Textile Wastewater Treatment by Peroxydisulfate/Fe(II)/UV: Operating Cost Evaluation and Phytotoxicity Studies

  • Nadia BougdourEmail author
  • Rachid Tiskatine
  • Idriss Bakas
  • Ali Assabbane
Original Article


The discharges of the wastewater from the textile industry generate a substantial quantity of effluents which can cause various environmental problems, if disposed of without any prior treatment. Therefore, the treatment of these textile effluents is necessary. The present study aims to investigate the removal efficiency of colors from wastewater containing mixed primary direct dyes and real textile industry wastewater using PDS (Peroxydisulfate)/Fe(II)/UV process. A simulated mixture, based on an industrial recipe and containing Reactive Yellow 17 (RY17), Reactive Red 120 (RR120), and Reactive Blue 19 (RB19), was investigated. The obtained results showed that the mineralization rate is around 96.1% for RY17, 99.2% for RR120, 100% for RB19 and 80% for their mixed during 2 h of the treatment. The degradation of real textile wastewater was about 66% under similar conditions. The evaluations showed that ~ 93.82 MAD/m3 (~ 8.64 EURO/m3) is needed to supply the operating cost. As a vital industrial criterion, it was estimated that the conditions of initial pH of 3, [PDS] = 1 mM and T = 25 °C the highest cost effective case of the process for degrading the mixed dyes. Phytotoxicity studies revealed that the degradation products of mixed dyes and textile effluent were scarcely toxic in nature, thereby increasing the applicability of PDS/Fe(II)/UV for the treatment of textile wastewater. This will open a perspective for the reuse of treated water in crop irrigation. Based on the results of the advanced oxidation technologies experiments, it was found that PDS/Fe(II)/UV is the best treatment method for real textile wastewater.


Textile wastewater Peroxydisulfate Degradation Mixed dyes Cost evaluation Phytotoxicity 



Advanced oxidation technology


Chemical cost


Degradation efficiency


Reactive blue 19


Electricity cost


Ultra violet


Rate constant


Reactive Red 120




Reactive Yellow 17


Chemical oxygen demand


Mixed dyes


Reaction time


Moroccan Dirham


Operating cost


Textile wastewater


Biochemical oxygen demand


Electrical energy consumption

1 Introduction

Control of water pollution is a very important scientific research area. The textile industry is among the principle polluting and the largest consumers of water, dyes and chemicals used during the various stages of textile processing. The presence of very small quantities of dyes in water can create aesthetic problems, hinders the photosynthesis, and badly affects the aquatic life thereby posing significant risk to the food chain [1]. Conventional methods including physico-chemical methods, coagulation, activated carbon adsorption and membrane technologies have been used for decolorizing the textile wastewater [2, 3, 4].However, these methods non-destructive, indeed, all these processes are either ineffective in front of the scale of this pollution, or source of secondary pollution (sludge formation) and requires a long time of the treatment. One of the global objectives in controlling the environmental pollution is the remediation of dye wastewater before being released into the wild [5].

The advanced oxidation technologies (AOTs) showcased good result in removing organic pollutants, due to the high oxidation potential of hydroxyl radicals (E0 = 2.7 V) as the most important interactive species [6, 7]. Actually, sulfate radicals (SO 4 · )-based technology has received increasing attention. Sulfate radical-based AOTs have a series of advantages in comparison with HO· based methods, for example: higher oxidation potential, higher selectivity and efficiency to oxidize pollutants containing unsaturated bonds or aromatic ring, wider pH range, relatively stable nature and cheap [8, 9]. The peroxydisulfate activation was done via UV irradiation, heat, transition metals, or other ways to forming the strong oxidant (SO 4 · ) (E0 = 2,6 V) [10, 11, 12, 13]. This last relatively a selective oxidant that reacts especially with benzene and its derivatives [14].Furthermore, (SO 4 · ) has a longer life time (3–4 × 10−5 s) than (HO·) (2 × 10−8 s).Therefore, sulfate radicals are capable of degrading the emerging contaminants more efficiently [15]. Peroxydisulfate is slowly reacting with contaminants in water, its activation is therefore necessary for accelerating the degradation process. Peroxydisulfate can be activated using iron ions as a catalyst because it is an important catalyst in the PDS/UV process, a cost-effective, eco- friendly and no toxic and it directly affects the performance of sulfate radical SO4·-, by catalytically decomposing PDS as shown in Eq. (1) [16, 17]. The mechanism describing the Fe2+ activated peroxydisulfate process includes primarily the following reactions [17]:
$${\text{S}}_{2} {\text{O}}_{8}^{2 - } + {\text{Fe}}^{2 + } \to {\text{Fe}}^{3 + } + {\text{SO}}_{4}^{ \cdot - } + {\text{SO}}_{4}^{2 - }$$
$${\text{SO}}_{4}^{ \cdot - } + {\text{SO}}_{4}^{ \cdot - } \to {\text{S}}_{2} {\text{O}}_{8}^{2 - }$$
$${\text{SO}}_{4}^{ \cdot - } + {\text{Fe}}^{2 + } \to {\text{SO}}_{4}^{2 - } + {\text{Fe}}^{3 + }$$
$${\text{SO}}_{4}^{ \cdot - } + {\text{S}}_{2} {\text{O}}_{8}^{2 - } \to {\text{SO}}_{4}^{2 - } + {\text{S}}_{2} {\text{O}}_{8}^{ \cdot - }$$

Therefore, emerging pollutants are destroyed by the sulfate radicals more efficiently [15].The AOT is presently a hot topic for researchers who aim to decrease the amount of chemical with increasing color removal percentage. Some studies [18, 19] with single dye were targeted. Since textile wastewater usually contains a variety of chemical dyes, the efficiency of such a process is uncertain when treating real wastewaters. Therefore, studies using a mixture of primary dyes are necessary for the evaluation of such a process.

In this study, RY17 (Reactive Yellow 17), RB19 (Reactive Blue 19) and RR120 (Reactive Red 120) were selected for dedicated treatment by AOTs based the peroxydisulfate. Since there is no research about the treatment of synthetic or real dyeing wastewater by PDS/Fe(II)/UV, the scopes of this study is to investigate the application of a Peroxydisulfate process for dyes in a simulated mixture based on an industrial dyeing recipe. The selection was based on mixture of three dyes as a model dyes. The treatment of a real effluent of the textile industry was also conducted. Several steps were done in the order to reach our objective: (1) Study of the degradation kinetics of the three reactive dyes to provide a broad overview of sulfate radical-based decontamination technology, (2) The mineralization individual of the reactive dyes and their mixed, (3) The changes in the chemical oxygen demand. UV–Vis and color spectra during PDS treatment were monitored to better explain the degradation process for the real textile wastewater treatment, (4) The evaluation of the operating cost of the PDS/Fe(II)/UV process and consumption energy and finally the investigation of phytotoxicity of the degradation products upon plant seeds Lens culinaris in order to determine the environmental impact of the treated water.

2 Materials and Methods

2.1 Materials

Reactive Yellow 17, Reactive Red 120, and Reactive Blue 19 were purchased from Sigma-Aldrich, as industrial dyes. Their chemical structures and other characteristics are listed in Table 1 and absorption spectrums are shown in the Fig. 1. Sodium peroxydisulfate (Na2S2O8, ≥ 99%), Sulfuric acid (H2SO4, 98%), Sodium hydroxideand Iron (II) sulfate heptahydrate (FeSO4·7H2O, ≥ 98%) are of analytical grade bought from Sigma-Aldrich and Merck products.
Table 1

Main characteristics of tested dyestuff

C.I. generic name

Reactive Blue 19 (RB19)

Reactive Red 120 (RR120)

Reactive Yellow 17 (RY17)


Remazol brilliant blue R (spec.)

SenarcionRed BF2R réactive

Zenative yellow BF3R reactive

Molecular formula




M (g/mol)




Chemical class








Fig. 1

Absorption spectrum and maximum wavelength of a RY17, b and RB19, c RR120

Aqueous solutions were prepared by using distilled water.

2.2 Experimental Procedure

All experiments were carried in a Pyrex glass reactor with an internal diameter of 80 mm and a height of 120 mm with a double walled cooling water jacket around the reactor to keep the temperature of the solutions constant throughout the experiments (23 °C). The reactor contain a high-pressure mercury lamp (125 W, Philips HPK) emitting UV light at 365.5 nm. A 500 mL of the dye solution was placed in the reactor. The pH value (pH = 3) was adjusted by adding concentrated solution of Sulfuric acid H2SO4 using a pH meter (HANNA Instrument Ph209, HI 1332). Before starting the UV irradiation, ferric salt (catalyst) and Sodium Peroxydisulfate were introduced into the photoreactor and the reaction solution was mixed by a magnetic stirrer to ensure homogeneity during the reaction. After irradiation, 3 mL of the samples was collected regularly and filtered through 0.45 µm nylon filter (Millipore) membrane before the analysis.

2.3 Analytical Methods

The azo dyes single RB19, RR120, RY17(fixed at 10 mg/l) and their mixed with a proportion of 33.33% for each dyes) were filtered by Millipore membrane filter type 0.45 µm, and the concentrations was determined by measuring the absorbance from 200 to 800 nm using a UV–Vis spectroscopy (JASCO V-630 Spectrophotometer). The dye decolorization (degradation efficiency DE) used is calculated as follows:
$$\%\, {\text{DE}} = {\raise0.7ex\hbox{${({\text{C}}_{0} - {\text{C}}_{\text{t}} )}$} \!\mathord{\left/ {\vphantom {{({\text{C}}_{0} - {\text{C}}_{\text{t}} )} {{\text{C}}_{0} }}}\right.\kern-0pt} \!\lower0.7ex\hbox{${{\text{C}}_{0} }$}} \times 100$$
where C0 and C are respectively the initial concentration of dye and at different time intervals.
The mineralization rate in terms of chemical oxygen demand (COD) is a measure of the oxygen equivalent of the organic matter present in textile wastewaters content of a sample that is susceptible to oxidation by a strong chemical oxidant [20]. It was evaluated by using colorimetric method, as described in the standard methods for the examination of water and wastewater. Percentage COD removal was calculated using the following equation (Eq. 6):
$$\% {\text{COD}} = {\raise0.7ex\hbox{${({\text{COD}}_{0} - {\text{COD}}_{\text{t}} )}$} \!\mathord{\left/ {\vphantom {{({\text{COD}}_{0} - {\text{COD}}_{\text{t}} )} {{\text{COD}}_{0} }}}\right.\kern-0pt} \!\lower0.7ex\hbox{${{\text{COD}}_{0} }$}} \times 100$$

COD0 and CODt are respectively the values of chemical oxygen demand (COD) at initial and final oxidation reaction.

The data presented in this work were obtained from duplicate experiments and the errors of measurement were estimated to be within 5%.

2.4 Characterization of Textile Dyeing Wastewater

The characterizations of raw effluent from the textile industry are: pH 6.78–7.90, COD 760 mg/L, BOD5 289 mg/L, Turbidity 82.5 NTU, Conductivity 19. 5 mS/cm and the biodegradability ratio BOD5/COD = 0.38. Thus, AOTs based peroxydisulfate are the best option to treat such types of wastewater as mentioned earlier.

3 Results and Discussion

The previous works on the dyes photo-degradation are generally related to the solutions containing a single dye molecule [18, 19]. Nonetheless, industrial wastewaters are charged with many organic pollutants, dyes molecules and considered as a complex matrices. Reactive Yellow 17 (RY17), Reactive Red 120 (RR120) and Reactive Blue 19, were used in the present study as a model molecules. The optimized process was applied to the treatment of the real effluent from the textile industry.

3.1 Mineralization Analysis

The COD test was used to follow the efficiency of dyes removal by measuring the organic compounds amount in the solution (the converting of organics into the CO2, H2O and related mineral oxides). In this research, we started by the mineralization of the single dye in the solution (RY17, RR120, and RB19) separately then their mixture. In order to compare the COD values, the test analysis was done twice before and after treatment, under the optimum operating conditions. The mineralization rate was found to be 96.1% for the RY17, 99.2% for RR120 and 100% for RB19, with a treatment time of 2 h. The mineralization rate of a mixture of three dyes was about 80% after 2 h of treatment. To reach a mineralization rate of about 97% (see Fig. 2a) the dyes mixture requires a longer processing time around 3 h of irradiation. The Fig. 2b shows that exponential decay over time of dyes COD variation, which suggests that the degradation process follows a first order kinetics. Therefore, prolonged irradiation time would be reasonable for the complete mineralization. From these results, the PDS/Fe(II)/UV seem to be an effective process for the dyes textile degradation.
Fig. 2

a Evolution of COD, b kinetics of degradation as a function of irradiation time of the three dyes and their mixture. [Dye] = 10 mg/L, pH = 3, [PDS] = 1 Mm and [Fe(II)] = 0.05 Mm

3.2 Application to a Real Effluent of the Textile Industry

3.2.1 Textile Wastewater

The textile wastewater was obtained from the textile industry in (Casablanca), Morocco, at Juin 2017. The taken samples were kept in at 4 °C in accordance with the standard methods for the Water and Wastewater Examination.

The characterization of the raw effluent has been done by collecting raw effluent samples from equalization tank in the industry. Sampling cans were cleaned using distilled water during sample collection.

3.2.2 Industrial Textile Wastewater Treatment

The experimental results are shown in Fig. 3a. About 40% of the reduction in color of wastewater treatment after 10 min has been achieved. During wastewater treatment by PDS/Fe(II)/UV process, a complete color removal at time 200 min was observed. As can be seen in Fig. 3b, the efficiency of mineralization increases with a time and reached about 90% after 240 min. The analysis of the COD reduction during the PDS/Fe(II)/UV process revealed a mineralization of the tested wastewater.
Fig. 3

a Changes of the UV–Vis spectra of textile dye for different time intervals. b COD removal of textile dye

3.3 The Process Operating Cost Evaluation and Consumption Energy

Electric energy represents one of the major fractions of the operating costs. Simple figures-of-merit based on electric energy consumption are informative and very useful. Low operating cost (OC) is one of the economic parameters which play an important role in chemical process. For economic evaluation of our work, chemicals and electricity cost (EC) were taken into account as major constituents of the OC [21, 22]. Energy efficiency of UV based AOPs is usually quoted in terms of electrical energy per order. Based on the photochemistry commission proposal of the international union of pure and applied chemistry (IUPAC) for photochemical processes, the electrical energy consumption (EEC in kWh/m3) is accessible. The chemicals and industrial price are show in the Table 2.
Table 2

Industrial costs of the used chemicals and unit of the electricity

Energy cost

Reagents costs





170 MAD/kg

120 MAD/L

300 MAD/kg

10.87 Euro/KWh

15.64 Euro/kg

11.04 Euro/L

27.61 Euro/kg

The electrical energy consumption for the process can be calculated by the following equation [23, 24, 25]:
$$EEC = \frac{1000 \times P \times t}{{60{\text{V}} \times {\raise0.7ex\hbox{${{\text{logC}}_{ 0} }$} \!\mathord{\left/ {\vphantom {{{\text{logC}}_{ 0} } {\text{C}}}}\right.\kern-0pt} \!\lower0.7ex\hbox{${\text{C}}$}}}}$$
where P is the applied electrical power (kW) in the photochemical system, t is the process time (min), V is the treated water volume (L), C0 and C are respectively the initial concentrations of pollutant and at any time (mg/L).Combining Eqs. (5) and (4) simply gives an equation for the EEC in the form:
$$EEC = \frac{38.4 \times P}{V \times K}$$
The comparative analysis of the processes in terms of the first-order kinetic rate constant, percentage degradation and time required for degradation is presented in Table 3 which indicates that UV/PDS/Fe(II) is much more efficient compared to the UV/PDS.
Table 3

Kinetic rate constant and time requirement for mixed dye degradation of two processes


k (min−1)

t 0.9(min)










The EEC required for degradation of mixed dyes PDS/Fe/UV and PDS/UV was 41.53 and 83.87 kWh/m3, respectively. EEC can be correlated to the energy costs. Considering the cost of electricity and the time taken for the process, the PDS/Fe/UV process will prove highly the cost effective which save up to 42.34 kWh/m3 of electrical energy.

The electrical power and volume values were 0.125 kW and 0.5 L respectively. Also, the required time to achieve 90% of the DE and kinetic characteristic of UV/PDS and PDS/Fe(II)/UV were reported in Table 4. The summation of the CC (in MAD/m3) pertinent to the used oxidants in 1 m3 of the solution and the relevant EC (in MAD/m3) of the process were considered as the OC. The amounts of electricity, chemicals and operating costs for UV/PDS and UV/PDS/Fe(II) system have been compared in Fig. 4. The Figure showed that UV/PDS consume a double EC than PDS/Fe(II)/UV process. Therefore, the UV/PDS/Fe(II) system is more cost-effective than PDS/UV process. This system can attract the most attention. From economic and chemical point of view, it is the most effective (t0.9 = 9 min) and the lowest-cost (93.82 MAD/m3) process for degrading the mixed dyes.
Table 4

Phytotoxicity test of mixed dyes, textile wastewater and its degradation products on the seeds of Lens culinaris


Mixed dye

Textile wastewater







Germination (%)







Shoot length(cm)

12.41 ± 0.04

9.08 ± 0.12**

13.02 ± 0.2*

12.22 ± 0.05

5.25 ± 0.072**

12.98 ± 0.22**

Root length (cm)

5.31 ± 0.21

4.25 ± 0.07**

4.76 ± 0.09*

5.55 ± 0.40

2.06 ± 0.16**

6.49 ± 0.05*

(I) seeds germinated with distilled water; (II) *seeds germinated with MD ** with TW; (III)*seeds germinated in metabolites obtained after degradation of MD** of TW

Data was analyzed by one way analysis of variance (ANOVA) with Turkey–Kramer multiple comparison test using mean values of germinated seeds of three experiments (replicates). Seeds germinated with MD and TW are significantly different from the seeds germinated in plain Distilled water at *P < 0.05, **P < 0.01

Fig. 4

The EC, CC and OC amount for UV/PDS and UV/PDS/Fe(II) system

3.4 Phytotoxicity Studies

In order to assess the toxicity dyes and degraded compound of dye, phytotoxicity test was performed on Lens culinaris. The mixed dyes (RR120, RY17 and RB19) (33, 33% for each) were dissolved in 500 mL distilled water for phytotoxicity tests. The study was carried out at room temperature on seeds of Lens culinaris (20 seeds of each) by watering 5 mL of mixed dyes and effluent textile. Control set was carried out using irrigation water at the same time. Germination (%), Shoot length and Root length were recorded after 8 days.

The results obtained indicate that the germination of the seeds of Lens culinaris is reduced with the addition of MD and TW, whereas the degradation products gave the plant an extremely significant growth. In addition, the shoot length and the root length of Lens culinaris are improved compared to controls (distilled water). This observation suggests that metabolites, obtained after bleaching of MD and TW, are not only nontoxic, but they may play a nutritious role in the plant germination and growth.

Similar results were found by Saratale et al. [26]. The shoot length and roots length of this plant (Phaseolus mungo) were improved during the phytotoxicity studies degraded metabolites formed after catalytic degradation on Phaseolus mungo.

4 Conclusion

In this research, a system (UV/PDS/Fe) was studied to degrade and mineralize the Industrial Textile Wastewater. The core findings of this research can be summarized as follow:
  • The fast decolorization of three primary dyes by PDS/Fe/UV follows pseudo first-order kinetics in acidic solutions.

  • The operating cost estimation showed that the most cost effective conditions for the UV/PDS/UV are the [PDS] = 1 mM, [Fe(II)] = 0.05 mM, pH = 3 and T = 25 °C, in which the process will reach to 100% and 79.5% of degradation and mineralization efficiencies, after 45 and 120 min, respectively.

  • The evaluations showed that 93.82 MAD/m3 is needed to supply the operating cost of the process for degrading the mixed dyes with considering industrial and environmental criteria and energy consumption.

  • Using the low amount of iron ions, peroxydisulfate and pH 3, the real industrial textile effluents were degraded up to 60% after 30 min. 40% of the degradation efficiency was obtained after only 10 min. Based on the advanced oxidation technologies experiments, it was found that PDS/Fe(II)/UV is the best treatment method for real textile wastewater.

Phytotoxicity tests demonstrated lower percentage of germination in Lens culinaris (59%) for textile wastewater, compared to the seeds treated with the degradation products (100%).Finally, the real time application of the system PDS/Fe2+/UV through successful repeated treatment for actual industrial wastewater. The phytotoxicity assay (with respect to Lens culinaris) revealed that the degradation of the textile effluent produced nontoxic metabolites on the growth of this plant, which increases its potential application. This will open a perspective for the reuse of treated water in crop irrigation.


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Copyright information

© The Tunisian Chemical Society and Springer Nature Switzerland AG 2019

Authors and Affiliations

  1. 1.Team Catalysis and Environment, Faculty of ScienceIbn Zohr UniversityAgadirMorocco
  2. 2.Thermodynamics and Energetics Laboratory, Faculty of ScienceIbn Zohr UniversityAgadirMorocco

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