J.D. Méndez-Díaz

Environmental impact of phthalic acid esters and their removal from water and sediments by different technologies – A review

This article describes the most recent methods developed to remove phthalic acid esters (PAEs) from water, wastewater, sludge, and soil. In general, PAEs are considered to be endocrine disrupting chemicals (EDCs), whose effects may not appear until long after exposure. There are numerous methods for removing PAEs from the environment, including physical, chemical and biological treatments, advanced oxidation processes and combinations of these techniques. This review largely focuses on the treatment of PAEs in aqueous solutions but also reports on their treatment in soil and sludge, as well as their effects on human health and the environment.

Kinetic study of the adsorption of nitroimidazole antibiotics on activated carbons in aqueous phase.

The adsorption kinetics of four nitroimidazoles, Dimetridazole (DMZ), Metronidazole (MNZ), Ronidazole (RNZ) and Tinidazole (TNZ), were studied on three activated carbons: two commercial carbons from Sorbo-Norit (S) and Merck (M) and a third prepared by chemical activation of petroleum coke (C). Experimental data of the corresponding adsorption kinetics were analyzed by applying pseudo-first and pseudo-second-order models and a general diffusion model. Application of pseudo-first and pseudo-second-order kinetic models verified the following: (i) The kinetic model used that better predicts the adsorption rates depends of both the adsorbent and adsorbate studied. (ii) Nitroimidazole adsorption rate decreases in the order MNZ>DMZ>RNZ>TNZ; therefore, in the case of MNZ, molecular size does not appear to be a determining factor in the process. (iii) Nitroimidazole adsorption rate on carbons increases in the order C<S<M, which is related to the increase in carbon hydrophobicity. Hence, in general, hydrophobic interactions appear to govern the kinetics of the adsorption process. Finally, a general diffusion model was applied that combines external mass transport and intraparticle diffusion, achieving an adequate fit to the experimental data. There are notable differences among the diffusivity values for the different nitroimidazoles that do not appear to be exclusively related to carbon textural parameters or adsorbate size. Therefore, adsorbent and adsorbate chemical characteristics are highly important to establish the adsorption mechanism of nitroimidazoles on activated carbons.

Removal of diethyl phthalate from water solution by adsorption, photo-oxidation, ozonation and advanced oxidation process (UV/H2O2, O3/H2O2 and O3/activated carbon)

The objective of this work was to compare the effectiveness of conventional technologies (adsorption on activated carbon, AC, and ozonation) and technologies based on advanced oxidation processes, AOPs, (UV/H(2)O(2), O(3)/AC, O(3)/H(2)O(2)) to remove phthalates from aqueous solution (ultrapure water, surface water and wastewater). Diethyl phthalate (DEP) was chosen as a model pollutant because of its high water solubility (1,080 mg/L at 293 K) and toxicity. The activated carbons showed a high adsorption capacity to adsorb DEP in aqueous solution (up to 858 mg/g), besides the adsorption mechanism of DEP on activated carbon is governed by dispersive interactions between π electrons of its aromatic ring with π electrons of the carbon graphene planes. The photodegration process showed that the pH solution does not significantly affect the degradation kinetics of DEP and the first-order kinetic model satisfactorily fitted the experimental data. It was observed that the rate of decomposition of DEP with the O(3)/H(2)O(2) and O(3)/AC systems is faster than that with only O(3). The technologies based on AOPs (UV/H(2)O(2), O(3)/H(2)O(2), O(3)/AC) significantly improve the degradation of DEP compared to conventional technologies (O(3), UV). AC adsorption, UV/H(2)O(2), O(3)/H(2)O(2), and O(3)/AC showed a high yield to remove DEP; however, the disadvantage of AC adsorption is its much longer time to reach maximum removal. The best system to treat water (ultrapure and natural) polluted with DEP is the O(3)/AC one since it achieved the highest DEP degradation and TOC removal, as well as the lower water toxicity.

Modeling adsorption rate of organic micropollutants present in landfill leachates onto granular activated carbon

The overall adsorption rate of single micropollutants present in landfill leachates such as phthalic acid (PA), bisphenol A (BPA), diphenolic acid (DPA), 2,4-dichlorophenoxy-acetic acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid (MCPA) on two commercial activated carbons was studied. The experimental data obtained were interpreted by using a diffusional model (PVSDM) that considers external mass transport, intraparticle diffusion, and adsorption on an active site. Furthermore, the concentration decay data were interpreted by using kinetics models. Results revealed that PVSDM model satisfactorily fitted the experimental data of adsorption rate on activated carbon. The tortuosity factor of the activated carbons used ranged from 2 to 4. The contribution of pore volume diffusion represented more than 92% of intraparticle diffusion confirming that pore volume diffusion is the controlling mechanism of the overall rate of adsorption and surface diffusion can be neglected. The experimental data were satisfactorily fitted the kinetic models. The second-order kinetic model was better fitted the experimental adsorption data than the first-order model.

Adsorption/bioadsorption of phthalic acid, an organic micropollutant present in landfill leachates, on activated carbons.

This study investigated the adsorption of phthalic acid (PA) in aqueous phase on two activated carbons with different chemical natures, analyzing the influence of: solution pH, ionic strength, water matrix (ultrapure water, ground water, surface water, and wastewater), the presence of microorganisms in the medium, and the type of regime (static and dynamic). The activated carbons used had a high adsorption capacity (242.9 mg/g and 274.5 mg/g), which is enhanced with their phenolic groups content. The solution pH had a major effect on PA adsorption on activated carbon; this process is favored at acidic pHs. PA adsorption was not affected by the presence of electrolytes (ionic strength) in solution, but was enhanced by the presence of microorganisms (bacteria) due to their adsorption on the carbon, which led up to an increase in the activated carbon surface hydrophobicity. PA removal varies as a function of the water type, increasing in the order: ground water<surface water≈ultrapure water<wastewater. The effectiveness of PA adsorption was lower in dynamic than in static regime due to the shorter adsorbent-adsorbate contact time in dynamic regime.

Removal of the surfactant sodium dodecylbenzenesulfonate from water by processes based on adsorption/bioadsorption and biodegradation.

This study analyzed the bioadsorption/biodegradation kinetics of the surfactant sodium dodecylbenzenesulfonate (SDBS) on commercial activated carbons and on activated carbons prepared in the laboratory by activation of almond shells. The effect of surface oxygen species on these processes was also investigated by using an activated carbon from almond shells oxidized with H2O2 or HNO3. SDBS removal kinetics followed a first-order kinetic model, with rate constants between 1.25×10(-2) h(-1) and 2.14×10(-2) h(-1). The removal rate constants of total organic carbon (TOC) were also determined, obtaining values ranging between 0.51×10(-2) h(-1) and 1.76×10(-2) h(-1). TOC removal rate constants were lower than SDBS removal rate constants, demonstrating that SDBS is also biodegraded during bioadsorption. Both the inorganic carbon concentration and the colony forming units confirm this biodegradation. The amount of SDBS removed from water varies between 109.0 and 232.3 mg SDBS/g of carbon. When SDBS adsorption on activated carbon is conducted in the presence of bacteria, which is the real situation in water treatment plants, a fraction of bacteria are adsorbed on the surface of activated carbon. A part of the SDBS is removed by adsorption (bioadsorption) and other part by biodegradation.

Behavior of two different constituents of natural organic matter in the removal of sodium dodecylbenzenesulfonate by O3 and O3-based advanced oxidation processes

The objective of this study was to analyze the role played by two components of natural organic matter (NOM), gallic acid (GAL) and humic acid (HUM), in the removal of the surfactant sodium dodecylbenzenesulfonate (SDBS) from waters by O(3)-based oxidation processes, i.e., O(3)/H(2)O(2), O(3)/granular activated carbon (GAC), and O(3)/powdered activated carbon (PAC). It was found that the presence of low concentrations of these compounds (1 mg/L) during SDBS ozonation increases both the ozone decomposition rate and the rate of SDBS removal from the medium. Because of the low reactivity of SDBS with ozone, these effects are mainly due to an increase in the transformation rate of ozone into HO(*) radicals. Results obtained demonstrate that the presence of GAL and HUM during SDBS ozonation increases the concentration of O(2)(-*) radicals in the medium, confirming that GAL and HUM act as initiating agents of ozone transformation into HO(*). It was also found that this effect was smaller with a larger molecular size of the acid. Presence of GAL and HUM during SDBS removal by O(3)/H(2)O(2), O(3)/GAC, and O(3)/PAC systems also increases the SDBS degradation rate, confirming the role of these compounds as initiators of ozone transformation into HO(*) radicals.

Removal of surfactant dodecylbenzenesulfonate by consecutive use of ozonation and biodegradation

Successful surfactant removal from wastewater is often limited by the high concentration of the surfactant. The use of advanced oxidation processes can be the key to aid biological treatment of water containing high amounts of surfactants. The present study analyzes the biodegradation of the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) and the effects of its combination with ozonation. SDBS pre‐ozonation favors the metabolism by microorganisms. Experimental results indicate that the application of a concentration of up to 60 μM of ozone for 60 min, prior to contact with microorganisms, increases the percentage of SDBS removed by biodegradation alone. These results demonstrate that the removal of SDBS and of the total organic carbon is increased by the consecutive use of ozonation and biodegradation.

Effectiveness of different oxidizing agents for removing sodium dodecylbenzenesulphonate in aqueous systems

The present study investigates the efficacy of various oxidizing treatments (ClO(-), ClO(2), KMnO(4), O(3), O(3)/H(2)O(2), O(3)/activated carbon) to remove from waters sodium dodecylbenzenesulphonate (SDBS), considered as model surfactant. Results obtained show that the use of ClO(-) and ClO(2) does not cause appreciable SDBS degradation. Additionally, in the case of ClO(-), trihalomethanes are generated, increasing system toxicity. Because the reaction kinetics between SDBS and KMnO(4) is very slow, a decrease in contaminant concentration is not observed, even at very acid pH values. SDBS reactivity with ozone is very low, with a kinetic constant (k(O)(3)) of 3.68 M(-1)s(-1), but its reactivity with HO() radicals is very high (k(OH)=1.16 x 10(10)M(-1)s(-1)), therefore O(3)/H(2)O(2) and O(3)/activated carbon, which can also generate HO(), appear as promising advanced oxidation processes to remove this contaminant from waters. The method based on ozone and activated carbon was the only process studied that produced both an increase in SDBS removal rate (due to the generation of HO() radicals in the O(3)-PAC or O(3)-GAC interaction) and a considerable reduction in the concentration of dissolved organic carbon in the system due to the PAC adsorbent properties.