Easy Removal of Methylparaben and Propylparaben from Aqueous Solution Using Nonionic Micellar System Safia Habbal, Boumediene Haddou, Jean-Paul Canselier, Christophe Gourdon To cite this version: Safia Habbal, Boumediene Haddou, Jean-Paul Canselier, Christophe Gourdon. Easy Removal of Methylparaben and Propylparaben from Aqueous Solution Using Nonionic Micellar System. Tenside Surfactants Detergents, Carl Hanser Verlag 2019, 56 (2), pp.112-118. 10.3139/113.110611. hal- 02330481 HAL Id: hal-02330481 https://hal.archives-ouvertes.fr/hal-02330481 Submitted on 24 Oct 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Open Archive Toulouse Archive Ouverte OATAO is an open access repository that collects the work of Toulouse researchers and makes it freely available over the web where possible This is an author’s version published in: http://oatao.univ-toulouse.fr/24275 Official URL: https://doi.org/10.3139/113.110611 To cite this version: Habbal, Safia and Haddou, Boumediene and Canselier, Jean- Paul and Gourdon, Christophe Easy Removal of Methylparaben and Propylparaben from Aqueous Solution Using Nonionic Micellar System. (2019) Tenside Surfactants Detergents, 56 (2). 112-118. ISSN 0932-3414 Any correspondence concerning this service should be sent to the repository administrator: [email protected] y S. Habbal1,B. Haddou1, J. P. Canselier2 and C. Gourdon2 Easy Removal of Methylparaben and Propylparaben from Aqueous Solution Using Nonionic Micellar System This study aimed to investigate the simultaneous removal of 1 Introduction methylparaben (MePB) and propylparaben (PrPB) from efflu- ents (each one at 16 mg/L) using a nonionic micellar system p-Hydroxybenzoic acid esters, known as parabens (PBs), were containing Triton X-114. Response surface methodology (RSM) widely used as preservatives in pharmaceuticals, foods and has been carried out. Extraction results using nonionic surfactant personal care products [1]. Methylparaben and propylparaben two-phase system were considered as a function of surfactant are usually used and often present together in the products concentration and temperature variation. Four responses were [2]. The maximum concentration in cosmetics formulation is investigated: MePB and PrPB extraction yield (E), solute (Xs,w) limited to 0.4% for individual paraben molecules and to 0.8% and surfactant (Xsf,w) concentrations in the aqueous phase and in combination [3]. However, the paraben concentration in the volume fraction of micellar phase (uC) at equilibrium. Very pharmaceutical products seldom exceeds 1%. They are used high extraction efficiencies (99% for PrPB and 84% for MePB) as excipients to preserve the active ingredient from microbial were achieved at optimal conditions. Thereby, the amounts of contamination and prevent degradation [4]. In front of this PrPB and MePB were reduced 80 and 5 times, respectively. The craze for parabens, many papers led to a discussion about extraction improvement using sodium sulfate was also shown. their possible carcinogenicity and estrogenic effects [5, 6]. Finally, the solute stripping from micellar phase by pH change They are suspected to change the hormone concentration in was proved. organisms and were found in breast tumors [7, 8]. Further- more, due to their potential toxicity and estrogen-mimicking Key words: Methylparaben, propylparaben, non-ionic surfac- properties, parabens are resistant to biological treatment in tant, response surface methodology, extraction wastewater treatment plants [9–11]. As an alternative to conventional and more recent waste- water treatments such as aerated biofilm system [12, 13], Einfaches Entfernen von Methylparaben und Propylpara- ozonation [14], electrochemical methods [15, 16], sonochem- ben aus wässriger Lösung mit einem nichtionischen Mizel- ical degradation [17], photodegradation [18, 19] and photoly- lensystem. Ziel dieser Untersuchung war, Methylparaben sis [20], Cloud Point Extraction (CPE) is a relatively simple (MePB) und Propylparaben (PrPB) aus Abwässern (jeweils mit and environmentally friendly technique [21–26]. Involving 16 mg/l) unter Verwendung eines nichtionischen Mizellensystems a thermoseparating system, it avoids the use of an organic (Triton X-114) simultan zu entfernen. Die Response-Surface-Me- solvent, produces a small sludge volume and requires low thode (RSM) wurde durchgeführt. Die Extraktionsergebnisse un- energy consumption. This process is very efficient for water ter Verwendung eines nichtionischen Tensid-Zweiphasensystems treatment containing hazards of different organic or metal wurden als Funktion der Tensidkonzentration und der Tempera- ions [21, 27–42]. CPE could even be implemented in a con- turänderung betrachtet. Es wurden vier Antworten untersucht: tinuous process [42–47]. MePB- und PrPB-Extraktionsausbeute (E), Konzentrationen von On the basis of this finding, the simultaneous CPE of gelöstem Stoff (Xs,w) und Tensid (Xsf,w) in der wässrigen Phase methylparaben (MePB) and propylparaben (PrPB) from their und der Volumenanteil der mizellaren Phase (uC) im Gleichge- aqueous solutions at 16 mg/L was studied. Triton X-114 (TX- wicht. Unter optimalen Bedingungen wurde eine sehr hohe Ex- 114) which is characterized by fast separation kinetics and a 8 traktionswirkung (99% für PrPB und 84% für MePB) erreicht. Da- low clouding temperature (Tc =23 C), was further investi- durch wurden die Mengen an PrPB und MePB um das 80- bzw. 5- gated concerning its phase behavior in water and its ability fache reduziert. Die Extraktionsverbesserung unter Verwendung to extract the two solutes. Hence, we measured the cloud von Natriumsulfat wurde ebenfalls gezeigt. Schließlich wurde das point (Tc) of the water-surfactant, water-surfactant-solute as Ablösen der gelösten Substanz aus der mizellaren Phase durch well as water-surfactant-sodium sulfate systems. Extraction pH-Wert-Änderung nachgewiesen. experiments in batch mode were conducted in order to de- monstrate the applicability of nonionic micellar system to Stichwörter: Methylparaben, Propylparaben, nichtionisches the CPE of parabens. All the extraction results were modeled Tensid, Response-Surface-Methode, Extraktion by an experimental design as a function of temperature and surfactant concentration. Finally, sodium sulfate addition and pH effects on extraction yield were investigated. 2 Materials and Methods 2.1 Materials 1 Laboratory of Physical Chemistry of Materials: Catalysis and Environment, Uni- versity of Science and Technology of Oran, BP 1505, M’Nouar, Oran, Algeria 2 Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INP, UPS, 4 allé The commercial nonionic surfactant investigated in this study, Emile Monso, CS 84234, 31432 Toulouse cedex 4 Toulouse, France Triton X-114, belongs to the polyethoxylated alkylphenol family (formula: (CH3)3-C-(CH3)2-CH-C6H4O(C2H4O)n-H, with n = 7 surfactant and salt concentrations allows the CPE of heat 8 or 8), was supplied by Sigma Aldrich (Tc =23.1 C. Its critical sensitive products at room temperature. Furthermore, the micelle concentration was 2 · 10–4 M. MePB (methyl 4-hydro- cloud point control contributes to the reduction of heating xybenzoate), PrPB (propyl 4-hydroxybenzoate), methanol energy cost of large scale CPE process. (HPLC grade), acetonitrile (HPLC grade) and sodium sulfate were provided by Sigma Aldrich. Distilled water was used for 3.2 Experimental design dilutions and deionized water for HPLC analyses. Extraction results using micellar phase of TritonX-114 were 2.2 Methods considered as a function of surfactant concentration (Xsf), and temperature (T). Four responses (Y) were investigated: Cloud point measurement was achieved using a Mettler FP MePB and PrPB extraction yield (E), solute (Xs,w) and surfac- 900 device. The cloud point temperature (CPT) was defined tant (Xsf,w) concentrations in the aqueous phase and volume as the temperature at which the sample turned turbid. fraction of micellar phase (uc) at equilibrium. A polynomial The distribution of parabens (MePB and PrPB) in the two- model was used to correlate the relationship among the in- phase system TX-114/water was studied in batch experi- dependent variables (Xsf and T) and the four responses: E, ments. Samples (5 mL) containing 16 mg/L of each paraben Xs,w,Xsf,w and uc [50]. The quadratic equations examined and TX-114 (at concentrations of 1–5 wt.%) were prepared the effects of each independent variable on the response: in distilled water. The homogenized samples were placed 2 2 in a precision oven for 2 h (at temperatures between 208C Y ¼ a0 þ a1Xsf þ a2T þ a12Xsf T þ a11Xsf þ a22T ð1Þ and 408C). Parabens and surfactant concentrations in aque- A central composite design was considered to determine the ous phase were determined by using a Shimadzu RP-HPLC polynomial model constants of the predictive equation. The system, with a quaternary pump, degasser, tempered auto- models were checked by plotting computed data against ex- sampler, column thermostat. Column RP18 (ODS), 1 mL/ perimental results. min, UV detector