An alternative approach to the kinetic modeling of pharmaceuticals degradation in high saline water by electrogenerated active chlorine species.

A semiempirical approach considering the rate of reactive chlorine species-RCS- production (ΦE) as a function of current and Cl- concentration for the modeling of acetaminophen (ACE) degradation is presented. A filter-press reactor having a Ti/RuO2-ZrO2 (Sb2O3 doped) anode, NaCl (0.04-0.1 mol L-1) as supporting electrolyte, and operated in continuous mode, was considered. A current of 100 mA and a flow of 11 mL min-1 favored the electrogeneration of RCS and ACE degradation. Hydraulic retention time and ΦE were the most relevant parameters for the RCS production. These two parameters, plus the pollutant concentration, were very determinant for the ACE degradation. The model successfully reproduced the ACE removal in distilled water at different concentrations (10, 20, 40, and 60 mg L-1). The electrochemical system achieved removals between 80 and 100% of ACE in distilled water. The ACE treatment in actual seawater (a chloride-rich matrix, 0.539 mol L-1 of Cl-) was assessed, and the degradation was simulated using the developed model. The competing role toward electrogenerated RCS by intrinsic organic matter (3.2 mg L-1) in the seawater was a critical point, and the simulated values fitted well with the experimental data. Finally, the action of the electrochemical system on ciprofloxacin (CIP) in real seawater and its antimicrobial activity was tested. CIP removal (100% at 120 s) was faster than that observed for ACE (100% of degradation after 180 s) due to CIP has amine groups that are more reactive toward RCS than phenol moiety on ACE. Moreover, the system removed 100% of the antimicrobial activity associated with CIP, indicating a positive environmental effect of the treatment.

The Metal Catalyst Influences the Kinetics and Mechanisms of MS2 Inactivation in Fenton-like Systems.

Human enteric viruses are frequent microbial contaminants of surface water and groundwater. Waterborne viruses can be effectively inactivated by oxidants, such as those generated in Fenton-like systems. However, the mechanisms by which this inactivation occurs are not understood. Here we investigated how two Fenton-like systems, Cu/H2O2 and Fe/H2O2/light, affect the infectivity and structural integrity of MS2 coliphage, a frequently used surrogate for human enteric viruses. The extent of MS2 genome and capsid protein degradation was evaluated by quantitative PCR and protein mass spectrometry, and was related to the observed level of inactivation. Even though inactivation in both systems occurred via the same oxidant, hydroxyl radical, the contributions of genome and capsid protein degradation to inactivation differed. Inactivation in the Cu/H2O2 system was rapid and involved both genome and protein damage. In contrast, inactivation in Fe/H2O2/light proceeded at a slower rate and encompassed solely genome damage. Our findings demonstrate that not only the oxidant, but also its source, the metal catalyst, determines the inactivation kinetics and mechanism in Fenton-like systems. This work provides the first evidence of the impact of the metal catalyst on virus inactivation in Fenton-like systems.

Virus removal and inactivation by iron (hydr)oxide-mediated Fenton-like processes under sunlight and in the dark.

Advanced oxidation processes (AOPs) have emerged as a promising alternative to conventional disinfection methods to control microbial water quality, yet little is known about the fate of viruses in AOPs. In this study, we investigated the fate of MS2 coliphage in AOPs that rely on heterogeneous Fenton-like processes catalyzed by iron (hydr)oxide particles. Both physical removal of viruses from solution via adsorption onto particles as well as true inactivation were considered. Virus fate was studied in batch reactors at circumneutral pH, containing 200 mg L(-1) of four different commercial iron (hydr)oxide particles of similar mesh sizes: hematite (α-Fe2O3), goethite (α-FeOOH), magnetite (Fe3O4) and amorphous iron(iii) hydroxide (Fe(OH)3). The effect of adsorption and sunlight exposure on the survival of MS2 was considered. On a mass basis, all particles exhibited a similar virus adsorption capacity, whereas the rate of adsorption followed the order FeOOH > Fe2O3 > Fe3O4 ≈ Fe(OH)3. This adsorption behavior could not be explained by electrostatic considerations; instead, adsorption must be governed by other factors, such as hydrophobic interactions or van der Waals forces. Adsorption to three of the particles investigated (α-FeOOH, Fe3O4, Fe(OH)3) caused virus inactivation of 7%, 22%, and 14%, respectively. Exposure of particle-adsorbed viruses to sunlight and H2O2 resulted in efficient additional inactivation, whereas inactivation was negligible for suspended viruses. The observed first-order inactivation rate constants were 6.6 × 10(-2), 8.7 × 10(-2), 0.55 and 1.5 min(-1) for α-FeOOH, α-Fe2O3, Fe3O4 and Fe(OH)3 respectively. In the absence of sunlight or H2O2, no inactivation was observed beyond that caused by adsorption alone, except for Fe3O4, which caused virus inactivation via a dark Fenton-like process. Overall our results demonstrate that heterogeneous Fenton-like processes can both physically remove viruses from water as well as inactivate them via adsorption and via a particle-mediated (photo-)Fenton-like process.

Searching for pharmaceutically active products and metabolites in environmental waters of Peru by HRMS-based screening: Proposal for future monitoring and environmental risk assessment.

The presence of pharmaceutical active products (PhACs) in the aquatic environment is a matter of current concern, and there is an increasing trend to include these compounds in water quality monitoring programs and environmental risk assessments. Several studies have reported the presence of PhACs in environmental waters worldwide, but only a few studies have focused on Latin American countries. Thus, available information on the occurrence of parent pharmaceuticals, especially their metabolites, is very scarce. Peru is one of the less monitored countries in terms of contaminants of emerging concern (CECs) in waters, and only one study has been found, which was focused on the quantification of selected PhACs in urban wastewater and surface water. The aim of this work is to complement the previous data reported on PhACs in the aquatic environment by application of a wide-scope high-resolution (HRMS)-based screening, making use of target and suspect approaches. In the present work, 30 pharmaceuticals, drugs or other compounds (sweeteners, UV filters, etc.) and 21 metabolites have been identified, with antibiotics (and metabolites) being the most prevalent compounds. The use of liquid chromatography (LC) coupled to ion mobility-HRMS allowed the tentative identification of parent compounds and metabolites, for which the analytical reference standard was not available, with a high level of confidence in their identification. Based on the results obtained, a strategy for the monitoring of PhACs and relevant metabolites in environmental waters from Peru and for subsequent risk assessment is proposed. Our data will also help to focus future studies to evaluate the removal efficiency of wastewater treatment plants and the impact of treated water in receiving water bodies.

High-frequency ultrasound processes as alternative methods for degrading meropenem antibiotic in water.

ß-lactam, more specifically carbapenems, are antibiotics used as last resort pharmaceuticals to deal with infections. Despite the medical relevance, they are considered contaminants of emerging concern in water because of their recalcitrance to conventional systems in the municipal wastewater treatment plants. This work aimed to show alternative methods based on the use of high-frequency ultrasound (200-1000 kHz) at a laboratory scale to degrade meropenem (a representative carbapenem antibiotic) in water. The ability of the sonochemical method alone to eliminate meropenem was tested initially. Then, the improvements of degradation by the addition of ferrous iron, or Fe (II) plus UVA light (sono-Fenton, or sono-photo-Fenton methods) were assessed. Finally, the effect of the best ultrasound-based method on the removal of biological activity of meropenem was determined. • Three high-frequency ultrasound processes were applied to degrade meropenem in water. • Sono-photo-Fenton degraded 67% of imipenem at 60 min of treatment and decreased significantly H2O2 accumulation. • Antimicrobial activity was removed after only 30 min of sono-photo-Fenton action.

Pharmaceuticals and environmental risk assessment in municipal wastewater treatment plants and rivers from Peru.

This is the first study dealing with removal of the pharmaceutical substances in municipal wastewater treatment plants (MWWTPs) from Peru and the impact of these compounds in surface waters receiving treated wastewater. To this aim, samples from MWWTP of Lima (Peruvian Coast), MWWTP of Cusco, Puno and Juliaca (Peruvian Highlands), as well surface water (confluence of Torococha and Coata rivers in Juliaca) were analyzed. A total of 38 target pharmaceuticals were included in this study and were determined by Liquid Chromatography coupled to tandem Mass Spectrometry (LC-MS/MS). Around 60% and 75% of the target pharmaceuticals could be quantified in surface water and MWWTPs, respectively. Acetaminophen was the drug found at the highest concentration, and it was present in all the treated wastewater samples reaching average values above 100 µg/L in the department of Puno. The gabapentin anti-epileptic drug (up to 11.85 µg/L in MWWTP Lima) and the antibiotics clarithromycin, trimethoprim, ciprofloxacin, sulfamethoxazole and azithromycin (1.86 to 4.47 µg/L in MWWTP Lima) were also found at moderate concentrations in the treated wastewater. In surface water, the highest concentration corresponded also to acetaminophen (28.70 µg/L) followed by sulfamethoxazole (4.36 µg/L). As regards the pharmaceuticals removal, data of this work showed that the MWWTP Cusco (aerobic biologic process by synthetic trickling filters as secondary treatment) was more efficient than the MWWTP Lima (a preliminary treatment that combines grilles, sand trap, degreaser-aerated and sieved of 1.0 mm). However, many pharmaceuticals (around 50% of the compounds investigated) presented concentrations in treated wastewater similar or even higher than in influent wastewater. The environmental ecological risk of pharmaceuticals was assessed based on calculated Risk Quotient (RQ) in the treated wastewater and surface water from the concentration data found in the samples. According to our data, three antibiotics (clarithromycin, ciprofloxacin, clindamycin) and the analgesic acetaminophen posed high environmental risk (RQ ≥ 1) on the aquatic environment. In the river, all antibiotics (except norfloxacin) as well as the analgesic-anti-inflammatory compounds acetaminophen, diclofenac posed a high environmental risk (RQ ≥ 1). Based on data reported in this work for the first time in water samples from Peru, it can be deduced that the treatment processes applied in important cities from Peru are not enough efficient to remove pharmaceuticals in wastewater. As a consequence, severe environmental risks associated to the presence of pharmaceuticals in treated wastewater and surface water are expected; so complementary treatment processes should be implemented in the MWWTPs for a more efficient elimination of these compounds.

Inactivation of MS2 coliphage in Fenton and Fenton-like systems: role of transition metals, hydrogen peroxide and sunlight.

The inactivation of coliphage MS2 by iron- and copper-catalyzed Fenton systems was studied to assess the importance of this process for virus inactivation in natural systems and during water treatment by advanced oxidation processes. The influence of H(2)O(2) (3-50 microM) and metal (1-10 microM) concentrations, HO(*) production, and sunlight on inactivation was investigated. Inactivation was first order with respect to H(2)O(2), but the dependence on the metal concentration was more complex. In the Cu/H(2)O(2) system, the inactivation rate constant k(obs) increased with added Cu up to 2.5 microM, and then leveled off. This was consistent with Cu saturation of the solution, indicating that only soluble Cu contributed to inactivation. In contrast, inactivation in the Fe/H(2)O(2) system was governed by colloidal iron. Irradiation by sunlight only affected the Fe/H(2)O(2) system, leading to a 5.5-fold increase in k(obs) (up to 3.1 min(-1)). HO(*) production, measured by electron spin resonance, could not account for the observed inactivation in the Fe/H(2)O(2) system. Other oxidants, such as ferryl species, must therefore play a role. Experiments using bulk oxidant scavengers revealed that inactivation occurred by a caged mechanism involving oxidant production by metals located in close proximity to the virus. Overall, our results show that the Fenton/photo-Fenton process may serve as an efficient technology for virus disinfection.