Investigation of effect of electrochemical process on detergent removal from synthetic wastewater with Bioassay test

Abstract

LAS is an anionic surfactant which is widely used in household and industrial detergents usage and after use it usually finds a
way to the waste water treatment systems. Conventional treatment due to the long residence time and enlarged cost are not
recognized efficiently. So advanced oxidation processes including electrochemical techniques are important. In this paper,
electrochemical degradation of a synthetic solution of LAS with initial concentration 200 ppm has been investigated .The
experiment using eight stainless steel electrodes as the cathode and the anode and with the mono-polar arrangement was
performed. The effects of current density and current intensity as operational parameters on detergent removal efficiency were
studied. The results showed that at each current intensity, by reducing the current density, removal efficiency increases. So that
maximum removal efficiency 94 % was achieved at current intensity equal to 300 mA and current density equal to 6 mA/cm2.
To assess the toxicity of remaining solution after electrolysis, bioassay test using Molly fish carried out on samples and the
results of this test showed that there is minimum mortality in the optimum conditions .

1. Introduction

Municipal and industrial wastewater are a major cause of pollution of water resources. One of the major components forming
the wastewater are detergents that a lot of damage caused to the environment by entrance into the water and soil (1). One of
the main constituents of detergents are surfactants. Surfactants are amphiphilic substances that due to their chemical properties
can reduce the surface tension of water and to increase the its washing effect (2). They are composed of two parts of water
soluble (hydrophilic) and water insoluble (hydrophobic) (3). Based on the nature of the hydrophilic part , the surfactants can be
classified as cationic, anionic, nonionic and amphoteric (4).

Anionic surfactants are the largest type of surfactants used in detergents formulation(5). LAS is the largest type of anionic
surfactants (6). LAS has used widely in household cleaners , health and cosmetics products and other industries (7,8). Annual
consumption of surfactants in Europe in the year 2011 has been 2.95 Mt (9). Due to the high consumption of surfactants in
various applications , their presence in wastewater have also increased and after the use , they discharged into the wastewater
system and from there, find their way to the treatment plants (10,11). Thus the surfactant concentration in municipal and
industrial wastewater effluent can be very high. For example, LAS concentration in laundry wastewater was observed to
several hundred mg per liters (12). To reduce the environmental impacts, surfactants and particularly LAS, has been intensely
studied and various physical, chemical and biological methods have been used to remove it (13). The methods such as
ultrafiltration and ion exchange (14) and adsorption (15), and etc. have been studied for removing surfactants from
wastewater.

Over the years, conventional physico-chemical and biological methods such as absorption , coagulation and filtration and etc.
have been used to remove contaminants. Since these methods, especially for toxic contaminants including surfactants and high
concentrations of contaminants are not recognized very effective and moreover, are relatively costly therefore, researches has
continued to find new techniques (16). Among these new techniques are advanced oxidation processes (17). Advanced
oxidation processes due to advantages such as high efficiency and versatility have been identified as promising alternatives.
AOPs are based on the production of hydroxyl radicals, a strong oxidant, (18). AOPs were first introduced in the 1980s for
water purification and later have been used for treatment of various types of sewages because strong oxidants generated in this
process can easily degrade organic pollutants (19).

Electrochemical methods are among of AOPs and have provided appropriate field in the environmental pollutants treatment
(20). The main advantage of this method is that it does not require chemical and electrical energy is only used to decompose
pollutants (21). In recent years electrochemical methods such as electrooxidatin, electrocoagulation and electroflotation have
attracted a lot of attention and widely been used for treatment of sewage and water disinfection (22). The widespread use of
different types of surfactants and their entry into the environment, particularly aquatic environment, can have harmful effects
on ecosystems and living organisms (23,24). To assess the toxicity effects of these pollutants on aqutic biota, physical and
chemical tests alone are not enough and toxicity tests are necessary to assess the quality (25). Toxicity tests usually is done on
fish, daphnia and algae.

The aim of this work was to study the electrochemical degradation of a synthetic solution containing LAS . The influence of
operating parameters such as current density and current intensity were studied , in order to find the optimal conditions for
electrolysis. To assess toxicity of remaining solution after electrolysis , biological test were performed on samples . As a result
of the studies , the removal of surfactant of 200 mg/L was achieved with an efficiency of 94 % and energy consumption of 2.7
W.hr/gr .
2. Materials and methods

2.1 Reagents

Sodium dodecylbenzenesulfonate as a representative of LAS used in the present study was commercially obtained from
Sigma-Aldrich Co. and used without further purification. Methylene Blue reagent was commercially obtained from CARLO
ERBA. Other chemicals such as H2SO4, Phenolphthalein, CHCl3, NaOH and NaH2PO4.H2O were supplied by Merck Co.

2.2 Apparatus

The absorbance of solutions was measured by a spectrophotometer (DR/2010; HACH Co.)

Eight stainless steel electrodes were used as both the anode and the cathode. The experiments were conducted in ambient
conditions. In figure 1 a simple schematic of apparatus has showed.

Fig. 1- Schematic of experimental set up

2.3 Experimental procedure

Step a. At first 2 liters tap water was taken from urban network and with the addition of the LAS, synthetic wastewater with
certain concentration (200 mg/L) was prepared. The polluted water was poured in an electrolytic cell (a 2 liter beaker) and
using stainless steel electrodes (15 cm length, 3 cm width and 1 mm thickness) electrochemical process was applied on it. In
this stage run, 3 cm height of electrodes was submerged in the solution. The electrochemical process was done , without any
change in pH (about 7-8), temperature (about 20 C) and electroconductivity (about 900 S/cm) , by the aforementioned
electrodes at the current intensity of 200 mA for one hour. Then a sample was taken to determine the concentration of LAS
residue. LAS residue was measured using Methylene Blue Active Substance (MBAS) on the basis of the 5540 C method in the
22nd edition of Standard Methods for The Examination of Water and Wastewater book. Finally, a total of 10 fish was leaved in
the rest of cell content transferred to another vessel. The experiments were repeated three times for good accuracy.

Step b. Such as step a. but with current intensity of 300,400,500,600,700,800 and 900 mA were done.

Step c. At this stage the submerged height of electrodes was increased to 6 cm and the steps a. and b. were repeated.

Step d. This stage is similar to the step c. with the exception of 9 cm submerged electrodes.

It is noticed that the bioassay test was done with black molly fish ( poecilia sphenops ) in number of 10 and in 51 cm length ,
20.5 gr weight. The fish survival status was monitored up to 96 hours. The number of dead and live fish at the end of each 24
hours was recorded.

3. Results and discussion

In Figure 2 , LAS removal percent in terms of current intensity and three electrode immersion heights is shown . As can be
seen with increasing height of electrode immersion which is associated with a reduced current density , LAS removal
efficiency increases . Optimum current intensity and electrode height was 300 mA and 9 cm respectively which is equivalent
of current density of about 6 mA/cm2 . In this condition , the maximum removal efficiency of LAS,was 94% and the used
electrical consumption energy was equal to 2.7 W.hr/gr . Electrical consumption energy was calculated as follows:
Electrical energy consumption = (C0U.I.t
C).V

which U is potential difference between cathode and anode as volt, I is current intensity as mA , t is periode of process time as
hour, V is volume of initial solution as liter, C0 is initial concentration of LAS and C is final concentration of LAS as mg/L.

100 100
3 cm electrode immersion height
6 cm electrode immersion height
90 90 3 cm electrode immersion height
9 cm electrode immersion height

LAS removal eff. %

LAS removal eff. %

6 cm electrode immersion height

9 cm electrode immersion height
80 80

70 70

60 60

50 50
100 200 300 400 500 600 700 800 900 1000 0 5 10 15 20 25 30 35 40 45 50 55

a current intensity ( mA ) b current density ( mA/cm2 )

100 10
3 cm electrode immersion height 3 cm electrode immersion height
6 cm eelctrode immersion height

potential difference ( volt )

6 cm electrode immersion height
90 9 cm electrode immersion height 9 cm electrode immersion height
8
LAS removal eff. %

80
6
70
4
60

2
50
100 200 300 400 500 600 700 800 900 1000
0 5 10 15 20 25 30 35

c energy consumption ( W.hr/gr ) d current intensity ( mA )

Fig. 2. variations of LAS removal eff. Percent vs current intensity (a) , current density (b) , energy consumption (c) and
voltage vs current intensity (d) .

nder et al (20) which conducted a study on Removal of LAS in concentration of 10 mg/L , achieved to 100% removal
efficiency after a period of one hour . The energy consumption of about 6 KWhr/gr under these conditions was calculated . So
the situation is much better in terms of energy consumption in our test .

Koparal et al (1) in another study on the LAS in concentration of 50 mg/L using electrodes of ruthenium oxide , Removal
efficiency of 94% with a energy consumption of 11.3 KW.hr/gr was achieved . Here the energy consumption is higher than
that obtained in our experiment .

To assess the toxicity of LAS in remaining solution after electrolysis , a biological test carried out on samples . In this test ,
Molly fish ( poecilia sphenops ) was used . In each container which was containing 2 liter of remaining solution , a total of 10
fish were thrown and their vital status at 24, 48, 72 and 96 hours after the start of the test was evaluated . Bioassay studies
conducted on the contaminated water samples that the electrochemical process applied to them , showed a good alignment
between chemical test results the and bioassay results . These findings suggest that detoxification of LAS has happened to the
fish in optimum conditions and only 80 percent of the fishes survive in these conditions . Fisher's test results showed
significant differences in optimal conditions and other process conditions ( PV < 0.05 ) .

In the below figure , the number of live fishes in terms of current intensity and and different electrode immersion heights has
been showed .
 10
3 cm electrode immersion height
8 6 cm electrode immersion height
No. of live fishes

9 cm electrode immersion height

6
4
2
0
200 300 400 500 600 700 800 900
current intensity ( mA )

4. conclusion

The aim of this article was finding optimal current intensity and current density to remove LAS from solution using stainless
steel electrodes . From the results it can be concluded that LAS can be effectively removed from water by electrochemical
process . The main mechanism of this technique is electrocoagulation .

Acknowledgements

This paper is extracted from the results of research project No. 9501, which was conducted at Kashan University of Medical
Sciences . The authors are grateful to the deputy of research of Kashan University of Medical Sciences for fnancial support .

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