M. Sánchez-Polo

Pharmaceuticals as emerging contaminants and their removal from water. A review

The main objective of this study was to conduct an exhaustive review of the literature on the presence of pharmaceutical-derived compounds in water and on their removal. The most representative pharmaceutical families found in water were described and related water pollution issues were analyzed. The performances of different water treatment systems in the removal of pharmaceuticals were also summarized. The water treatment technologies were those based on conventional systems (chlorine, chlorine dioxide, wastewater treatment plants), adsorption/bioadsorption on activated carbon (from lotus stalks, olive-waste cake, coal, wood, plastic waste, cork powder waste, peach stones, coconut shell, rice husk), and advanced oxidation processes by means of ozonation (O₃, O₃/H₂O₂, O₃/activated carbon, O₃/biological treatment), photooxidation (UV, UV/H₂O₂, UV/K₂S₂O₈, UV/TiO₂, UV/H₂O₂/TiO₂, UV/TiO₂/activated carbon, photo-Fenton), radiolysis (e-Beam, ⁶⁰Co, ¹³⁷Cs. Additives used: H₂O₂, SO₃²⁻, HCO₃⁻, CH₃₋OH, CO₃²⁻, or NO₃⁻), and electrochemical processes (Electrooxidation without and with active chlorine generation). The effect of these treatments on pharmaceutical compounds and the advantages and disadvantages of different methodologies used were described. The most important parameters of the above water treatment systems (experimental conditions, removal yield, pharmaceutical compound mineralization, TOC removal, toxicity evolution) were indicated. The key publications on pharmaceutical removal from water were summarized.

Activated carbon modifications to enhance its water treatment applications. An overview.

The main objective of this study was to list and compare the advantages and disadvantages of different methodologies to modify the surface of activated carbons (ACs) for their application as adsorbents to remove organic and inorganic pollutants from aqueous phase. These methodologies have been categorized into four broad groups: oxidation, sulfuration, ammonification, and coordinated ligand anchorage. Numerous investigations into the removal of metals from water have modified carbon surfaces to increase their content of acidic surface functional groups by using H(2)O(2), O(3) and HNO(3). Because these treatments can reduce the AC surface area, researchers are seeking alternative methods to modify and/or create surface functional groups without the undesirable effect of pore blockage. The nitrogenation or sulfuration of the AC surface can increase its basicity favoring the adsorption of organic compounds. The introduction of nitrogen or sulfur complexes on the carbon surface increases the surface polarity and, therefore, the specific interaction with polar pollutants. Different coordinated ligands have also been used to modify ACs, showing that coordinated ligand anchorage on the AC surface modifies its textural and chemical properties, but research to date has largely focused on the use of these modified materials to remove heavy metals from water by complexes formation.

Ozonation of 1,3,6-naphthalenetrisulphonic acid catalysed by activated carbon in aqueous phase

This paper presents experimental results of the ozonation of a model aromatic sulphonic compound, 1,3,6-naphthalenetrisulphonic acid (NTS), in the presence of different activated carbons with different physical and chemical surface properties. Carbons used were commercial activated carbons (Ceca AC40, Norit, Merck, Witco, Ceca GAC, Filtrasorb 400, Sorbo) with or without demineralisation pre-treatment. Carbon samples were texturally and chemically characterised using N 2 adsorption isotherms, mercury porosimetry, pHPZC, selective neutralisation and elemental analysis. Results show that NTS was degraded by ozone at a faster rate in the presence of activated carbon, especially in the case of Sorbo, Ceca GAC and Norit carbons, which display catalytic activity, probably by enhancing ozone decomposition in aqueous phase in highly oxidative species. These catalytic properties seem to be favoured by both the basicity of the carbon surface and the higher macropore volume. Dissolved total organic carbon from the NTS degradation compounds was removed in the presence of activated carbon through both the catalytic activity of activated carbon to mineralise organic matter and the adsorption of these organic compounds on activated carbon.

Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon.

The objective of the present study was to analyse the behaviour of activated carbon with different chemical and textural properties in nitroimidazole adsorption, also assessing the combined use of microorganisms and activated carbon in the removal of these compounds from waters and the influence of the chemical nature of the solution (pH and ionic strength) on the adsorption process. Results indicate that the adsorption of nitroimidazoles is largely determined by activated carbon chemical properties. Application of the Langmuir equation to the adsorption isotherms showed an elevated adsorption capacity (X(m)=1.04-2.04 mmol/g) for all contaminants studied. Solution pH and electrolyte concentration did not have a major effect on the adsorption of these compounds on activated carbon, confirming that the principal interactions involved in the adsorption of these compounds are non-electrostatic. Nitroimidazoles are not degraded by microorganisms used in the biological stage of a wastewater treatment plant. However, the presence of microorganisms during nitroimidazole adsorption increased their adsorption on the activated carbon, although it weakened interactions between the adsorbate and carbon surface. In dynamic regime, the adsorptive capacity of activated carbon was markedly higher in surface water and groundwater than in urban wastewaters.

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.

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cπ-cation interactions

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

Gamma irradiation of pharmaceutical compounds, nitroimidazoles, as a new alternative for water treatment.

The main objectives of this study were: (1) to investigate the decomposition and mineralization of nitroimidazoles (Metronidazole [MNZ], Dimetridazole [DMZ], and Tinidazole [TNZ]) in waste and drinking water using gamma irradiation; (2) to study the decomposition kinetics of these nitroimidazoles; and (3) to evaluate the efficacy of nitroimidazole removal using radical promoters and scavengers. The results obtained showed that nitroimidazole concentrations decreased with increasing absorbed dose. No differences in irradiation kinetic constant were detected for any nitroimidazole studied (0.0014-0.0017 Gy(-1)). The decomposition yield was higher under acidic conditions than in neutral and alkaline media. Results obtained showed that, at appropriate concentrations, H(2)O(2) accelerates MNZ degradation by generating additional HO(); however, when the dosage of H(2)O(2) exceeds the optimal concentration, the efficacy of MNZ degradation is reduced. The presence of t-BuOH (HO() radical scavenger) and thiourea (HO(), H() and e(aq)(-) scavenger) reduced the MNZ irradiation rate, indicating that degradation of this pollutant can take place via two pathways: oxidation by HO() radicals and reduction by e(aq)(-) and H(). MNZ removal rate was slightly lower in subterranean and surface waters than in ultrapure water and was markedly lower in wastewater. Regardless of the water chemical composition, MNZ gamma irradiation can achieve i) a decrease in the concentration of dissolved organic carbon, and ii) a reduction in the toxicity of the system with higher gamma absorbed dose.

Effect of the ozone–carbon reaction on the catalytic activity of activated carbon during the degradation of 1,3,6-naphthalenetrisulphonic acid with ozone

The present work investigated the evolution of catalytic activity of activated carbon in 1,3,6-naphthalenetrisulphonic acid (NTS) ozonation in aqueous phase. Activated carbons pre-treated with ozone showed a reduction in NTS oxidation rate and efficacy of TOC removal that increased with ozone exposure time. The ozone treatment increased the number of surface oxygenated (electron-withdrawing) groups on the carbon, therefore reducing its basic character and its reductive properties. This effect reduced the reactivity of the activated carbon to ozone and, therefore, the extent of the ozone decomposition into highly oxidative species.

Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system.

The main objective of this study was to analyze the effectiveness of technologies based on the use of ozone and activated carbon for the removal of nitroimidazoles from water, considering them as model of pharmaceutical compounds. A study was undertaken of the influence of the different operational variables on the effectiveness of each system studied (O(3), O(3)/activated carbon), and on the kinetics involved in each process. Ozone reaction kinetics showed that nitroimidazoles have a low reactivity, with K(O)(3) values <350 M(-1)s(-1) regardless of the nitroimidazole and solution pH considered. However, nitroimidazoles have a high affinity for HO radicals, with radical rate constant (k(HO)) values of around 10(10)M(-1)s(-1). Among the nitroimidazole ozonation by-products, nitrate ions and 3-acetyl-2-oxazolidinone were detected. The presence of activated carbon during nitroimidazole ozonation produces (i) an increase in the removal rate, (ii) a reduction in the toxicity of oxidation by-products, and (iii) a reduction in the concentration of dissolved organic matter. These results are explained by the generation of HO radicals at the O(3)-activated carbon interface.

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.