Electronic Tongue Coupled to an Electrochemical Flow Reactor for Emerging Organic Contaminants Real Time Monitoring.

Triclosan, which is a bacteriostatic used in household items, has raised health concerns, because it might lead to antimicrobial resistance and endocrine disorders in organisms. The detection, identification, and monitoring of triclosan and its by-products (methyl triclosan, 2,4-Dichlorophenol and 2,4,6-Trichlorophenol) are a growing need in order to update current water treatments and enable the continuous supervision of the contamination plume. This work presents a customized electronic tongue prototype coupled to an electrochemical flow reactor, which aims to access the monitoring of triclosan and its derivative by-products in a real secondary effluent. An electronic tongue device, based on impedance measurements and polyethylenimine/poly(sodium 4-styrenesulfonate) layer-by-layer and TiO2, ZnO and TiO2/ZnO sputtering thin films, was developed and tested to track analyte degradation and allow for analyte detection and semi-quantification. A degradation pathway trend was observable by means of principal component analysis, being the sample separation, according to sampling time, explained by 77% the total variance in the first two components. A semi-quantitative electronic tongue was attained for triclosan and methyl-triclosan. For 2,4-Dichlorophenol and 2,4,6-Trichlorophenol, the best results were achieved with only a single sensor. Finally, working as multi-analyte quantification devices, the electronic tongues could provide information regarding the degradation kinetic and concentrations ranges in a dynamic removal treatment.

Emerging organic contaminants in wastewater: Understanding electrochemical reactors for triclosan and its by-products degradation.

Degradation technologies applied to emerging organic contaminants from human activities are one of the major water challenges in the contamination legacy. Triclosan is an emerging contaminant, commonly used as antibacterial agent in personal care products. Triclosan is stable, lipophilic and it is proved to have ecotoxicologic effects in organics. This induces great concern since its elimination in wastewater treatment plants is not efficient and its by-products (e.g. methyl-triclosan, 2,4-dichlorophenol or 2,4,6-trichlorophenol) are even more hazardous to several environmental compartments. This work provides understanding of two different electrochemical reactors for the degradation of triclosan and its derivative by-products in effluent. A batch reactor and a flow reactor (mimicking a secondary settling tank in a wastewater treatment plant) were tested with two different working anodes: Ti/MMO and Nb/BDD. The degradation efficiency and kinetics were evaluated to find the best combination of current density, electrodes and set-up design. For both reactors the best electrode combination was achieved with Ti/MMO as anode. The batch reactor at 7 mA/cm2 during 4 h attained degradation rates below the detection limit for triclosan and 2,4,6-trichlorophenol and, 94% and 43% for 2,4-dichlorophenol and methyl triclosan, respectively. The flow reactor obtained, in approximately 1 h, degradation efficiencies between 41% and 87% for the four contaminants. This study suggests an alternative technology for emerging organic contaminants degradation, since the combination of a low current density with the flow and matrix induced disturbance increases and speeds up the compounds' elimination in a real environmental matrix.

Aging effects on the mobility of Pb in soil: Influence on the energy requirements in electroremediation.

This paper studies the possible differences in the behavior of lead as a contaminant in soil samples when it is present as "naturally-aged" for decades after the contamination, and when it has been spiked in the laboratory. This behavior differences are stablished mainly in two ways: as changes in the fractionation analysis obtained after a sequential extraction procedure (SEP) and as changes in the efficiency of the acid-enhanced electroremediation (EKR) technique. Additionally, aging effects have been studied for almost five years. In the case of the lead-spiked soil the influence of storage conditions on contaminant behavior have also been explored: 1) samples stored in capped containers at constant moisture conditions, and 2) samples in containers open to the atmosphere, with periods of water flooding and drying. Lab-spiked and the "naturally-aged" contaminants show very different behavior with respect not only to SEP analysis but also to EKR experiments. The soil spiked with a soluble lead salt presents a higher percent in the more mobile fractions. Regarding storage conditions, some changes were observed in the lead distribution along the vertical soil profile for samples stored in uncapped containers. The EKR results were also in agreement with those from fractionation analysis. Energy requirements for the remediation were estimated by a mathematical model with important differences obtained for the different soil samples. Results are indicating that it will be very unreliable to draw estimations for the "naturally-aged" soils from contaminant-spiked samples.

Effects of the buffering capacity of the soil on the mobilization of heavy metals. Equilibrium and kinetics.

Understanding the possible pH-buffering processes is of maximum importance for risk assessment and remediation feasibility studies of heavy-metal contaminated soils. This paper presents the results about the effect of the buffering capacity of a polluted soil, rich in carbonates, on the pH and on the leaching evolution of its main contaminant (lead) when a weak acid (acetic acid) or a strong one (nitric acid) are slowly added. In both cases, the behavior of lead dissolution could be predicted using available (scientifically verified freeware) models assuming equilibrium between the solid and the aqueous phase. However, the experimental results indicate that the dissolution of calcium and magnesium carbonates is kinetically controlled. These kinetic limitations affect the overall behavior, and should be considered to understand also the response of the metals under local equilibrium. The well-known BCR sequential extraction procedure was used before- and after-treatment, to fractionate the lead concentration in the soil according to its mobility. The BCR results were also in agreement with the predictions of the equilibrium model. This agreement allows new insights about the information that could be derived from the BCR fractionation analysis.