Synthesis and Characterization of Environmentally Friendly Chitosan-Arabic Gum Nanoparticles for Encapsulation of Oregano Essential Oil in Pickering Emulsion.

The encapsulation of bioactive agents through the utilization of biodegradable nanoparticles is a topic of considerable scientific interest. In this study, microcapsules composed of chitosan (CS) and Arabic gum (GA) nanoparticles were synthesized, encapsulating oregano essential oil (OEO) through Pickering emulsions and subsequent spray drying. The optimization of hybrid chitosan and Arabic gum (CS-GA) nanoparticle formation was carried out via complex coacervation, followed by an assessment of their behavior during the formation of the emulsion. Measurements of the size, contact angle, and interfacial tension of the formed complexes were conducted to facilitate the development of Pickering emulsions for encapsulating the oil under the most favorable conditions. The chitosan-Arabic gum capsules were physically characterized using scanning electron microscopy and fitted to the Beerkan estimation of soil transfer (BEST) model to determine their size distribution. Finally, the OEO encapsulation efficiency was also determined. The optimum scenario was achieved with the CS-GA 1-2 capsules at a concentration of 2% wt, featuring a contact angle of 89.1 degrees, which is ideal for the formation of oil/water (O/W) emulsions. Capsules of approximately 2.5 µm were obtained, accompanied by an encapsulation efficiency of approximately 60%. In addition, the hybrid nanoparticles that were obtained showed high biodegradability. The data within our study will contribute fundamental insights into CS-GA nanoparticles, and the quantitatively analyzed outcomes presented in this study will hold utility for forthcoming applications in environmentally friendly detergent formulations.

Antagonistic Toxic Effects of Surfactants Mixtures to Bacteria Pseudomonas putida and Marine Microalgae Phaeodactylum tricornutum.

Surfactants can be found in an ever-widening variety of products and applications, in which the combination of several types of surfactants is used to reinforce their properties, looking for synergistic effects between them. After use, they tend to be discarded into wastewater, ending up in aquatic bodies with concerning harmful and toxic effects. The aim of this study is the toxicological assessment of three anionic surfactants (ether carboxylic derivative, EC) and three amphoteric surfactants (amine-oxide-based, AO), individually and in binary mixtures of them (1:1 w/w), to bacteria Pseudomonas putida and marine microalgae Phaeodactylum tricornutum. Critical Micelle Concentration (CMC) was determined to demonstrate the capacity to reduce surface tension and the toxicity of the surfactants and mixtures. Zeta potential (ζ-potential) and micelle diameter (MD) were also determined to confirm the formation of mixed surfactant micelles. The Model of Toxic Units (MTUs) was used to quantify the interactions of surfactants in binary mixtures and to predict if the concentration addition or response addition principle can be assumed for each mixture. The results showed a higher sensitivity of microalgae P. tricornutum to the surfactants tested and their mixtures than bacteria P. putida. Antagonism toxic effects have been detected in the mixture of EC + AO and in one binary mixture of different AOs; this is to say, the mixtures showed lower toxicity than expected.

Environmental impact assessment of nanofluids containing mixtures of surfactants and silica nanoparticles.

Due to widespread use of nanoparticles in surfactant-based formulations, their release into the environment and wastewater is unavoidable and toxic for biota and/or wastewater treatment processes. Because of concerns over the environmental impacts of nanofluids, studies of the fate and environmental impacts, hazards, and toxicities of nanoparticles are beginning. However, interactions between nanoparticles and surfactants and the biodegradability of these mixtures have been little studied until now. In this work, the environmental impacts of nanofluids containing mixtures of surfactants and silica nanoparticles were valuated. The systems studied were hydrophilic silica nanoparticles (sizes 7 and 12 nm), a nonionic surfactant (alkyl polyglucoside), an anionic surfactant (ether carboxylic acid), and mixtures of them. The ultimate aerobic biodegradation and the interfacial and adsorption properties of surfactants, nanoparticles, and mixtures during biodegradation were also evaluated. Ultimate biodegradation was studied below and above the CMCs of the individual surfactants. The interfacial and adsorption properties of surfactant solutions containing nanoparticles were influenced by the addition of silica particles. It was determined that silica nanoparticles reduced the capability of the nonionic surfactant alkyl polyglucoside to decrease the surface tension. Thus, silica NPs promoted a considerable increase in the surfactant CMC, whereas the effect was opposite in the case of the anionic surfactant ether carboxylic acid. Increasing concentrations of surfactant and nanoparticles in the test medium caused decreases in the maximum levels of mineralization reached for both types of surfactants. The presence of silica nanoparticles in the medium reduced the biodegradability of binary mixtures containing nonionic and anionic surfactants, and this effect was more pronounced for larger nanoparticles. These results could be useful in modelling the behaviour of nanofluids in aquatic environments and in selecting appropriate nanofluids containing nanoparticles and surfactants with low environmental impact.

Occurrence of Textile Dyes and Metals in Tunisian Textile Dyeing Effluent: Effects on Oxidative Stress Status and Histological Changes in Balb/c Mice.

Although it is known that textile wastewater contains highly toxic contaminants whose effects in humans represent public health problems in several countries, studies involving mammal species are scarce. This study was aimed to evaluate the toxicity profile of 90-days oral administration of textile dyeing effluent (TDE) on oxidative stress status and histological changes of male mice. The TDE was collected from the textile plant of Monastir, Tunisia and evaluated for the metals, aromatic amines, and textile dyes using analytical approaches. Metal analysis by ICP-MS showed that the tested TDE exhibited very high levels of Cr, As, and Sr, which exceeded the wastewater emission limits prescribed by WHO and Tunisian authority. The screening of TDE through UPLC-MS/MS confirmed the presence of two textile dyes: a triphenylmethane dye (Crystal violet) and a disperse azo dye (Disperse yellow 3). Exposure to TDE significantly altered the malondialdehyde (MDA), Conjugated dienes (CDs), Sulfhydryl proteins (SHP) and catalase levels in the hepatic and renal tissues. Furthermore, histopathology observation showed that hepatocellular and renal lesions were induced by TDE exposure. The present study concluded that TDE may involve induction of oxidative stress which ensues in pathological lesions in several vital organs suggesting its high toxicity. Metals and textile dyes may be associated with the observed toxicological effects of the TDE. These pollutants, which may have seeped into surrounding rivers in Monastir city, can cause severe health malaise in wildlife and humans.

Persistent organic and inorganic pollutants in the effluents from the textile dyeing industries: Ecotoxicology appraisal via a battery of biotests.

Today, the textile industry is considered as a leading economic sector in Tunisia. However, this sector demands a huge volume of water and a wide spectrum of chemicals, which is converted into potentially toxic wastewater leading to environmental perturbation and human health toxicity. Assessment of the environmental risks associated with textile wastewater becomes a necessity. In this study, textile dyeing wastewater samples were collected before and after the physico-chemical treatment carried out by textile companies located in Monastir-city-Tunisia and subjected to chemical analyzes in order to determine their physicochemical characteristics and the content of metals and textile dyes. The ecotoxicological assessment was performed using four organisms, namely Selenastrum capricornutum, Vibrio fischeri, Daphnia magna and Lepidium sativum, to represent different trophic levels. Based on chemical data, some physicochemical parameters (e.g. TSS, COD and TSS levels) and metals (e.g. Cr, Hg and Sb) in the textile dyeing effluents were revealed not in compliance with the Tunisian standard. Moreover, high quantities of three disperse dyes have been detected even in the textile dyeing wastewater samples before and after treatments. The ecotoxicological data confirmed that the textile dyeing influents displayed toxic effects to all the test organisms, with Selenastrum capricornutum being the most sensitive organism. While, the above toxic effects were decreased slightly when evaluating the treated effluents. Metals and textile disperse dyes could be associated with the observed toxic effects of the textile influents and effluents. In fact, the treatment process applied by the evaluated companies was only partially efficient at removing metals, disperse dyes and effluent ecotoxicity, suggesting potential risks to aquatic biota. These findings emphasize the importance of applying integrated chemical and biological approaches for continuous evaluation of the toxicity of the treated effluents to predict hazards on the environment.

Ecotoxicity profile of heavily contaminated surface water of two rivers in Tunisia.

Persistent organic and inorganic contaminants generated by industrial effluent wastes poses a threat to the maintenance of aquatic ecosystems and public health. The Khniss and Hamdoun rivers, located in the central-east of Tunisia, receive regularly domestic and textile wastewater load. The present study aimed to survey the water quality of these rivers using physicochemical, analytical and toxicological approaches. In the physicochemical analysis, the recorded levels of COD and TSS in both samples exceed the Tunisian standards. Using the analytical approach, several metals and some textile dyes were detected. Indeed, 17 metals were detected in both samples in varying concentrations, which do not exceed the Tunisian standards. The sources of metals pollution can be of natural and anthropogenic origin. Three textile disperse dyes were detected with high levels compared to other studies: the disperse orange 37 was detected in the Khniss river with a concentration of 6.438 µg/L and the disperse red 1 and the disperse yellow 3 were detected in the Hamdoun river with concentrations of 3.873 µg/L and 1895 µg/L, respectively. Textile activities were the major sources of disperse dyes. For both samples, acute and chronic ecotoxicity was observed in all the studied organisms, however, no genotoxic activity was detected. The presence of metals and textile disperse dyes could be associated with the ecotoxicological effects observed in the river waters, in particular due to the industrial activity, a fact that could deteriorate the ecosystem and therefore threaten the human health of the population living in the study areas. Combining chemical and biological approaches, allowed the detection of water ecotoxicity in testing organisms and the identification of possible contributors to the toxicity observed in these multi-stressed water reservoirs.

Calcium Alginate as a Novel Sealing Agent for Colloidosomes.

We report on the preparation of colloidosomes formed with a poly(methyl methacrylate-co-butyl acrylate) latex shell, sealed using calcium alginate as a novel nontoxic and biodegradable sealing agent. The aim is to encapsulate enzymes in detergent formulations. The proposed method, with vegetable oil as the continuous phase, avoids the use of harmful organic solvents. Allura Red has been used as a water-soluble dye, in the core, to analyze the influence of variables such as sodium alginate and latex concentrations on the sealing and release profiles. After formation, the capsules were dispersed in either water or propylene glycol. The capsules have been examined using optical, confocal, and scanning electron microscopies. Working with the highest sodium alginate concentration and latex volume, the encapsulation efficiency is between 60 and 80%. Propylene glycol enables a better dispersion of the capsules compared with water. Dye release data have been fitted to exponential and Michaelis-Menten-type equations, leading to kinetic parameters that allow the simulation of the release process.

Silica micro- and nanoparticles reduce the toxicity of surfactant solutions.

In this work, the toxicity of hydrophilic fumed silica micro- and nanoparticles of various sizes (7 nm, 12 nm, and 50 µm) was evaluated using the luminescent bacteria Vibrio fischeri. In addition, the toxicity of an anionic surfactant solution (ether carboxylic acid), a nonionic surfactant solution (alkyl polyglucoside), and a binary (1:1) mixture of these solutions all containing these silica particles was evaluated. Furthermore, this work discusses the adsorption of surfactants onto particle surfaces and evaluates the effects of silica particles on the surface tension and critical micellar concentration (CMC) of these anionic and nonionic surfactants. It was determined that silica particles can be considered as non-toxic and that silica particles reduce the toxicity of surfactant solutions. Nevertheless, the toxicity reduction depends on the ionic character of the surfactants. Differences can be explained by the different adsorption behavior of surfactants onto the particle surface, which is weaker for nonionic surfactants than for anionic surfactants. Regarding the effects on surface tension, it was found that silica particles increased the surface activity of anionic surfactants and considerably reduced their CMC, whereas in the case of nonionic surfactants, the effects were reversed.

Anaerobic digestion of amine-oxide-based surfactants: biodegradation kinetics and inhibitory effects.

Recently, anaerobic degradation has become a prevalent alternative for the treatment of wastewater and activated sludge. Consequently, the anaerobic biodegradability of recalcitrant compounds such as some surfactants require a thorough study to avoid their presence in the environment. In this work, the anaerobic biodegradation of amine-oxide-based surfactants, which are toxic to several organisms, was studied by measuring of the biogas production in digested sludge. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R12), Myristamine oxide (AO-R14) and Cocamidopropylamine oxide (AO-cocoamido). Results show that AO-R12 and AO-R14 inhibit biogas production, inhibition percentages were around 90%. AO-cocoamido did not cause inhibition and it was biodegraded until reaching a percentage of 60.8%. Otherwise, we fitted the production of biogas to two kinetic models, to a pseudo first-order model and to a logistic model. Production of biogas during the anaerobic biodegradation of AO-cocoamido was pretty good adjusted to the logistics model. Kinetic parameters were also determined. This modelling is useful to predict their behaviour in wastewater treatment plants and under anaerobic conditions in the environment.

Ecotoxicological characterization of polyoxyethylene glycerol ester non-ionic surfactants and their mixtures with anionic and non-ionic surfactants.

This paper reports on a study that investigated the aquatic toxicity of new non-ionic surfactants derived from renewable raw materials, polyoxyethylene glycerol ester (PGE), and their binary mixtures with anionic and non-ionic surfactants. Toxicity of pure PGEs was determined using representative organisms from different trophic levels: luminescent bacteria (Vibrio fischeri), microalgae (Pseudokirchneriella subcapitata), and freshwater crustaceans (Daphnia magna). Relationships between toxicity and the structural parameters such as unit of ethylene oxide (EO) and hydrophilic-lipophilic balance (HLB) were evaluated. Critical micellar concentration (CMC) in the conditions of the toxicity test was also determined. It was found that the toxicity of the aqueous solutions of PGE decreased when the number of EO units in the molecule, HLB, and CMC increased. PGEs showed lower CMC in marine medium, and the toxicity to V. ficheri is lower when the CMC was higher. Given their non-polar nature, narcosis was expected to be the primary mode of toxic action of PGEs. For the mixture of surfactants, we observed that the mixtures with PGE that had the higher numbers of EO units were more toxic than the aqueous solutions of pure surfactants. Moreover, we found that concentration addition was the type of action more likely to occur for mixtures of PGE with lower numbers of EO units with non-ionic surfactants (alkylpolyglucoside and fatty alcohol ethoxylate), whereas for the mixture of PGE with lower EO units and anionic surfactant (ether carboxylic derivative), the most common response type was response addition. In case of mixtures involving amphoteric surfactants and PGEs with the higher numbers of EO units, no clear pattern with regard to the mixture toxicity response type could be observed.

Aerobic biodegradation of amphoteric amine-oxide-based surfactants: Effect of molecular structure, initial surfactant concentration and pH.

The present study was designed to provide information regarding the effect of the molecular structure of amphoteric amine-oxide-based surfactants and the initial surfactant concentration on their ultimate biodegradation. Moreover, given this parameter's pH-dependence, the effect of pH was also investigated. Three amine-oxide-based surfactants with structural differences in their hydrophobic alkyl chain were tested: Lauramine oxide (AO-R12), Myristamine oxide (AO-R14) and Cocamidopropylamine oxide (AO-Cocoamido). We studied the ultimate biodegradation using the Modified OECD Screening Test at initial surfactant concentrations ranged from 5 to 75 mg L-1 and at pH levels from 5 to 7.4. The results demonstrate that at pH 7.4, amine-oxide-based surfactants are readily biodegradable. In this study, we concluded that ω-oxidation can be assumed to be the main biodegradation pathway of amine-oxides and that differences in the biodegradability between them can be explained by the presence of an amide group in the alkyl chain of AO-Cocoamido; the CN fission of the amide group slows down their mineralization process. In addition, the increase in the concentration of the surfactant from 5 to 75 mg L-1 resulted in an increase in the final biodegradation of AO-R12 and AO-R14. However, in the case of AO-Cocoamido, a clear relationship between the concentration and biodegradation cannot be stated. Conversely, the biodegradability of AO-R12 and AO-R14 was considerably lower in an acid condition than at a pH of 7.4, whereas AO-Cocoamido reached similar percentages in acid conditions and at a neutral pH. However, microorganisms required more time to acclimate.

Kinetic study of the anaerobic biodegradation of alkyl polyglucosides and the influence of their structural parameters.

This paper reports a study of the anaerobic biodegradation of non-ionic surfactants alkyl polyglucosides applying the method by measurement of the biogas production in digested sludge. Three alkyl polyglucosides with different length alkyl chain and degree of polymerization of the glucose units were tested. The influence of their structural parameters was evaluated, and the characteristics parameters of the anaerobic biodegradation were determined. Results show that alkyl polyglucosides, at the standard initial concentration of 100 mgC L(-1), are not completely biodegradable in anaerobic conditions because they inhibit the biogas production. The alkyl polyglucoside having the shortest alkyl chain showed the fastest biodegradability and reached the higher percentage of final mineralization. The anaerobic process was well adjusted to a pseudo first-order equation using the carbon produced as gas during the test; also, kinetics parameters and a global rate constant for all the involved metabolic process were determined. This modeling is helpful to evaluate the biodegradation or the persistence of alkyl polyglucosides under anaerobic conditions in the environment and in the wastewater treatment.

Aerobic biodegradation of a nonylphenol polyethoxylate and toxicity of the biodegradation metabolites.

In this paper a study was made of the biodegradation of a non-ionic surfactant, a nonylphenol polyethoxylate, in biodegradability tests by monitoring the residual surfactant matter. The influence of the concentration on the extent of primary biodegradation, the toxicity of biodegradation metabolites, and the kinetics of degradation were also determined. The primary biodegradation was studied at different initial concentrations: 5, 25 and 50 mg/L, (at sub-and supra-critical micelle concentration). The NPEO used in this study can be considered biodegradable since the primary biodegradation had already taken place (a biodegradation greater than 80% was found for the different initial concentration tested). The initial concentration affected the shape of the resulting curve, the mean biodegradation rate and the percentage of biodegradation reached (99% in less than 8 days at 5 mg/L, 98% in less than 13 days at 25 mg/L and 95% in 14 days at 50 mg/L). The kinetic model of Quiroga and Sales (1991) was applied to predict the biodegradation of the NPEO. The toxicity value was measured as EC(20) and EC(50). In addition, during the biodegradation process of the surfactant a toxicity analysis was made of the evolution of metabolites generated, confirming that the subproducts of the biodegradation process were more toxic than the original.