Efficient removal of 2,4,6-trinitrotoluene (TNT) from industrial/military wastewater using anodic oxidation on boron-doped diamond electrodes.

With growing public concern about water quality particular focus should be placed on organic micropollutants, which are harmful to the environment and people. Hence, the objective of this research is to enhance the security and resilience of water resources by developing an efficient system for reclaiming industrial/military wastewater and protecting recipients from the toxic and cancerogenic explosive compound-2,4,6-trinitrotoluene (TNT), which has been widely distributed in the environment. This research used an anodic oxidation (AO) process on a boron-doped diamond (BDD) electrode for the TNT removal from artificial and real-life matrices: marine water and treated wastewater. During experiments, TNT concentrations were significantly decreased, reaching the anodic degradation efficiency of above 92% within two hours and > 99.9% after six hours of environmental sample treatment. The presented results show the great potential of AO performed on BDD anodes for full-scale application in the industry and military sectors for TNT removal.

Conductive printable electrodes tuned by boron-doped nanodiamond foil additives for nitroexplosive detection.

An efficient additive manufacturing-based composite material fabrication for electrochemical applications is reported. The composite is composed of commercially available graphene-doped polylactide acid (G-PLA) 3D printouts and surface-functionalized with nanocrystalline boron-doped diamond foil (NDF) additives. The NDFs were synthesized on a tantalum substrate and transferred to the 3D-printout surface at 200 °C. No other electrode activation treatment was necessary. Different configurations of low- and heavy-boron doping NDFs were evaluated. The electrode kinetics was analyzed using electrochemical procedures: cyclic voltammetry and electrochemical impedance spectroscopy. The quasi-reversible electrochemical process was reported in each studied case. The studies allowed confirmation of the CV peak-to-peak separation of 63 mV and remarkably high heterogeneous electron transfer rate constant reaching 6.1 × 10-2 cm s-1 for 10 k ppm [B]/[C] thin NDF fitted topside at the G-PLA electrode. Differential pulse voltammetry was used for effective 2,4,6-trinitrotoluene (TNT) detection at the studied electrodes with a 87 ppb limit of detection, and wide linearity range between peak current density and the analyte concentration (0.064 to 64 ppm of TNT). The reported electrode kinetic differences originate primarily from the boron-dopant concentration in the diamond and the various contents of the non-diamond carbon phase.

Simultaneous opto-electrochemical monitoring of carbamazepine and its electro-oxidation by-products in wastewater.

The growing human impact on aquatic environments deriving from the extensive use of pharmaceuticals and the release of persistent pollutants necessitates the implementation of new, widespread methods for characterising and quantifying such contaminants and their related degradation products. Carbamazepine, 5 H-dibenzo[b,f]azepine-5-carboxamide, (CBZ) is a widely used anti-epileptic drug characterised by limited removal by conventional wastewater treatments and high persistency in the environment. In this work, CBZ detection and quantification was performed in phosphate buffer, as well as in samples of complex matrix-like landfill leachates and treated wastewater originating from a medical facility, and simultaneously by optical and electrochemical methods using a novel transparent carbon-based nanostructured electrode. Coupling electrochemical (differential pulse voltammetry) with optical (UV-visible spectroscopy) methods, it has been possible to reach the limit of detection (LOD) for CBZ at the levels of 4.7 µM for the electrochemical method, 10.3 µM for the spectroscopic method, and 3.6 µM for the opto-electrochemical method. Raman spectroscopy and ultra-high performance liquid chromatography coupled with tandem mass spectrometry techniques were employed to support and validate the combined technique. The novel developed technique showed high selectivity to carbamazepine and its by-products, even in environmental samples. Thus, this environmentally friendly, fast and accurate detection method is believed to be successfully implementable in investigating other pharmaceutical and chemical contaminates of concern.

Highly selective impedimetric determination of Haemophilus influenzae protein D using maze-like boron-doped carbon nanowall electrodes.

This study reports a novel impedimetric immunosensor for protein D detection in purified and bacterial (Haemophilus influenzae, Hi) samples. The detection was based on antigen recognition by anti-protein D antibodies (apD) immobilised at the maze-like boron-doped carbon nanowall electrodes (B:CNW). The B:CNW electrodes were synthesised, and their surface was characterised by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) methods. The sensor was prepared in a two-step procedure: apD were covalently linked on the previously modified B:CNW electrodes using diazonium salt. Modification steps were controlled by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) measurements. The immunosensor exhibited excellent electrochemical performance, stability, satisfactory sensitivities, and linear ranges for antigen detection. Protein D was detected down to 2.39 × 102fg/mL with a linear range extending from 3.37 × 10-11to 3.37 × 10-3µg/mL (in purified sample). Next, Hi's LOD was 5.20 × 102CFU/mL with a linear range of 8.39 × 101-8.39 × 103CFU/mL. Selectivity studies showed no reaction with negative samples as Streptococcus pyogenes, Streptococcus pneumoniae or Bordetella parapertussis bacteria. Therefore, the new approach is suitable for rapid and quantitative detection of Hi, and is a good candidate for further tests on clinical samples.

Cortical activity associated with the perception of temporal asymmetry in ramped and damped noises.

Human listeners are very sensitive to the asymmetry of time-reversed pairs of ramped and damped sounds. When the carrier is noise, the hiss -component of the perception is stronger in ramped sounds and the drumming component is stronger in damped sounds (Akeroyd and Patterson 1995). In the current study, a paired comparison technique was used to establish the relative "hissiness" of these noises, and the ratings were correlated with (a) components of the auditory evoked field (AEF) produced by these noises and (b) the magnitude of a hissiness feature derived from a model of the internal auditory images produced by these noises (Irino and Patterson 1998). An earlier AEF report indicated that the peak magnitude of the transient N100m response mirrors the perceived salience of the tonal perception (Rupp et al. 2005). The AEFs of 14 subjects were recorded in response to damped/ramped noises with half-lives between 1 and 64 ms and repetition rates between 12.5 and 100 ms. Spatio-temporal source analysis was used to fit the P50m, the P200m, and the sustained field (SF). These noise stimuli did not produce a reliable N100m. The hissiness feature from the auditory model was extracted from a time-averaged sequence of summary auditory images as in Patterson and Irino (1998). The results show that the perceptual measure of hissiness is highly correlated with the hissiness feature from the summary auditory image, and both are highly correlated with the magnitude of the transient P200m. There is a significant but weaker correlation with the SF and a nonsignificant correlation with the P50m. The results suggest that regularity in the carrier effects branching at an early stage of auditory processing with tonal and noisy sounds following separate spatio-temporal routes through the system.