DEGRADATION OF LINEAR ALKYLBEZENE-SULFONATE IN LIQUID DETERGENT

WASTE BY SONOLYSIS AND PHOTOLYSIS IN THE PRESENCE OF TiO2

Safni Safni1, Annisa Issakinah1, Deswati Deswati1*, Hilfi Pardi2

1
Department of Chemistry, Faculty of Mathematics and Natural Science, Andalas
University, Kampus Limau Manis, Padang, 25163 Indonesia
2
Department of Chemistry Education, Faculty of Teacher Training and Education Raja Ali Haji
Maritime University, Senggarang, Tanjungpinang, 29100 Indonesia
*E-mail: deswati@sci.unand.ac.id, deswati_ua@yahoo.co.id

ABSTRACT

Linier Alkylbenzene-Sulfonate (LAS) is an anionic surfactant that is widely used as an

active ingredient in synthetic liquid detergent formulations. The use of liquid detergent
has resulted in domestic liquid waste containing LAS so that it can pollute river
ecosystems. Furthermore, in this study, LAS degradation was carried out in liquid
detergent waste (such as soklin, rinso, attact, and chemist) by sonolysis and photolysis
with UV A lamp (λ = 365 nm) with and without the addition of TiO2 catalyst. In this
study, a UV-Vis spectrophotometer was used at λ 200-700 nm, and the optimum
catalyst mass of TiO2 was 15 mg. The results of LAS degradation by sonolysis and
photolysis for 90 minutes were 53.98% and 56.28%, respectively. Furthermore, with the
addition of TiO2 catalyst, the percentage of LAS degradation increased to 68.20% and
93.94% respectively, so that the photolysis method is faster in degrading LAS in
detergent waste than the sonolysis method. Furthermore, the photolysis method was
applied to the LAS degradation of liquid detergent waste (soklin, rinso, attack, and
chemist) of 82.81%, 91.59%, 93.79%, and 96.02%, respectively. Chemist liquid
detergent waste has a higher percentage of degradation compared to the other three
detergent wastes, so the chemist liquid detergent is more environmentally friendly.
Kata kunci: LAS, Degradation, fotolisis, sonolisis, TiO2.
 INTRODUCTION
The use of synthetic detergents in household and small industrial activities, such
as laundry in kilos, can cause pollution to rivers and beaches. The kilogram laundry
business is one of the biggest contributors to the detergent foam in rivers and on
beaches. Foam on the surface of the water is one of the causes of limited contact
between air and water so that it can reduce the surface tension of the water, reduce
dissolved oxygen levels and can cause water organisms to lack oxygen [1].

Pollutants contained in household and small industrial laundry detergent waste

kilo is linear alkylbenzene sulfonate (LAS). LAS is an anionic surfactant that is currently
widely used as an active ingredient in synthetic detergent formulations [2]. The use of
LAS surfactants as active detergent compounds continued to increase from 13 million
tonnes in 1977 to 18 million tonnes in 1996. LAS anionic surfactants are currently used
around 1.5 million tonnes per year in synthetic detergent formulations due to their
superior cleaning properties and price. Economical[3]. According to the Decree of the
Minister of Health of the Republic of Indonesia Number 907 / MENKES / SK / VII / 2002,
the LAS content allowed for drinking water quality is 0.05 mg / L. If the content of these
compounds exceeds the stipulated provisions it will cause harmful effects such as
irritation (heat, itching, even peeling) on the skin and have a carcinogenic effect[4].

There are three conventional waste treatment processes, namely physics,

biology, and chemistry. Physical waste treatment only changes the form of waste to
form secondary waste which requires further waste processing. Biological waste
processing has several shortcomings, including the difficulty of controlling microbial
development, producing several products that require a long time to decompose,
processing waste can be carcinogenic, and for toxic waste treatment sometimes it can
even kill the microbes that treat the waste. chemistry has several advantages, among
others, that it can overcome almost all inorganic pollutants, is not affected by toxic or
toxic pollutants, and does not depend on changes in concentration [5].

The conventional waste treatment has several drawbacks, so a more effective

waste treatment method using alternative methods is needed. The alternative method
used to treat detergent waste is the photolysis method and the sonolysis method.
Photolysis of detergent waste processing has been carried out using a TiO2 catalyst, but
no one has treated detergent waste using the sonolysis method [6]. In this study, a
comparison of two methods for detergent waste degradation is photolysis and sonolysis
with the addition of a TiO2 catalyst. The benefits of this study are to provide information
on several effective methods to degrade liquid detergent waste in overcoming
environmental pollution in waters, with and without the addition of a TiO 2 catalyst by
sonolysis and photolysis.
 EXPERIMENTAL

1. Tools and Materials

The equipment used is the Ultraviolet-Visible Spectrophotometer (Thermo

Scientific Evolution 201 UV-Vis Spectrophotometer), analytical balance (AA-200,
Denver Instrument Company), sonicator, UV A lamp 10 watts (λ = 365 nm), HPLC
(Shimadzu with column chromatography C18 (250x4.6mm), methanol and doubly
distilled water phase (3 : 2 v/v), injection volume used 10μL and flow rate 1.0
mL/minute), centrifuge (NASCO at 3000 rpm), measuring pipette, pipette goiter,
Handmade Irradiation Box, and other glassware.

The materials used in this study were 90% active LAS, detergent waste, TiO 2
catalyst, and doubly distilled water.

2. Research Procedure

Manufacture and Measurement of the LAS Absorption Spectrum

LAS 90% pipette 1.1 mL was dissolved with 1000 mL distilled water, pipette 25
mL from the first solution was diluted with 250 mL doubly distilled water, and obtained
100 mg/L main solution. The main solution of 100 mg/L was made with varying
concentrations of 1, 3, 5, 7, and 9 mg/L, the absorption was measured at a
concentration of 1 mg/L with a UV-Vis spectrophotometer 200-700 nm wavelength.
Absorbance data is taken at λ which provides maximum absorption.

Degradation of LAS without a catalyst

Effect of sonolysis time

The 5 mg / L LAS solution was put in as much as 25 mL into the vial bottle. The
solution was sonolysed at various times (5, 15, 30, 60, and 90) minutes. The absorption
of each solution was measured by a UV-Vis spectrophotometer at a certain wavelength
and HPLC.

Effect of photolysis time

The 5 mg / L LAS solution was added as much as 25 mL into the petridish. The
solution was irradiated with UV A light at various times (5, 15, 30, 60, and 90) minutes.
The absorption of each solution was measured by a UV-Vis spectrophotometer at a
certain wavelength and HPLC.

Degradation of LAS by Addition of Catalyst

Determination of the Optimal Catalyst Mass

The 5 mg/L LAS solution was put in as much as 25 mL into the petridish and
added with variations of the catalyst (5, 10, 15, 20, and 25) mg. Each solution was
irradiated photolysis for 90 minutes and centrifuged for 10 minutes. The absorption of
each solution was measured by a UV-Vis spectrophotometer at a certain wavelength.

Effect of sonolysis time

The 5 mg/L LAS solution was put in as much as 25 mL into the vial and 15 mg of
catalyst was added. The solution was sonolysed at various times (5, 15, 30, 60, and 90)
minutes and centrifuged for 10 minutes. The absorption of each solution was measured
by a UV-Vis spectrophotometer at a certain wavelength and HPLC.

Effect of photolysis time

The 5 mg/L LAS solution was added as much as 25 mL into the petridish and 15
mg of catalyst was added. The solution was irradiated with UV A light at various times
(5, 15, 30, 60, and 90) minutes and centrifuged for 10 minutes. The absorption of each
solution was measured by a UV-Vis spectrophotometer at a certain wavelength and
HPLC.

Application of the Degradation Method in Detergent Waste

As much as 25 mL of detergent waste was added to the petridish and 15 mg of

catalyst was added. The solution was irradiated with UV A light for 90 minutes and
centrifuged for 10 minutes. The absorption of each solution was measured by a UV-Vis
spectrophotometer at a certain wavelength and HPLC.

LAS Analysis by HPLC Method

LAS and detergent waste with the highest percentage degradation were injected
into the column, then methanol and water flowed through the column with a ratio (3: 2),
the flow rate was fixed at 1 mL/minute, the injection volume was 10 µL.
 RESULTS AND DISCUSSION
LAS Absorption Spectrum Measurement
The measurement of the absorption spectrum of the LAS solution using a UV-Vis
spectrophotometer was carried out at a wavelength range of 200–700 nm. The LAS
absorption spectrum can be seen in Figure 1 which shows the maximum absorption
peak at a wavelength of 224 nm.

1.0

0.8
Absorbance

0.6

0.4

0.2

0.0
200 300 400 500 600 700
Wavelength (nm)

Figure 1. The LAS absorption spectrum (oA) in different wavelength (nm)

Figure 2 shows the LAS absorption spectrum at several concentration variations to see
the linearity relationship between absorbance and concentration. The higher the
concentration, the greater the absorbance value.
 1.0
Y = 0.0683x + 0.1365
R = 0.9713

0.8

0.6
Absorbance

0.4

0.2

0.0
0 2 4 6 8 10
LAS Concentration (mg/L)

Figure 2. Absorbance value (oA) in different LAS Concentration (mg/L)

Based on the Lambert-Beer law, a good absorbance value is between 0.2 to 0.8.
The linearity of the calibration curve in Figure 5 shows the regression equation of LAS, y
= 0.0683x + 0.1365 and R2 = 0.9785. Subsequent research was carried out at a
concentration of 5 mg/L to degrade LAS by sonolysis and photolysis using UV A light (λ
= 365 nm).

Determination of the optimum catalyst mass of TiO2 in the degradation process

The optimum TiO2 catalyst mass was determined by varying the weight of the
TiO2 catalyst, namely 5-25 mg. LAS was degraded by photolysis by adding TiO2 catalyst
according to variations. The degradation process was carried out by the photolysis
method for 90 minutes. The optimum TiO2 catalyst weight can be seen in Figure 6,
which is a curve showing the relationship between the percentage of degradation and
the weight of TiO2 catalyst.
 100

90
LAS Degradation (%)

80

70

60

50

40
0 5 10 15 20 25 30
Weight of TiO2 (mg)

Figure 3. LAS degradation (%) in different weight of TiO2 (mg)

Figure 3 shows that the addition of TiO2 5 mg to the addition of 15 mg in the
degradation process of the LAS compound shows that the increase in the percentage of
degradation is directly proportional to the addition of the amount of TiO 2 used as a
catalyst, where the optimum mass of TiO2 obtained is 15 mg with the percentage
degradation of 82.64%. . This is because the amount of TiO 2 in the solution will affect
the number of OH radicals formed, in the photolysis method, OH radicals are produced
through surface oxidation of hydroxide anions and absorption of organic compound
molecules on the surface of TiO2 semiconductors with holes in the valence band, the
more TiO2 in the solution. irradiated with 365 nm UV light, the more holes will be formed
later. The OH radicals formed will reactively attack the LAS compound. This
degradation will continue until the catalyst capacity is no longer able to degrade LAS
compounds optimally[7,8].
From Figure 6, it can be seen that the percentages on the addition of TiO2
catalyst 20 mg and 25 mg have decreased. The decrease in degradation occurs
because the absorption of UV light is blocked by TiO2 which has been excess of the
optimum amount of TiO2 which can produce hydroxyl radicals in solution[9].
Sonolytic degradation of LAS
Effect of sonolysis time
LAS sonolysis was carried out at a concentration of 5 mg/L as much as 25 mL
with time variations of 5, 15, 30, 60, and 90 minutes using a sonicator. The effect of
sonolysis time on the percent degradation can be seen in Figure 4. From Figure 4 it can
be seen that there is an increase in the percent degradation of LAS compounds with
increasing irradiation time, because the longer the irradiation time, the more OH radicals
formed in the sonolysis process, the OH radicals formed will attack. reactively the LAS
compound until the optimum time of 90 minutes with the percentage degradation of
53.98%[10].

80

70
LAS Degradation (%)

60

50

40

30

20
0 20 40 60 80 100
Time (minutes)

Figure 4. LAS degradation (%) in different time (minutes)

The effect of adding a TiO2 catalyst

A comparison of the percentage of LAS degradation with and without the addition
of 15 mg TiO2 by sonolysis with increasing degradation time can be seen in the Figure
5. From Figure 5 it can be seen that the longer the sonolysis time, the more LAS will be
degraded. This is because the longer the time, the more ultrasonic radiation that hits the
TiO2 catalyst, so that more OH radicals are produced. The percentage of LAS
degradation by ultrasonic radiation at 90 minutes is 68.20%. From the data, it can be
seen that the effect of the TiO2 catalyst performance for the sonolysis method
increased by 14.22%.

Without Catalyst
100 With Catalyst TiO2

80
LAS Degradation (%)

60

40

20

0
0 20 40 60 80 100
Time (minutes)

Figure 5. LAS degradation (%) with and without the addition of 15 mg the TiO2
catalyst by sonolysis in diferent time (minutes)

Photolytic degradation of LAS

Effect of photolysis time
LAS photolysis was carried out at a concentration of 5 mg/L as much as 25 mL with
time variations of 5, 15, 30, 60, and 90 minutes using a UV A lamp source (λ = 365 nm).
The effect of photolysis time with a UV A lamp (λ = 365 nm) on the percent degradation
can be observed in Figure 7.
 60

58
LAS Degradation (%)

56

54

52

50
0 20 40 60 80 100
Time (minutes)

Figure 6. LAS degradation (%) in different time (minutes)

From Figure 6 above, it can be seen that there is an increase in the percentage
of degradation of LAS compounds with increasing irradiation time, because the longer
the irradiation time, the greater the number of OH radicals formed which play a role in
degrading LAS compounds. From the graph above, the increase in the percentage of
degradation is quite significant until 90 minutes, where the percentage of degradation of
56.28% shows the stability of the graph. This occurs because the degradation process
has not changed much, the cause is the maximum number of hydroxyl radicals
produced by the photolysis process. Although the length of time the radiation is
extended, it will not affect the formation of hydroxyl radicals[7].

The effect of adding a TiO2 catalyst

Comparison of the percent degradation of LAS with and without the addition of
15 mg TiO2 by photolysis with UV A lamp (λ = 365 nm) with increasing degradation time
can be seen in Figure 7.
 Without Catalyst
100
With Catalyst TiO2

90
LAS Degradation (%)

80

70

60

50

40
0 20 40 60 80 100
Time (minutes)

Figure 7. LAS degradation in different time (minutes) with the addition of 15 mg

TiO2 catalyst by photolysis
Based on Figure 8 it can be seen that the longer the irradiation time, the more LAS is
degraded. This is because the longer the irradiation time, the more UV rays hit the TiO2
catalyst so that more OH radicals are produced. The percentage of LAS degradation
under UV A lamp (λ = 365 nm) at 90 minutes is 93.94%. From the data, it can be seen
that the effect of the TiO2 catalyst performance for UV A lamps (λ = 365 nm) increased
by 37.66%.
Application of the Degradation Method in Detergent Waste
Table 1. Degradation of liquid detergent waste by photolysis at optimum conditions

No Deterjen Time Weight Absorbance0 Absorbancet Degradation

(minutes) TiO2 (mg)

1. Soklin 90 15 2.763 0.475 82.81%

2. Rinso 90 15 2.163 0.182 91.59%

3. Attack 90 15 1.756 0.109 93.79%

4. Kemist 90 15 1.484 0.059 96.02%

In this study, liquid detergent waste was degraded by photolysis with a UV A

lamp (λ = 365 nm) under optimum conditions, namely 15 mg of catalyst weight and 90
minutes of irradiation time, liquid detergent waste used was liquid detergent soklin,
rinso, attack, and chemist. obtained percent LAS degradation of 82.81; 91.59; 93.79,
and 96.02%, respectively.
In Figure 5, the regression equation for LAS is obtained, y = 0.0683x + 0.1365,
where x is the LAS concentration, and y is the absorbance, the LAS concentration in
liquid detergent waste (soklin, rinso, attack, and chemist) was 48; 29.67; 23.71, and
19.73 mg/L,respectively. Absorbance is directly proportional to concentration and
inversely proportional to percent degradation. From the table it can be seen that the
chemist liquid detergent waste has a smaller absorbance value and LAS concentration
and a higher percentage of degradation, the higher the percentage of degradation, the
more LAS is degraded in the chemist liquid detergent waste compared to the other
three detergent wastes, so that the chemist liquid detergent more environmentally
friendly.

LAS Analysis by HPLC Method

In this study, LAS and liquid detergents were selected which had been degraded
by the photolysis method using a UV A lamp (λ = 365 nm) which was then tested
employing High-Performance Liquid Chromatography (HPLC) using a UV detector at a
wavelength of 224 nm. Column chromatography C18 (250 x 4.6mm) with a mobile
phase of methanol and water (60: 40v / v), the injection volume used was 10μL and a
flow rate of 1.0 mL/minute. Figure 8 is the HPLC test for LAS 5 mg / L, and Figure 9 is
the HPLC test for liquid detergent waste which was carried out using the photolysis
method as one of the supporting research results. Figure 8 shows that LAS has been
degraded which is indicated by a decrease in the peak of the chromatogram, where at
the initial peak before degradation the peak height is 5024 mm with a retention time of
2.773 minutes. However, after being degraded using a UV A lamp (λ = 365 nm) for 900
minutes the resulting chromatogram decreased to 1151 mm with a retention time of
2.674 (minutes). This shows that the organic compounds contained in LAS have been
degraded as evidenced by the decrease in the chromatogram. The difference in
retention time is due to the degradation process experiencing a shift in wavelength [11].
From Figure 9 it can be seen that the liquid detergent chromatograms of soklin, rinso,
attack, and chemist appear at nearly the same retention time as the LAS solution that
has been degraded (2.674 minutes), the retention time of each liquid detergent waste
respectively. 2.866; 2.833; 2.836; 2.809 minutes, this proves that the LAS in the liquid
detergent has been degraded by photolysis[12].
 Peak curent (mm)

LAS sebelum degradasi

LAS setelah degradasi

Retention time (minutes)

Figure 8. Chromatogram of the LAS degradation solution by photolysis,
mobile phase methanol: water (3: 2), flow rate 1 mL / minute, Injection volume
P 10μL, Chromatography
column C18 (250 x 4.6mm), UV detector 224 nm.

Peak curent (mm)

Kemist Rinso

Attack Soklin

Retention time (minutes)

Figure 9. Chromatogram of degradation of liquid detergent waste by photolysis,
mobile phase methanol: water (3: 2), flow rate 1 mL / minute, Injection volumeP10μL, Chromatography column
C18 (250 x 4.6mm), UV detector 224 nm.
 CONCLUSION
It can be concluded that the two methods of LAS degradation by sonolysis and
photolysis the longer the irradiation time, the more LAS is degraded. The addition of
TiO2 catalyst to LAS degradation by sonolysis and photolysis can increase the
percentage of LAS degradation by 53.98% to 68.20% and 56.28% to 93.94%,
respectively. The photolysis method is used for the application of LAS degradation in
liquid detergent waste (soklin, rinso, attack and chemist) with LAS degradation
percentages of 82.8; 91.59; 93.7, and 96.02%. Chemist liquid detergent waste has a
higher percentage of degradation compared to the other three detergent wastes, so the
Kemist liquid detergent is more environmentally friendly.
REFERENCES
[1] Maharani M & Wesen P, 2013. Degradation of LAS and BOD by Activated Sludge Process
Using a Combination of Pseudomonasi Aeruginosa Bacteria and Pseudomonasi Putida. Jurnal
Envirotek. 9(2) : 50-62.

[2] Hendra, Barlian E, Razak A, & Sanjaya H, 2012. Photo-degradation of surfactant compounds
using UV Rays with additon of TiO2 catalysts in laundry waste . Jurnal Kimia. 7(3) : 66-75.

[3] Natawidha CN, 2012. Degradation of Detergent Waste (Linear Alkylbenzene Sulfonate
Compounds) with TiO2-Based Composite Photocatalyst and Pumice Stone. Depok, Faculty of
Chemical Engineering. University of Indonesia.

[4] Retno P S, 2009. Water Treatment Technology Containing Linear Alkylbenzene Sulfonate
(LAS) and Ammonia with Advanced Oxidation Process and Membrane Filtration. Depok: Faculty
of Chemical Engineering, University of Indonesia.

[5] Stylidi M, Kondarides DI, & Verykios X E, 2003. Pathways of Solar Light-induced
Photocatalytic Degradation of Azo Dyes in Aqueous TiO2 Suspensions. Applied Catalysis.
Applied Catalysis B: Environmental. 40(3) : 271-286.

[6] Maryani Y, Kustiningsih I, Rakhma MY, & Nufus H, 2010. Activity Test of Several Catalysts in
the Degradation Process of Detergent Active Compounds by Photocatalyst. Chemical and
Process Engineering Seminar, 15(6) : 145-153.

[7] Schleheck, Dong W, K. Dnger, E. Heinzle and AM Cook. 2000. An a-Proteobacterium

Converts Linear Alkylbenzene sulfonate Surfactants into Sulfophenyl carboxylates and Linear
Alkyldiphenyl etherdisulfonate Surfactants into Sulfodiphenyl ethercarboxylates. Applied. and
Env. Microb. 66(5) : 1911–16.

[8] Sanjaya H, Aziz H,&Syukri. 2013. Photodegradation of linear alkyl sulfonate surfactants (LAS)
using 254 nm UV light with the help of ZnO as a catalyst. Jurnal sainstek Universitas Gorontalo,
3(2) : 23-29.

[9] Ghanbarian M, Nabizadeh R, Mahvi AH, Nasseri S, & Naddafi K, 2011. Photocatalytic
Degradation of Linear Alkylbenzene Solfunate from Aqueous Solution by TiO2 Nanoparticle.
Iran Journal of Environmental Health Science English. 8(4) :309-316.

[10] Safni, Sari F, Maizatisna, & Zulfarman. 2007. Degradation of Methanyl Yellow by Sonolysis
and Photolysis with the Addition of TiO2 Anatase.Jurnal Sains Meteri Indonesia, 11(1) : 47-51.
[11] Safni, Anggraini D, Welllia DV, & Khoiriyah K, 2015. Degradasi Zat Warna Direct Red-23 dan
Direct Violet Dengan Metode Ozonolisis, Fotolisis Dengan Sinar Uv dan Cahaya Matahari
Menggunakan Katalis N-Doped TiO2. Jurnal Litbang Industri, 5(2): 123-130.

Safni, Anggraini D, Welllia DV, & Khoiriyah K, 2015. Degradation of Direct Red-23 and Direct
Violet Dyes Using Ozonolysis Method, Photolysis with Uv Light and Sunlight Using N-Doped
TiO2 Catalyst. Journal of Industrial Research and Development, 5 (2): 123-130.

[12] Budiawan, Fatisa Y, & Khairani N, 2009. Optimization of Biodegradability and Toxicity Test
of Degradation Result of Linear Alkyl Benzene Sulfonate (LAS) Surfactants as Cleaning Detergent
Materials. Makara Science. 13 (2): 125-133.