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 and after use it usually finds a way to
the waste water treatment systems . Conventional treatment due to the long residence time and increased cost are not
recognized efficientiy . 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 . Current density and current intensity as operational parameters were studied . The results showed that at each
current intensity , by reducing the current density , removal efficiency increases . So that maximum removal efficiency 94 % ,
at current intensity equal to 300 mA and current density equal to 6 mA/cm2 was achived .

1. Introduction

Municipal wastewater is one of the important pollution sources affecting the water quality adversely in many developed
countries. Especially wastewaters containing detergents are among the basic constituents of organic pollution and they cause
great environmental damage by entering the soil, sea, lakes and rivers .(1) Surfactants are the active cleaning ingredients in
synthetic detergents used for all kinds of washing. Surfactants are amphiphilic substances of synthetic or natural origin, able to
adsorb at interfaces, thus reducing the surface or interfacial tension.( 2). They consist of a water-soluble (hydrophilic) and a
water-insoluble (hydrophobic) component.(3) . depending on the nature of the hydrophilic group, surfactants are classifed as
Anionic,Cationic,Nonionic and Zwitterionic (4) .

Anionic surfactants are the major class of surfactants used in detergent formulations(5) . LAS is the largest group of anionic
surfactants (6) . Over 40 years, LAS has been widely used in household cleaning detergents, personal care products and
industries such as textiles, paints, polymers, pesticide formulations, pharmaceuticals, mining, oil recovery and pulp and paper
(7). Surfactants find application in almost every chemical industry, including detergents, paints, dyestuffs, cosmetics,
pharmaceuticals, agrochemicals, fibres, plastics .(8) The annual European consumption of surfactants in 2011 was 2.95 Mt, of
which 1.40 Mt was non-ionic and 1.22 Mt was anionic according to the data reported by the European Committee of Organic
Surfactants and their Intermediates (9) Increased use of surfactants in various applications and the per capita increase in
consumption have increased the percentage of these compounds in sewage.(10)

After application LAS usually is discharged to the sewer system and appears in municipal wastewater treatment plants (11). As
common constituents in municipal effluents , concentrations of surfactants in municipal and industrial wastewaters, especially
those from laundries, appear to be very high. Concentrations of linear alkylbenzene sulfonates (LAS), a major contributing
anionic surfactant in laundry wastewater, can be as high as 116-454 mg/L . It is thus of significance and indispensable to find
effective ways to remove surfactants once released to water. (12) To minimize environmental problems, this molecule has been
the subject of a series of studies regarding its chemical, physical and biological removal. (13) So far, various approaches such
as ultrafiltration and ion-exchange (14) adsorption (15.) and etc. have been studied to remove detergents from wastewaters .

In the past years, conventional biological and physical treatment methods (adsorption, ultrafiltration, coagulation, etc.) have
been used to remove the organic pollutants. These methods are not efficient and cost effective for wastewaters containing high
concentration of more toxic pollutants. This requires some novel techniques to transfer the highly toxic pollutants chemically
into benign species. (16 ) For this reason, many investigations are exploring the advanced oxidation processes for
degradation of surfactants. (17).

Advanced Oxidation Processes (AOPs) are considered to be the most promising alternative due to their high efficiency and
versatility . The AOP are based on the generation of hydroxyl radicals (HO ),which have a very high oxidation potential (E =
+2.80 V vs. SHE) and are capable of initiating a cascade of reactions that often results in the total degradation or
mineralization of the organic substance . (18) Advanced oxidation processes (AOPs) were first proposed in the 1980s for
potable water treatment . Later, AOPs were broadly applied for treatment of different types of wastewaters because the strong
oxidants can readily degrade recalcitrant organic pollutants and remove certain inorganic pollutants in wastewater. (19)

Electrochemical techniques have an important role among the advanced treatment technologies and offer a good opportunity to
prevent and remedy pollution problems . (20) The main advantage of this technology is that no chemicals are used. In fact,
only electrical energy is consumed for the mineralisation of organic pollutants . (21) Electrochemical technologies, such as
electro-oxidation (EO), electrochemical coagulation (EC) and electrochemical flotation (EF) have also received major attention
in recent years . Electrochemical techniques have been applied extensively to treat various wastewaters, disinfect drinking
water or enhance the remediation of polluted soils . (22)
Excessive use of any type of surfactants and their disposal in the environment, especially in aquatic bodies, could seriously
affect the ecosystem .(23) Suafactants can also affect living organisms and abiotic parts of the environment. They can be toxic
for different types of organisms (24) . Toxicity tests are desirable in water quality evaluations because chemical and physical
tests alone are not sufficient to assess potential effects on aquatic biota.(25)

Aquatic toxicity is usually measured on fish, daphnia and algae. The toxicity index is expressed as LC 50 (for fish) or EC50 (for
daphnia and algea), where LC and EC stand for lethal and effective concentration, respectively. Values below 1 mg/L after 96 h
testing on fish and algae and 48 h on daphnia are considered toxic.(8)

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 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 electrode was used as both the anode and the cathode. The experiments were conducted in ambient
conditions .

Fig. 1. Schematic of experimental set up

2.3 Experimental procecdure

Step a. 2 liters of water taken first from urban network and with the addition of the LAS, handmade contaminated water with
certain concentration (200 mg/L) provided .

Step b. Prepared contaminated water is poured in an electrolytic cell (a 2 liter beaker ) and Using electrodes made of stainless
steel ( 15 cm length and 3 cm width and 1 mm thickness which initially is immersed in solution in 3 cm height ) and without
change in pH ( about 7-8 ) , temprature ( about 20 C ) and conductivity , electrochemical process with the aforementioned
electrode at the current intensity of 200 mA for one hour is applied on it . After one hour , the sample is taken to determine the
concentration of LAS residues . LAS was measured using methylene blue active substance (MBAS) on the basis of the 5540 C
method in the Standard Methods for The Examination of Water and Wastewater ( 22 ed. ) book . Then a total of 10 fish is
entered in the rest of cell content . The experiments were repeated three times for each sample .

Step c. Such as step b. but with current intensity of 300,400,500,600,700,800 and 900 mA will be act .

Step d. At this stage the electrodes are immersed in the solution up to 6 cm and steps b. and c. are repeated .

Step e. At this stage the electrodes are immersed in the solution up to 9 cm and steps b. and c. are repeated .
Biological test is done with black molly fish ( poecilia sphenops ) in number of 10 and in 52 cm length , 21 gr weight and up
to 96 hours the number and fish survie status will be monitored . The number of dead and live fish at the end of each 24 hours
will be 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/cm 2 . 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:

U . I .t
energy consumption =
( C0C ) . V
which U is potential difference between cathode and anode , I is current intensity , t is periode of process time , V is volume of
sample , C0 is initial concentration of LAS and C is final concentration of LAS .

a 3 cm electrode immersion height

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

90 90
LAS removal ef. %
LAS removal ef. %

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

c d
3 cm electrode immersion height 3 cm electrode immersion height
6 cm electrode immersion height 6 cm eelctrode immersion height
9 cm electrode immersion height 9 cm electrode immersion height

100 10
potential diferent ( volt )

90 8
LAS removal ef. %

80
6
70
60 4

50 2
0 5 10 15 20 25 30 35 100 200 300 400 500 600 700 800 900 1000
energy consumption ( W.hr/gr ) 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) .

Onder 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 of 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

8
3 cm electrode immersion height
No. of live fshes

6 cm electrode immersion height

6 9 cm electrode immersion height

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

4. conclusion

The aim of this article were 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 .

References

1- Koparal AS, nder E, tveren B. Removal of linear alkylbenzene sulfonate from a model solution by continuous
electrochemical oxidation. Desalination. 2006 Oct 2;197(1):262-72.

2- Mbius D, Miller R, Fainerman VB. Surfactants: chemistry, interfacial properties, applications. Elsevier; 2001 Dec 21.

3- Panizza M, Delucchi M, Cerisola G. Electrochemical degradation of anionic surfactants. Journal of applied

electrochemistry. 2005 Apr 1;35(4):357-61.

4- Rosen MJ, Kunjappu JT. Surfactants and interfacial phenomena. John Wiley & Sons; 2012 Mar 6.

5- Samadi MT, Dorraji MS, Atashi Z, Rahmani AR. Photo Catalytic Removal of Sodium Dodecyl Sulfate From Aquatic
Solutions With Prepared ZnO Nanocrystals and UV Irradiation. Avicenna Journal of Environmental Health Engineering.
2014;1(1).

6- Heibati B, Ghoochani M, Albadarin AB, Mesdaghinia A, Makhlouf AS, Asif M, Maity A, Tyagi I, Agarwal S, Gupta VK.
Removal of linear alkyl benzene sulfonate from aqueous solutions by functionalized multi-walled carbon nanotubes. Journal of
Molecular Liquids. 2016 Jan 31;213:339-44.

7- Guan Z, Tang XY, Nishimura T, Huang YM, Reid BJ. Adsorption of linear alkylbenzene sulfonates on carboxyl modified
multi-walled carbon nanotubes. Journal of hazardous materials. 2016 Mar 2.

8- Tadros TF. Applied surfactants: principles and applications. John Wiley & Sons; 2006 Mar 6.

9- Camacho-Muoz D, Martn J, Santos JL, Aparicio I, Alonso E. Occurrence of surfactants in wastewater: hourly and
seasonal variations in urban and industrial wastewaters from Seville (Southern Spain). Science of the Total Environment. 2014
Jan 15;468:977-84.
10- Ghaderpoori M, Dehghani MH. Investigating the removal of linear alkyl benzene sulfonate from aqueous solution by
ultraviolet irradiation and hydrogen peroxide process. Desalination and Water Treatment. 2016 Jul 8;57(32):15208-12.

11- Temmink H, Klapwijk B. Fate of linear alkylbenzene sulfonate (LAS) in activated sludge plants. Water research. 2004 Feb
29;38(4):903-12.

12- Gao Q, Chen W, Chen Y, Werner D, Cornelissen G, Xing B, Tao S, Wang X. Surfactant removal with multiwalled carbon
nanotubes. Water Research. 2016 Dec 1;106:531-8.

13- Delforno TP, Okada DY, Faria CV, Varesche MB. Evaluation of anionic surfactant removal in anaerobic reactor with Fe
(III) supplementation. Journal of Environmental Management. 2016 Dec 1;183:687-93.

14- Kowalska I. Surfactant removal from water solutions by means of ultrafiltration and ion-exchange. Desalination. 2008 Mar
1;221(1):351-7.

15- Nayak AK, Pal A. Performance evaluation of surfactant removal by adsorption technique and its comparative studies with
other existing treatment processes: A short review. JOURNAL OF THE INDIAN CHEMICAL SOCIETY. 2016 Jul
1;93(7):837-42.

16- Swaminathan M, Muruganandham M, Sillanpaa M. Advanced oxidation processes for wastewater treatment. International
Journal of Photoenergy. 2013 Jan 1.

17- Aonyas MM, Dojinovi BP, Doli SD, Obradovi BM, Manojlovi DD, Markovi MD, Rogli GM. Degradation of
Anionic Surfactants using the Reactor Based on Dielectric Barrier Discharge (DBD). J. Serb. Chem. Soc.. 2016 Jun 6.

18- Zanta CL, Friedrich LC, Machulek A, Higa KM, Quina FH. Surfactant degradation by a catechol-driven Fenton reaction.
Journal of hazardous materials. 2010 Jun 15;178(1):258-63.

19- Deng Y, Zhao R. Advanced Oxidation Processes (AOPs) in Wastewater Treatment. Current Pollution Reports. 2015 Sep
1;1(3):167-76.

20- nder E, Koparal AS, tveren B. An alternative method for the removal of surfactants from water: Electrochemical
coagulation. Separation and Purification Technology. 2007 Jan 31;52(3):527-32.

21- Comninellis C, Kapalka A, Malato S, Parsons SA, Poulios I, Mantzavinos D. Advanced oxidation processes for water
treatment: advances and trends for R&D. Journal of Chemical Technology and Biotechnology. 2008 Jun 1;83(6):769-76.

22- Srkk H, Bhatnagar A, Sillanp M. Recent developments of electro-oxidation in water treatmenta review. Journal of
Electroanalytical Chemistry. 2015 Oct 1;754:46-56.

23- Ivankovi T, Hrenovi J. Surfactants in the environment. Arhiv za higijenu rada i toksikologiju. 2010 Mar 17;61(1):95-109.

24- Olkowska E, Ruman M, Polkowska . Occurrence of surface active agents in the environment. Journal of analytical
methods in chemistry. 2014 Jan 16;2014.

25- Agency1991 UE. Technical support document for water quality-based toxics control. EPA/505/2-90-001. Washington, DC.