactivation of UV damaged microorganisms. However, reactivation decreases

21 significantly when the water is exposed to visible light, simultaneously or prior to UV

22 irradiation (Guo et al., 2009; Hallmich and Gehr, 2010).

23 This work intends to develop a real, effective and workable solution that avoids

24 and/or reduces the rejection of wastewaters from the fish canning industry, managing

25 them in the most appropriate way to obtain a product with higher added value (water)

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1 which can be reused. This objective will be achieved through the optimization of a

2 series of various treatment steps envisaging the wastewater reuse in the industrial

3 process, while reducing the discharge of effluent, limiting the water use and saving

4 money. To our knowledge this is the first investigation of a combined treatment for of

5 fish canning industrial wastewaters for water reuse.

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6

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7 2. Fish canning process

8 The fish canning production process begins with the reception of raw materials

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9 (fish, sauces and packaging materials). In the fishing boats, the fish is kept in water

10 tanks. At the factory, the water drains out and the fish is weighed and stored again in

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salted water. The main waste stream resulting from this operation is the water used in
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12 the fish transport, along with water used for preservation in the boats. The wastewater
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13 from this stage contains blood, fish, rocks and sand from the fishing boats tanks.

14 Then the fish is placed in brine, a process that requires water and produces an
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15 effluent especially rich in salt, blood and scales. Then unwanted fish parts are removed,
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16 particularly head and viscera, to which is also necessary the use of water. From this

17 process results an effluent mainly contaminated with salt, blood and fish waste that
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18 cannot be used as food. In the fish washing process water is used in abundance. From

19 this operation results a wastewater containing mainly blood, oil, flakes, salt and fish
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20 tissues.

21 The following process corresponds to the cooking and subsequent cooling of the

22 fish. The fish cooking is done through direct contact with steam. After cooking, the

23 water produced is drained and the fish is cooled by water spraying. There are two

24 sources for the wastewater generated in this process: one originated from the cooking,

25 which has a very high concentration of organic material and fats and other from

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1 washing and cooling (usually seawater) that has low organic load, but high salinity.

2 Hence, the fish goes to canning, sauces addition, spiking and cans washing processes.

3 This final wash leads also to an effluent that contains, essentially, fish fat. Finally, the

4 cans are sterilized with steam and cooled with water, which also results in a wastewater.

5 In addition to all these wastewaters produced, liquid spills occur due to shipping,

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6 handling, canning and cleaning of equipment, involving waste of raw materials.

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7 The water used in the various steps of the process can be replaced by reused

8 water from the treatment of the wastewaters generated.

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10 3. Materials and methods

11 3.1 Wastewater characterization

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12 A sampling program was carried out in a selected fish canning company with a
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13 production capacity of 100,000 cans/day, located at Póvoa de Varzim, in northern

14 Portugal. Several samples of 100 L of wastewater were collected weekly during 3

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15 months and characterized after a preliminary screening stage. Standard Methods for the
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16 Examination of Water and Wastewater (APHA, 2005) were adopted for the

17 measurement of total suspended solids (TSS), volatile suspended solids (VSS),

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18 dissolved organic carbon (DOC), chemical oxygen demand (COD), biological oxygen

19 demand (BOD5), oil and grease (O&G), total phosphorus (Ptotal), total soluble nitrogen
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20 (Ntotal soluble), ammoniacal nitrogen (Nammoniacal) and several anions and cations. A

21 Shimadzu 5000A Total Organic Carbon analyser was employed for DOC

22 measurements. The reported values represent the average of at least two measurements;

23 in most cases each sample was injected three times, validation being performed by the

24 apparatus only if the coefficient of variation (CV) was smaller than 2%.

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1 The pH was measured using a selective electrode (Hanna Instruments HI 1230)

2 and a pH meter (Hanna instruments HI 8424) and the conductivity at 20 ºC was

3 determined using a conductivity probe (WTW TetraCon 325) and a conductivity meter

4 (WTW LF538).

5 Anions were measured by ion chromatography (Dionex ICS-2100) using a

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6 Dionex Ionpac (column AS 11-HC 4 x 250 mm; suppressor ASRS 300 4 mm). Cations

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7 were analyzed also by ion chromatography (Dionex DX-120), using a Dionex Ionpac

8 (column CS12A 4 x 250 mm; suppressor CSRS 300 4 mm). Isocratic elution was

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9 achieved with NaOH 30 mM / methanesulfonic acid 20 mM at a flow rate of 1.5/1.0

10 mL/min for anions/cations analysis, respectively.

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12 3.2 Wastewater treatment sequence

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A sequential treatment for fish canning wastewaters was investigated for water reuse (Figure 1).

14 This sequence consists of sedimentation/flotation (gravity separation) for settleable solids,

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15 floatable oils and grease removal, coagulation-flocculation using FeCl3 as coagulant for
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16 additional removal of oil and grease and non-settleable solids, aerobic biological treatment

17 (conventional activated sludge process) for soluble organic matter degradation, reverse osmosis
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18 (low pressure composite membrane) for salts removal and, finally, UV disinfection (low

19 pressure mercury lamp) for microorganisms’ inactivation.

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21 3.2.1 Sedimentation/Flotation

22 The first stage of the wastewater treatment process was sedimentation/flotation.

23 The removal of suspended particles by sedimentation or flotation depends upon the size

24 and specific gravity of the particles. Suspended solids may remain in suspension if their

25 specific gravity is similar to water while very dense particles settle down. So, the

26 effluent was left in graduated cylinders (42 cm height and 5.8 cm internal diameter) for

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1 1.5 h. The optimum sedimentation time was determined in previous sedimentation tests.

2 The graduated cylinders are provided with a sampling port, 5 cm above the bottom,

3 which allows taking samples directly from the middle layer (Figure 2, (a)). These

4 samples were then analyzed for TSS, DOC and O&G.

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6 3.2.2 Coagulation/flocculation

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The coagulation/flocculation process is used to remove colloidal particles and,

8 whenever the natural settling of suspended material is not possible or is too slow, to provide

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9 effective clarification. The addition of coagulants causes the destabilization of the colloids,

10 followed by particles collision and flocs formation. Flocs are separated from the water by

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11 sedimentation or flotation. The performance of a particular coagulant depends upon the quality
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12 of the wastewater. Different types of coagulants were selected and their performance was

13 assessed by varying the dosages employed and the pH of the wastewater.

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14 So, the clarified wastewater, from the sedimentation/flotation stage, was

15 submitted to chemical coagulation/flocculation, using a standard jar test apparatus (Jar

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16 tester JLT6, VELP Scientifica) (Figure 2, (b)). The adequate coagulant dosage and the
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17 reaction pH were optimized by performing several jar-tests, using 7 coagulants (2

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18 organic compounds (RIPOL 070 and RIPOL 1815) and 5 inorganic salts (aluminum

19 sulphate (Al2(SO4)3.16H2O), ferric sulphate (Fe2(SO4)3), ferric chloride (FeCl3), calcium

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20 chloride (CaCl2) and polyaluminium chloride (PAX-18)), at 3 out of 5 different coagulant

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21 dosages (from 20 to 400 mg/L). The pH was varied between 5 and 9 for each optimum

22 coagulant dosage achieved. Each jar was filled with 500 mL of sample and the

23 coagulant dose and pH value were adjusted to the intended values. The experimental

24 procedure consisted of a rapid mixing at 150 rpm for 3 min and, after that, the

25 wastewater was moderately stirred at 20 rpm for 15 min to promote flocculation.

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1 Finally, a 1 h sedimentation stage allowed the flocs formed to settle. The supernatants

2 obtained were then characterized in terms of TSS and O&G.

4 3.2.3 Biological treatment

5 The biological treatment was applied to the fish canning wastewater after

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6 sedimentation/flotation and coagulation/flocculation steps in order to evaluate the

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7 organic matter removal efficiency by activated sludge. A sample of suspended biomass

8 from the aeration tank of a Municipal Wastewater Treatment Plant (Porto, Portugal) was

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9 used as inoculum. Aeration of the wastewater provides oxygen to aerobic

10 microorganisms’ metabolic process, causing the flocs formation – activated sludge –

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and allowing the reduction of the organic content of the wastewater. The flocs are
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12 separated from the treated effluent by sedimentation.
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13 The experiments for this study were performed in a biological system that

14 consists of a 110 L feed tank containing the wastewater to be treated, an aeration tank
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15 (internal diameter (ID) = 19 cm, height (H) = 33 cm, working volume (V) = 6 L)
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16 equipped with air diffusers at the bottom to ensure the oxygen supply and the mixing of

17 the whole reactor content (the air flow rate was about 6 L.min-1), a secondary
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18 sedimentation tank (ID = 19 cm, Hcylinder = 31 cm, Hconic = 15 cm, V = 6 L) equipped

19 with a sludge recirculation system and a storage tank to receivefor the final effluent
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20 (treated wastewater). There are also two peristaltic pumps operating at adjustable flow

21 rate: one for reactor feeding and another for sludge recirculation (Figure 3, (a)).

22 Before conducting the biological treatment studies themselves, an the

23 acclimatization and growing period of the activated sludge used as of the inoculum was

24 carried out in batch mode during 20 days in order to obtain a biomass concentration in

25 the reactor greater than 1500 mg SSV/L. Once reached this value, the operation was

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1 shifted to continuous mode. Temperature (T), pH and dissolved oxygen (DO) were

2 approximately T = 22 ± 2 ºC, pH = 7.5 ± 0.5, DO = 2.0 ± 0.5 mg/L, respectively,

3 throughout the experiments.

4 The reactor was operated at 3 different hydraulic retention times (HRT): 5.0, 6.0

5 and 8.0 hours, and the DOC of the feeding stream was between 600 and 700 mg/L,

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6 approximately. Influent and effluent samples were taken to measure DOC values.

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8 3.2.4 Filtration

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9 The sand filter allows the particles retention from the upstream treatments, as

10 well as of the biomass from the secondary clarifier. The wastewater passes downstream

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through several sand layers of decreasing particle size, which allows for the retention of
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12 the impurities.
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13 Paterniani and Conceição (2001) claim that sand filtration process has some

14 advantages over other technologies, highlighting the non-chemicals usage, not requiring
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15 process control sophisticated equipment, besides being of simple construction. These

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16 advantages, together with the use of alternative materials and simple hand work, can

17 reduce the initial costs of construction, operation and maintenance.

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18 So, in order to remove residual suspended solids found in the secondary effluent

19 that may interfere with the subsequent RO process, simultaneously reducing the
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20 concentration of organic matter and turbidity (Hamoda et al., 2004), the biologically

21 treated effluent was passed through a rapid sand filter, before reverse osmosis and UV

22 disinfection processes.

23 The filter used for in the filtration stage was a gravity sand filter (50 cm height

24 and 11.3 internal diameter) composed of a 40 cm layer of sand (density 2.6 g/cm3) with

25 diameter between 0.5 and 1 mm. Two 5 cm gravel layers were placed on the top and on

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1 the bottom of the filter column to better distribute the water over the sand column and to

2 act as support medium, respectively (Figure 3, (b)). The filter was designed and

3 operated to provide an average filtration rate of 2.4 m3.m-2.d-1. The efficiency of the

4 sand filter was determined assessed based on thein terms of TSS reduction of TSS.

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6 3.2.5 Reverse osmosis

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7 Reverse osmosis is a membrane separation process, under pressure, in order to

8 produce very high quality water, by removing some suspended contaminants, and

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9 separating low molecular weight dissolved substances (ions and soluble organic and

10 inorganic compounds), and microorganisms.

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The effluent from the sand filter was stored in a 600 L-capacity feed tank and
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12 then pumped to the reverse osmosis system by a MEW pump QB-70, at a maximum
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13 flow rate of 7.7 L/min.

14 The reverse osmosis pilot consisted of a RO 250 Model from AQUAQUÍMICA,

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15 Lda. (Figure 4), allowing a maximum permeate flow rate of 250 L/h and a pressure
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16 between 7 and 15 bar. This system consists of one Thin Layer Composite (TLC)

17 membrane (5 µm, 40 x 40 inch), membrane housing of plastic reinforced with fiberglass

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18 (PRFG) and works at operating temperatures between 13 and 30ºC. The installed pump
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19 is Efaflu/Lowara with a 2.2 kW/400 V motor, minimum pressure inlet alarm and pump
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20 protection.

21 The reverse osmosis (RO) tests were carried out at permeate flow rates between

22 192 and 216 L/h and concentrated flow rates between 60 and 270 L/h. The pressure was

23 varied between 8.5 and 10.0 bar. Feed flow rate and operational pressure were adjusted

24 by controlling valves of recirculation and concentrated streams and visualized in

25 pressure gauges and flow meters. The RO plant was operated at a recovery rate between

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1 50 and 75% by adjusting the concentrate drain valve according to the permeate flow

2 achieved.

3 The permeate stream is sent to the UV disinfection unit and the concentrate

4 stream is discharged into the sewerage system. Before sending the permeate to the last

5 treatment step some samples are were collected from time to time to be analyzed in the

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6 laboratory in terms offor DOC, Ntotal soluble, conductivity, anions and cations.

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7 The performance of RO membranes tends to decrease during operation as a

8 biomass layer builds up on the membrane surface, which reduces the flux and permeate

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9 quality with a concurrent increase in differential pressure. Blockage of the membranes

10 may lead to precipitation of salts on the membrane surface and in the feed inlets. A

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specific cleaning regime was developed to prevent the formation of the biomass layer,
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12 and consequently scaling and fouling, by passing chlorine solution (1 mg/L) throughout
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13 the system.

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15 3.2.6 UV Disinfection
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16 The UV disinfection system uses UV light at sufficiently short wavelength to

17 destroy the organism’s genetic material (DNA and RNA), leaving them unable to
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18 perform vital cellular functions, as reproduction.

19 The UV disinfection equipment is composed of one 45 W low-pressure mercury

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discharge lamp, 1 and 5 µm filters, an AISI 304 stainless steel chamber, an hour meter
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21 and electronic chokes. All components of the system are inside a steel AISI 316 L

22 cylindrical reactor (Figure 5). The equipment shall provide a minimum UV radiation

23 dose of 25 mW.s-1.cm-2 at the end of the lamp effective life.

24 The clarified effluent from the reverse osmosis system is sent directlyfed to the

25 UV disinfection system at a flow rate of 250 L/h. Then samples are collected after the

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1 disinfection and, finally, this effluent is evaluated as regards its suitability for water

2 reuse or recirculation. The samples before and after being subjected to UV disinfection

3 were analyzed for the presence of microorganisms presence, by performing

4 heterotrophic bacteria counts by scattering method with AGAR medium plates. The

5 plates were incubated at 22 and 37 °C, during 24 and 48 h. Several dilutions were made

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6 for each sample.

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8 4. Results and Discussion

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9 4.1 Analysis of wastewaters from fish canning industries

10 The quality of raw fish canning wastewaters varies according to the overall

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production of the fish canning industry. In order to obtain a representative set of
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12 information data on effluent properties, several samples were collected at different times
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13 and analyzed. Their characteristics are presented in Table 2, where maximum and

14 minimum values obtained from for several samples are reported. The high BOD5 and
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15 COD values indicate a heavy contamination by organic matter. High contents of O&G
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16 and salts are present, as indicated by the Cl- and Na+ concentrations and conductivity

17 values(corresponding to salinity between 2.5 and 15 ppt).

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19 4.2 Primary treatment by sedimentation/flotation and coagulation/flocculation

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20 The sedimentation/flotation and the coagulation/flocculation processes are the

21 most important physico-chemical treatment steps in the primary treatment of some

22 industrial wastewaters to reduce the suspended and colloidal materials particles

23 responsible for turbidity. A screening process device is also very importantusually

24 required; nevertheless, most fish canning industries already have implemented this kind

25 of pre-treatment.

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1 The results obtained show that sedimentation/flotation for 1.5 h, was very

2 effective for the removal of oilin removing oil and grease and settleable solids. The

3 mean values for TSS and O&G removals were 48% and 75%, respectively. Since this

4 physical treatment does not promote destabilization ora significant degradation of

5 organic matter, DOC removal was only 4%. These removal efficiencies are similar to

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6 values reported in the literature for other fish processing wastewaters. Muthukumaran

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7 and Baskaran (2013) concluded that the majority of the suspended solids that contribute

8 to the organic load would be difficult to remove using a typical sedimentation system.

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9 Following the sedimentation/flotation stage, a coagulation/flocculation step was

10 conducted employed to remove the resistant suspended and colloidal materials still

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present in the wastewater. The addition of coagulants causes the destabilization of the
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12 particulate matter present in the wastewater, followed by particles collision and flocs
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13 formation. Flocs are separated from the water by sedimentation or flotation. The

14 performance of a particular coagulant depends upon the quality of the wastewater.

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15 Different types of coagulants were selected to observe their effects on fish canning
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16 effluent. Performance of coagulants was also based on dosages used and pH value of the

17 wastewater. The most commonly used coagulants used in wastewater treatment are
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18 inorganic compounds (Amuda and Amoo, 2007; de Sena et al., 2008; Wang et al.,

19 2007). So, aluminum sulphate, ferric sulphate, ferric chloride, calcium chloride and
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20 polyaluminium chloride were employed in initial experiments at coagulant doses of

21 100, 200 and 400 mg/L. The results presented in Table 3 (a) show that there is not a

22 single optimum coagulant for the chemical treatment of the wastewaters under study.

23 The optimal coagulant and the respective optimal dosage depend on what it is wanted to

24 remove in the moment. However, ferric chloride was found to be an effective coagulant

25 in reducing both TSS (85.8%) and O&G (99.2%) in the fish canning wastewater, at a

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1 dosage of 400 mg/L. Regarding DOC, none of the studied coagulants achieved good

2 significant removals. Other works also showed that the coagulant choice to use depends

3 on the intended purpose. Amuda and Alade (2006) used alum, ferric chloride and ferric

4 sulfate for abattoir wastewater treatment by coagulation/flocculation and found that

5 alum was more effective in the reduction of TSS, whereas ferric sulfate was more

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6 effective in the COD reduction. Braz et al. (2010) The winery wastewater treatment was

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7 also studied winery wastewater treatment by coagulation/flocculation using four

8 different coagulants by Braz et al. (2010), who provedconcluding that the best turbidity

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9 removals were achieved with aluminum sulphate, while TSS higher removals were

10 obtained with calcium hydroxide. The same authors also reported the smallslight

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capacity ability of coagulation/flocculation treatment to remove COD from winery
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12 wastewaters.
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13 Organic coagulants can also be used in coagulation/flocculation. So, two

14 organic coagulants (RIPOL 070 and RIFLOC 1815) were also studied in the range 20 –
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15 400 mg/L were also employed (Cristóvão et al., 2012). Nevertheless, the best results
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16 obtained with these coagulants (78.7% of TSS and 99.2% of O&G with 150 mg/L

17 RIFLOC 1815) were not better than those obtained with the inorganic coagulants.
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18 Another parameter that may influence this type of treatment is the pH.

19 Therefore, in addition to the studies carried out at the raw wastewater pH, tests on the
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20 influence of pH in the range from 5.0 to 9.0 were also performed, in the best conditions

21 previously encountered. The obtained results (Table 3 (b)) show that despite the high

22 removals obtained at alkaline pH, the best removals were observedoccurred in the tests

23 carried out without wastewater pH adjustment. Similar results were achieved by Martín

24 et al. (2011) in the coagulation/flocculation treatment of wastewater derived resulting

25 from sauce manufacturing. Optimization showed similar results under all pH conditions.

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1 In this work, alkaline pH was selected as it permitted ease of operation and lower

2 operational costs due to the elimination of pH adjustment stages.

3 The removals obtained using 400 mg/L of ferric chloride led to a wastewater

4 with suitable characteristics to forward to a secondary biological process for organics

5 removal.

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6

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7 4.3 Secondary treatment by activated sludge

8 The previous steps, sedimentation/flotation and coagulation/flocculation, were

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9 not very effective to removein DOC removal, because soluble organics contribute

10 significantly to the overall organic matter content of the fish canning wastewater.

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Likewise, the pre-treated wastewater requires removal of organic components by a
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12 biological treatment process. In this case an aerobic biological treatment by activated
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13 sludge was selectedemployed. The biological aerobic reactor operated at HRT of 5, 6

14 and 8 h. The obtained results are presented in Table 4 and indicate that the biological
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15 treatability of this type of wastewaters, under aerobic conditions, is very satisfactory,

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16 since low DOC values were achieved at the reactor outlet. The highest DOC removal

17 efficiency (95.8%) corresponds to the highest HRT, which means that, if necessary,
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18 higher hydraulic retention times could be used, but greater aeration tanks would be

19 required. The biological treatment of fish processing wastewaters was also studied by
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20 other researchers. Riaño et al. (2011) studied the treatment of a fish processing

21 wastewater by in two photobioreactors inoculated with microalgae from a lagoon

22 containing aerobically treated swine slurry and with sludge from a membrane

23 submerged bioreactor treating winery wastewater. In such system approximately 70% of

24 total chemical oxygen demand (COD) removal was reached. A new pilot scale hybrid

25 biofilm-suspended biomass membrane bioreactor was used by Artiga et al. (2008) to

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1 treat wastewaters generated in a fish canning factory. A COD removal efficiency of

2 92% was obtained achieved after adaptation of the sludge to the salinity. Comparing

3 these organic matter removal values with that obtained in this work, it is possible to

4 confirm the feasibility and the reliability of the treatment by activated sludge, since the

5 removals obtained were even higher.

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6

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7 4.4 Tertiary treatment by filtration, reverse osmosis and UV disinfection

8 Due to the high chloride concentration and to the presence of microorganisms, a

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9 polishing process by reverse osmosis and UV disinfection is necessary in order to reuse

10 fish canning wastewater.

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The biological treatment by activated sludge significantly reduced the organic
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12 content of the wastewater, but suspended biomass still present after clarification may
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13 cause fouling of reverse osmosis (RO) membranes. Thus, to reduce the fouling of

14 reverse osmosis membrane and to prolong its life, a tertiary filtration of the pretreated
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15 wastewater is required.
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16 Paterniani and Conceição (2001) claim that sand filtration process has some

17 advantages over other technologies, highlighting the need for non-chemicals usage, not
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18 requiring process control sophisticated equipment, besides being of simple construction.

19 These advantages, together with the use of alternative materials and simple hand work,
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20 can reduce the initial costs of construction, operation and maintenance.

21 So, in order to remove residual suspended solids found in the secondary effluent

22 that may interfere with subsequent RO process, simultaneously reducing the

23 concentration of organic matter and turbidity (Hamoda et al., 2004), The biologically

24 treated effluent was passed through a rapid sand filter, before being sent pumped to

25 reverse osmosis and UV disinfection processes. TSS values before and after the sand

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1 filter were measured and an appreciable solids reduction of TSS was achieved (78%).

2 This removal efficiency lies within the values reported in the literature for rapid sand

3 filtration (Hamoda et al., 2004; Metcalf and Eddy, 1991).

4 The aim of this study was to obtain treated water with enough quality to be

5 reused in the industrial plant. The Portuguese legislation forlimit of salt content of in

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6 waters for human consumption (Decree-Law No. 306/2007), measured as conductivity

at 20 ºC, is 2500 µS/cm (European Directive 98/83/EC). Since reverse osmosis is an

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8 appropriate technology to remove salts from effluents, several tests were conducted in

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9 the RO unit (Figure 4), at permeate flow rates between 192 and 213 L/h, concentrate

10 flow rates between 60 and 270 L/h and pressures between 8.5 and 10.0 bar. The 10Ten

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trials were performed taking into account these variations are as described in Table 5.
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12 After passing through RO membrane a A complete water analysis was done on
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13 permeates from the RO membrane. The DOC, Ntotal soluble and conductivity removals

14 obtained at each test madedifferent operating conditions are presented in Table 5. It

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15 seems that for a similar pressure, the greater the permeate flow rate and the lower the
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16 concentrate flow rate, the better performance is achieved. The DOC and the

17 conductivity removals increase from 89.6 to 97.3% and from 98.4 to 99.1%,
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18 respectively, when increasing the permeate flow rate from 192 to 216 L/h. The best
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19 DOC, Ntotal soluble and conductivity removals (97.3, 99.8 and 99.1%, respectively) were
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20 achieved for the following conditions (test no. 10): permeate flow rate of 216 L/h,

21 concentrated flow rate of 60 L/h and pressure of 9.0 bar. Under the conditions of test no.

22 10, the permeate was also analyzed for cations and anions, and the following removals

23 were obtained: 98.9% for sodium, 97.0% for ammonium, 99.2% for potassium, 99.0%

24 for magnesium, 98.5% for calcium, above 96.0% for lithium, 99.2% for chloride, 97.1%

25 for nitrite, 99.8% for sulfate, 96.3% for bromide and 99.2% for phosphate. The overall

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1 performance of RO led to negligible concentrations of DOC, Ntotal soluble, conductivity,

2 anions and cations (estimated salinity of 0.03 ppt), as shown in Table 6. Similar results

3 were obtained by other authors. Scholz et al. (2005) used showed that a combined

4 treatment of MBR and RO allowing allowed for 90–100% reduction of COD, BOD and

5 ammonia in a mixed tannery effluent. Salt content was reduced to by 97.1%. Jin et al.

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6 (2013) verified that the combination of biological processes with and membrane

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7 processes, including reverse osmosis, applied to coking wastewater led to water suitable

8 for industrial reuse. Reuse of tannery wastewater was investigated by Ranganathan and

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9 Kabadgi (2011) employing conventional treatment methods like neutralization, clari-

10 flocculation and biological processes as pre-treatment before RO separation process.

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About 93–98%, 92–99% and 91–96% removal of TDS, sodium and chloride,
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12 respectively, were achieved for in 5 different tanneries. A large amount (70–85%) of
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13 water could be recovered and recycled.

14 Considering these results, it may be concluded that the present solution has
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15 substantial potential in the treatment of fish canning industry industrial wastewater for
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16 its subsequent reuse as process water or for irrigation. However, it is also necessary to

17 ensure that the microbiological quality also meets the legislation for water reuse in food
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18 industry (Decree-Law No. 306/2007European Directive 98/83/EC – Table 1), which

19 justifies requires the need to applyapplication of UV disinfection to the permeate of RO

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20 process.

21 So, after when subjecting to treating UV radiation (Figure 5) the effluent from

22 reverse osmosisRO, performed at the best conditions, by UV radiation (Figure 5), a

23 count of heterotrophic bacteria by the scattering method was carried out both before and

24 after the UV disinfection process, in order to check assess the treatment effectiveness

25 for the intended purpose. After incubation at 22 and 37 ºC for 24 and 48 h, it was found

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1 that the samples prior to UV disinfection still have plenty of microorganisms: 140,000

2 CFU/100 mL at 22ºC and 10,000 CFU/100 mL at 37ºC. However, when the count was

3 performed on the samples after disinfection, it was found that UV radiation is really

4 effective in the effluent disinfection, achieving as 100% removal of the bacteria present

5 in the feed stream was achieved.

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6 UV disinfection has also proved to be effective as regards other types of

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7 effluents to be reused in the industrial process. Mavrov and Bélières (2000) studied the

8 treatment of three low-contaminated process waters streams offrom the food industry by

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9 a combination of pre-treatment, membrane filtration and UV disinfection, achieving a

10 treated water with quality enough to be reused in accordance with company’s needs.

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Poultry slaughterhouse wastewater reclamation was investigated by de Nardi et al.
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12 (2011), using a lab-scale treatment system that consistsconsisting of a biological
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13 degradation (sequencing bath reactor), dissolved air flotation and UV disinfection. The

14 final effluent met the quality standards of the legislation for both potable water and
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15 effluents to be discharged into the receiving water bodies.

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16 Taking into account the characteristics of the clarified effluent after all the

17 overall treatment units proposed (Table 6) and knowing that after UV disinfection the
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18 wastewater does not present any microorganismsis 100% effective, one can conclude

19 that the treated water meets the values established for water intended for human
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20 consumption (Decree-Law No. 306/2007European Directive 98/83/CE). The water

21 reuse in the manufacturing process or, alternatively, for washing floors, irrigation, etc. is

22 also possible.

23 The accumulated removal efficiencies of in the different sequential treatment

24 stages of treatment are presented in Figure 6. Removals of 99.9% for DOC, 99.8% for

25 O&G, 98.4% for TSS, 99.1% for conductivity, above 96% for anions and cations and

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1 100% for heterotrophic bacteria (CFU) were attained at the end of the proposed

2 treatment sequence.

3 4.5 Energy and chemicals costs

4 Data on current energy and chemicals costs to operate the wastewater treatment

process on a basis at a flow rate of 10 m3 per day (working time 8 h.day-1) are

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5

6 summarized in this section. Operating costs regarding salaries, maintenance and others

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7 were not considered as they are less significant.

8 The first process comprises a flotation unit, 5 m3/h maximum flow capacity, 2.7

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9 kW electric power (including energy consumption for surface scraper). So, the energy

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10 consumption is 5.4 kWh per day. AN
11 Coagulation/flocculation unit comprises two steps: rapid mixing in a tank of

12 200 L during 5 minutes provided by an electrical agitator (shaft, coupling and four-
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13 bladed propeller at 45º, built in stainless steel), a 3-phase current motor 230/400 V,

14 nominal power of 0.55 kW and nominal speed 106 rpm (2.31 kWh per day); slow
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15 mixing at 32 rpm in a 1000 L tank during 30 minutes also using an electrical agitator
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16 (shaft, coupling and propeller type 2R, in stainless steel), a 3-phase current motor
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17 230/400 V with nominal power of 0.37 kW (represents a totalenergy consumption of

18 4.16 kWh/d). In this process the optimum results were obtained with a FeCl3 dosage of
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19 400 mg/L, which corresponds to a daily consumption of 4 kg. At a local supplier the
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20 cost of this chemical is about 290 € per tonne.

21 One of the main stages in the treatment plant is the activated sludge process. The

22 mixture and aeration in the biological reactor (total volume of 10 m3) is achieved by a

23 submersible aerator (0.55 kW) operating 10 hours a day and, in a 5 m3 secondary

24 clarifier (4 h detention time), a pump is installed for sludge recirculation (nominal

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1 power of 1.4 kW, 2 hours per day). This contributes to a daily energy consumption of

2 8.3 kWh.

3 Before the reverse osmosis stageRO the residual suspended solids are removed

4 using in a pressurized multimedia filter unit equipped with an automatic valve: flow rate

5 of 1400 L/h (at maximum filtration velocity 15 m/h), 0.09 m2 filtration area and

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6 working pressure 4 – 6 bar. According to the manufacturer this requires a 3000 L/h

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7 backwash flow (1.5 - 2.0 times the flow rate). So, a feeding/recirculating pump of 0.75

8 kW nominal power is needed to ensure Qmax = 3 m3/h at Hmax = 3 m.c.a. during a 20 min

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9 backwash daily period.

10 A reverse osmosis installation plant designed for a maximum production flow

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rate of 250 L/h (flow rate permeate flow rate equal to 75% of the inlet flow), including
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12 three RO membranes 40x40 (1016x180x180 mm) and a multistage pump of 2.2
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13 kW/400V motor can achieve the defined goals working 15 hours a day.

14 Finally, the permeate (7500 L/day) was submitted subjected to ultraviolet

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15 radiation in a cylindrical stainless steel reactor to promote its disinfection, using a 23 W

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16 low-pressure lamp operating continuously.

17 Table 7 summarizes the energy and the amount of reagent coagulant (FeCl3)
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18 consumed in each stage of the wastewater treatment process, as well as the total cost

19 associated. The value obtained considers the unit costs of energy and ferric chloride,
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20 0.1416 € / kWh and 290 € / tonne, respectively. On this basis, the unit treatment cost to

21 obtain a treated effluent suitable for reuse in the process is 0.85 € per cubic meter. As

22 shown in Table 7, we can reduce costs by about 60% if the goal is only to treat the

23 wastewater to meet the legislated discharge limits, i.e, if the tertiary treatment is

24 excluded. Taking into account that the tap water cost for the manufacturing process,

25 including taxes, is approximately 2.1 € per cubic meter, it is possible to conclude that

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1 even considering personnel, maintenance and produced sludge treatment/disposal costs,

2 the wastewater reuse, after treatment, will be a benefit to the fish canning industry in

3 study.

5 Conclusions

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6 The fish canning industry wastewater treatment was investigated in order to

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7 obtain water with quality requirements to reuse or recycle into in the industrial process.

8 The proposed sequential system, combining sedimentation/flotation,

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9 coagulation/flocculation, aerobic biological process degradation by activated sludge,

10 filtration, reverse osmosis and UV disinfection, proved to be very effective. Removals

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of 48% for TSS and 75% for O&G were observed in the sedimentation stage. For
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12 coagulation/flocculation, ferric chloride showed to be the better coagulant at a dosage of
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13 400 mg/L and raw wastewater pH. O&G and TSS removals attained 99.2 and 85.8%,

14 respectively. DOC was reduced by In the biological process by activated sludge 95.8%
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15 of DOC in the biological process by activated sludge removal was achieved for HRT =
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16 8 h. In the tertiary treatment, the rapid sand filtration retained 78% of TSS whereas

17 reverse osmosis removed 97.3% of DOC, 99.8% of Ntotal soluble, 99.1% of

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18 conductivity/salinity and above 96% of the analyzed ions. The removal of heterotrophic

19 bacteria (CFU) by UV disinfection reached 100%.

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20 The overall removals attained with by the treatment sequence under study were:

21 99.9% for DOC, 99.8% for O&G, 98.4 for TSS, 99.1% for conductivity/salinity, above

22 96% for the analyzed anions and cationsions and 100% for heterotrophic bacteria,

23 which led to achieve, as intended, water with quality requirements necessary to for

24 reuse or recycle back to in the industrial unit.

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1 The corresponding unit treatment cost is 0.85 € per cubic meter but it can be

2 reduced by about 60% if the goal is only to treat the wastewater in order to meet the

3 legislated discharge limits.

4 The implementation of this reuse process at large scale will bring both

5 environmental and economic benefits, since it allows the reduction of the effluent to be

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6 discharged and the water consumption, thus decreasing the associated costs.

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7

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8 Acknowledgments

9 This work is partially supported by project PEst-C/EQB/LA0020/2013, financed by

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FEDER through COMPETE – Programa Operacional Factores de Competitividade and
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11 by FCT – Fundação para a Ciência e a Tecnologia and by ValorPeixe – Valorização de

12 Subprodutos e Águas Residuais da Indústria de Conservas de Peixe, project in co-

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13 promotion I&DT QREN, nº 13634, financed by FEDER through POFC – Programa

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14 Operacional Factores de Competitividade for which the authors are thankful. Raquel O.
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15 Cristóvão thanks FCT for the Post-doc Scholarship (SFRH / BPD / 81564 / 2011).

16
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17 References
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18 Alexandre, V.M.F., Valente, A.M., Cammarota, M.C., Freire, D.M.G., 2011.

19 Performance of anaerobic bioreactor treating fish-processing plant wastewater
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20 pre-hydrolyzed with a solid enzyme pool. Renew. Energy 36, 3439-3444.

21 Amuda, O.S., Alade, A., 2006. Coagulation/flocculation process in the treatment of
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23 Amuda, O.S., Amoo, I.A., 2007. Coagulation/flocculation process and sludge
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26 APHA, 2005. Standard Methods for the Examination of Water and Wastewater, 21st ed.
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28 Artiga, P., García-Toriello, G., Méndez, E., Garrido, J.M., 2008. Use of a hybrid
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1 Braz, R., Pirra A., Lucas, M.S., Peres, J.A., 2010. Combination of long term aerated
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10 Cristóvão, R.O., Botelho, C.M.S., Martins, R.J.E., Boaventura, R.A.R., 2012. Chemical
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13 de Nardi, I.R., Del Nery, V., Amorim, A.K.B., Santos, N.G., Chimenes, F., 2011.
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16 de Sena, R.F., Moreira, R.F., José, H.F., 2008. Comparison of coagulants and
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19 Fahim, A.F., Fleita, D.H., Ibrahim, A.M., El-Dars, F.M.S., 2001. Evaluation of some

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20 Methods for Fish Canning Wastewater Treatment. Water Air Soil Pollut. 127,
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22 Gómez, M., de la Rua, A., Garrálon, G., Plaza, F., Hontoria, E., Gómez, M.A., 2006.
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25 Guo, M., Hu, H., Liu, W., 2009. Preliminary investigation on safety of post-UV
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31 Hallmich, C., Gehr, R., 2010. Effect of pre- and post-UV disinfection conditions on
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34 Hamoda, M.F., Al-Ghusain, I., Al-Mutairi, N., 2004. Sand filtration of wastewater for
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39 Jin, X., Li, E., Lu, S., Qiu, Z., Sui, Q., 2013. Coking wastewater treatment for industrial
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11 Palenzuela Rollón, A., 1999. Anaerobic digestion of fish processing wastewaters with
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17 Pérez-Gálvez, R., Guadix, E.M., Berge, J.P., Guadix, A., 2011. Operation and cleaning
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38 Zufía, J., Aurrekoetxea, G., 2002. Integrated Processing of Fish Canning Industry
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39 Wastewater. J. Aquatic Food Prod. Technol. 11, 303-315.

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1 Figure Captions

2 Figure 1 – Treatment sequence for fish canning wastewaters reuse.

3 Figure 2 – (a) Sedimentation/flotation and (b) coagulation/flocculation treatment lab-

4 scale plant for effluent primary treatment stage.
5 Figure 3 – Lab-scale plant for biological treatment with activated sludge (a) and sand
6 filtration (b).

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7 Figure 4 – Pilot plant for reverse osmosis studies.

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8 Figure 5 – UV disinfection system.

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9 Figure 6 – Accumulated removal efficiencies of the different sequential stages of the
10 fish canning wastewater treatment.

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1 Figure 1

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1 Figure 2

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1 Figure 6

100

80
Removal (%)

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SST
O&G
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DOC
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Anions
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1 Table 1 - Parametric values established by the European Directive 98/83/EC for water
2 intended for human consumption or used in food-processing industries.

Parameter Unit Parametric value

Aluminium µg Al/L 200

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Ammonium mg NH4/L 0.50
Calcium mg Ca/L -

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Chlorides mg Cl/L 250
Clostridium perfringens (including spores) N/100 mL 0
Color mg PtCo/L 20

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Conductivity µS/cm, 20ºC 2500
Total hardness mg CaCO3/L -
pH pH units ≥ 6.5 e ≤ 9

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Iron µg Fe/L 200
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Magnesium mg Mg/L -
Manganese µg Mn/L 50
Microcystin – full LR µg/L 1
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Smell, 25 ºC Dilution factor 3

Oxidability mg O2/L 5
Sulphates mg SO4/L 250
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Sodium mg Na/L 200

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Flavor, 25 ºC Dilution factor 3

Colony-forming units N/mL, 22ºC Without abnormal change
Coliform bacteria N/100 mL 0
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Total organic carbon (TOC) mg/L C without abnormal change

Turbidity UNT 4
α-total Bq/L 0.5
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β-total Bq/L 1
Tritium Bq/L 100
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Total indicative dose mSv/year 0.10

Residual desinfectant mg/L -
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1 Table 2 - Seasonal variation of fish canning wastewater characteristics.

Parameter Min Max

pH 6.13 7.14

Conductivity (mS cm-1) 4.73 24.8

TSS (mg·L-1) 324 3150

VSS (mg·L-1)

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315 2680

DOC (mg C·L-1) 90 2342

COD (mg O2·L-1) 1147 8313

RI
BOD5 (mg O2·L-1) 463 4569

Ptotal (mg P ·L-1)

SC
13 47

Ntotal soluble (mg N·L-1) 21 471

Nammoniacal (mg NH3.L-1) 3 1059

Oil and grease (mg ·L-1)

U
156 2808
AN
F- (mg ·L-1) 7 60

Cl- (mg ·L-1) 174 5047

M

NO2- (mg ·L-1) 3 355

Anions SO42- (mg ·L-1) 0.01 91

D

Br- (mg ·L-1) 0.01 214

NO3- (mg ·L-1)

TE

0.07 0.07

PO43- (mg ·L-1) 0.00 9

Li+ (mg ·L-1) 0 1

EP

Na+ (mg ·L-1) 86 2120

NH4+ (mg ·L-1) 24 217

C

Cations
K+ (mg ·L-1) 5 159
AC

Mg2+ (mg ·L-1) 7 40

Ca2+ (mg ·L-1) 60 221

36
 ACCEPTED MANUSCRIPT
1 Table 3 – O&G, TSS and DOC removal efficiencies of a fish canning wastewater at (a)
2 different dosages of several coagulants and (b) at different pH values.

4 (a)

O&G Removal (%) TSS Removal (%) DOC Removal (%)

PT
Coagulant Coagulant dosage (mg/L) Coagulant dosage (mg/L) Coagulant dosage (mg/L)
100 200 400 100 200 400 100 200 400

RI
Al2(SO4)3.16H2O 98.8 99.4 99.0 66.5 66.5 76.4 20.7 15.2 26.9
Fe2(SO4)3 99.4 99.5 99.5 56.7 0.0 0.0 29.8 32.1 33.7

SC
FeCl3 98.4 99.2 99.2 62.6 72.4 85.8 19.4 19.3 25.2
CaCl2 97.0 95.6 94.7 52.8 31.1 46.5 16.4 24.2 26.4
PAX-18 99.1 99.5 98.9 76.4 80.3 68.5 22.9 26.6 33.4

U
5 AN
6 (b)

O&G Removal (%) TSS Removal (%) DOC Removal (%)

M

Coagulant pH pH pH
5 6 7 8 9 5 6 7 8 9 5 6 7 8 9
Al2(SO4)3.16H2O
D

97.5 97.7 97.8 97.4 95.9 47.8 59.0 68.3 72.0 68.3 2.3 14.7 8.2 9.5 3.0
Fe2(SO4)3 97.0 98.5 97.0 98.6 97.1 45.9 45.9 45.9 51.5 64.6 10.1 10.5 17.8 21.9 8.8
FeCl3
TE

96.7 97.1 95.8 98.5 97.6 60.8 68.3 68.3 62.7 70.1 8.8 0.2 15.6 13.4 8.9
PAX-18 97.7 98.2 97.9 97.0 98.5 59.0 49.6 60.8 70.1 57.1 0.0 0.6 0.0 0.0 0.0
RIFLOC 1815 97.3 - 97.7 - 98.5 50.7 - 68.7 - 70.1 19.0 - 23.1 - 23.1
7
EP

8
C
AC

37
 ACCEPTED MANUSCRIPT
1 Table 4 – DOC removals from a fish canning wastewater by activated sludge under
2 different HRT.

HRT (h) DOCfeed (mg/L) DOCout (mg/L) DOC Removal (%)

5 696 183 73.7

PT
6 620 85 86.2

RI
8 594 25 95.8
4

SC
5

U
AN
M
D
TE
C EP
AC

38
 ACCEPTED MANUSCRIPT
1 Table 5 – Operating conditions and results from the tests carried out by reverse
2 osmosis.

Permeate Concentrated Removals (%)

Pressure
Tests Flow Rate Flow Rate Ntotal
(bar) DOC Conductivity
(L/h) (L/h) soluble

PT
1 192 270 8.5 93.9 95.2 98.7
2 192 240 8.5 96.6 96.0 96.0
3 192 204 9.0 89.6 95.0 98.4

RI
4 198 90 9.0 96.0 95.9 98.4
5 198 120 9.3 96.9 96.1 98.4
6 198 180 10.0 96.1 96.2 98.1

SC
7 198 225 9.0 90.1 99.8 95.7
8 210 120 9.0 95.5 99.8 99.0
9 210 240 8.5 93.9 99.8 99.0

U
10 216 60 9.0 97.3 99.8 99.1
4
AN
5
M
D
TE
C EP
AC

39
 ACCEPTED MANUSCRIPT
1 Table 6 – DOC, Ntotal soluble, cations and anions concentrations and conductivity values
2 achieved after treatment by reverse osmosis.

Parameter Value*
DOC (mg/L) 1.3
Ntotal soluble (mg/L) 0.1

PT
Conductivity (µS/cm) 50
Lithium (mg/L) 0.03
Sodium (mg/L) 8.0

RI
Ammonium (mg/L) 0.6
Potassium (mg/L) 0.6
Magnesium (mg/L) 0.2

SC
Calcium (mg/L) 1.5
Chloride (mg/L) 6.1
Nitrite (mg/L) 0.3

U
Sulfate (mg/L) 0.1
Bromide (mg/L) 0.1
AN
Nitrate (mg/L) 0.07
Phosphate (mg/L) 0.1
4
M
D
TE
C EP
AC

40
 ACCEPTED MANUSCRIPT
1 Table 7 – Operating costs for the wastewater treatment process on a basis of 10 m3 per
2 day (working time 8 h.day-1).

Process Unit Nominal Operation Energy Cost (€)

Power Time Consumption
(kW) (hour) (kWh/day)

PT
Flotation 2.7 2.0 5.40 0.76

Coagulation/Flocculation

RI
Coagulant (FeCl3)* 1.16
Rapid mixing 0.55 4.2 2.31 0.33

SC
Slow mixing 0.37 5.0 1.85 0.26

Activated Sludge

U
Mixture+Aeration 0.55 10 5.5 0.78
Recirculation pump 1.4 2.0 2.8 0.40
AN
Filtration 0.75 0.5 0.23 0.03
M

Reverse Osmosis 2.2 15 33 4.70

UV Disinfection 0.023 24 0.55 0.08

D

TOTAL 8.50
TE

4 * Optimum dosage = 400 mg/L (amount 4 kg/day; cost 290 €/ tonne)

C EP
AC

41
 ACCEPTED MANUSCRIPT
Highlights

1. Valorization of wastewaters from the fish canning industry.

2. Fish canning wastewater treatment for reuse or recycling into the industrial unit.

3. Reverse osmosis and UV disinfection were combined for effluent clarification.

PT
4. The proposed sequential system attained removal efficiencies above 96%.

RI
5. Reduction of effluents discharge, water use and its associated cost.

U SC
AN
M
D
TE
C EP
AC