Biochar-Supported TiO2-Based Nanocomposites for the Photocatalytic Degradation of Sulfamethoxazole in Water-A Review.

Sulfamethoxazole (SMX) is a frequently used antibiotic for the treatment of urinary tract, respiratory, and intestinal infections and as a supplement in livestock or fishery farming to boost production. The release of SMX into the environment can lead to the development of antibiotic resistance among the microbial community, which can lead to frequent clinical infections. SMX removal from water is usually done through advanced treatment processes, such as adsorption, photocatalytic oxidation, and biodegradation. Among them, the advanced oxidation process using TiO2 and its composites is being widely used. TiO2 is a widely used photocatalyst; however, it has certain limitations, such as low visible light response and quick recombination of e-/h+ pairs. Integrating the biochar with TiO2 nanoparticles can overcome such limitations. The biochar-supported TiO2 composites showed a significant increase in the photocatalytic activities in the UV-visible range, which resulted in a substantial increase in the degradation of SMX in water. The present review has critically reviewed the methods of biochar TiO2 composite synthesis, the effect of biochar integration with the TiO2 on its physicochemical properties, and the chemical pathways through which the biochar/TiO2 composite degrades the SMX in water or aqueous solution. The degradation of SMX using photocatalysis can be considered a useful model, and the research studies presented in this review will allow extending this area of research on other types of similar pharmaceuticals or pollutants in general in the future.

Assessment of groundwater geochemistry and diffusion of hexavalent chromium contamination in an industrial town of Italy.

Groundwater contamination by hexavalent chromium (Cr (VI)) is currently a very serious and challenging issue. Therefore, in the present study, 108 shallow groundwater samples were collected during the years 2012 to 2015 (n = 27 samples each year) from an industrial town (Aosta) to assess the contamination status of the area. To evaluate the Cr (VI) concentration level, sources of pollutants and groundwater geochemistry of the study area, a combined approach of the multi-statistical and hydrogeochemical techniques were used. Furthermore, a geographic information system (GIS) was applied for the spatial distribution of Cr (VI) so that the most contaminated sites can be identified for a quick decision by policymakers. Results show that the groundwater chemistry was dominated by HCO3- and SO42- in the anionic chemistry and Ca2+ and Na+ in the cationic chemistry, while Ca-Mg-HCO3 and Ca-Mg-Cl-SO4 were the main water types during the years 2012-2015 in the study area. The central part and some north-eastern parts of the Aosta town groundwater was contaminated with Cr (VI) and are unsafe for drinking use. Concentration levels of Cr (VI) in the groundwater were 0.09 µg/L (lowest value) and 165 µg/L (highest value) in the years studied, and the spatial analysis shows the diffusion of Cr (VI) to north-east direction from the source. Contamination of Cr (VI) in the groundwater was due to the superficial slag deposits from a steel company within the study area. This study would be helpful for current and future water resource management in the area concerned.

Evaluation of groundwater salinization and pollution level on Favignana Island, Italy.

Fifty-six groundwater samples were taken from the island of Favignana to evaluate the interaction between the groundwater and seawater, as well as the deterioration factors for the aquifers, using the combined hydrogeochemical and multivariate statistical approaches. Results show that the order of the groundwater chemistry in the study area was Na+> Ca2+>Mg2+>K+ and Cl->HCO3->SO42->NO3-. The groundwater samples were in the moderate saline zone to highly saline zone and indicate that the groundwater of the island of Favignana was recharged with seawater. The spatial distribution maps of Cl- and NO3- show that most of the groundwater samples had high concentrations of Cl- and NO3- in the study area. The ionic ratio diagrams, such as Na+/Cl- versus Cl-, Mg2+/Ca2+ versus Cl- and Ca2+/HCO3- versus Cl-, and other hydrogeochemical plots reveal that the groundwater chemistry of the study was primarily controlled by the seawater intrusion and reverse ion exchange process, with a small contribution from carbonate dissolution. Additionally, the NO3-/Cl- versus Cl- diagram and principal component analysis (PCA) show that the contamination of nitrate in the study area was due to human activities (i.e. agriculture and domestic sewage disposal). The outcome of the present research could be helpful for groundwater resource management in coastal environments.

Effect of Intrinsic Properties of Anions on the Electrocatalytic Activity of NiCo2O4 and NiCo2O x S4-x Grown by Chemical Bath Deposition.

Electrochemical water (H2O) splitting is one of the most promising technologies for energy storage by hydrogen (H2) generation but suffers from the requirement of high overpotential in the anodic half-reaction (oxygen evolution), which is a four-electron process. Though transition-metal oxides and oxysulfides are increasingly researched and used as oxygen evolution electrocatalysts, the bases of their differential activities are not properly understood. In this article, we have synthesized NiCo2O4 and NiCo2O x S4-x by a chemical bath deposition technique, and the latter has shown better oxygen evolution performance, both in terms of stability and activity, under alkaline conditions. Comprehensive analysis through time-dependent cyclic voltammetry, microscopy, and elemental analysis reveal that the higher activity of NiCo2O x S4-x may be attributed to the lower metal-sulfur bond energy that facilitates the activation process to form the active metal hydroxide/oxyhydroxide species, higher electrochemically active surface area, higher pore diameter and rugged morphology that prevents corrosion. This work provides significant insights on the advantages of sulfur-containing materials as electrochemical precatalysts over their oxide counterparts for oxygen evolution reaction.

Assessment of Sulphate and Iron Contamination and Seasonal Variations in the Water Resources of a Damodar Valley Coalfield, India: A Case Study.

The aim of the present study was to assess the sulphate [Formula: see text] and iron (Fe) contamination and seasonal variations in the water resources (groundwater, surface water, and mine water) of the West Bokaro coalfield region, India. One hundred and twenty-four water resources samples were collected from the coalfield during the post- and pre-monsoon seasons. The concentrations of [Formula: see text] were determined using ion chromatography and Fe concentrations were analyzed using inductively coupled plasma mass spectrometry. A statistical analysis was used to easily understand the seasonal variations of the elements in the water resources of the area. The concentrations of [Formula: see text] and Fe in the water resources were higher in the pre-monsoon season than in the post-monsoon season, irrespective of location. The water resources of the coalfield were contaminated with high concentrations of [Formula: see text] and Fe, and would require suitable treatment before drinking, domestic and industrial uses.

Assessment of Mine Water Quality Using Heavy Metal Pollution Index in a Coal Mining Area of Damodar River Basin, India.

A total no. of 16 mine water (underground and opencast coal mine pump discharges) samples were collected from East Bokaro coalfield during pre-monsoon, monsoon and post-monsoon seasons. The concentrations of Fe, Mn, Cu, Pb, Zn, Ni, As, Se, Al, Cd and Cr were determined using inductively coupled plasma mass spectrometry for the assessment of spatio-temporal variations, source apportionment and heavy metal pollution indexing. The results demonstrated that concentrations of the metals showed significant seasonality and most variables exhibited higher levels in the pre-monsoon season. The principle component analysis for ionic source identification was synthesized into three factors with eigen values cut off at greater than unity and explained about 64.8% of the total variance. The extracted factors seemed to be associated to the geogenic, extensive mining and allied transportation sources of the elements. The heavy metal pollution index (HPI) of the mine water calculated for the individual locations varied from 7.1 to 49.5. Most of the locations fall under low to medium classes of HPI except few locations which are under the influence of surface mining and associated transportation.

Automated Diagnosis of Epilepsy Using Key-Point-Based Local Binary Pattern of EEG Signals.

The electroencephalogram (EEG) signals are commonly used for diagnosis of epilepsy. In this paper, we present a new methodology for EEG-based automated diagnosis of epilepsy. Our method involves detection of key points at multiple scales in EEG signals using a pyramid of difference of Gaussian filtered signals. Local binary patterns (LBPs) are computed at these key points and the histogram of these patterns are considered as the feature set, which is fed to the support vector machine (SVM) for the classification of EEG signals. The proposed methodology has been investigated for the four well-known classification problems namely, 1) normal and epileptic seizure, 2) epileptic seizure and seizure free, 3) normal, epileptic seizure, and seizure free, and 4) epileptic seizure and nonseizure EEG signals using publically available university of Bonn EEG database. Our experimental results in terms of classification accuracies have been compared with existing methods for the classification of the aforementioned problems. Further, performance evaluation on another EEG dataset shows that our approach is effective for classification of seizure and seizure-free EEG signals. The proposed methodology based on the LBP computed at key points is simple and easy to implement for real-time epileptic seizure detection.

Estimation of Heavy Metal Contamination in Groundwater and Development of a Heavy Metal Pollution Index by Using GIS Technique.

Heavy metal (Al, As, Ba, Cr, Cu, Fe, Mn, Ni, Se and Zn) concentration in sixty-six groundwater samples of the West Bokaro coalfield were analyzed using inductively coupled plasma-mass spectroscopy for determination of seasonal fluctuation, source apportionment and heavy metal pollution index (HPI). Metal concentrations were found higher in the pre-monsoon season as compared to the post-monsoon season. Geographic information system (GIS) tool was attributed to study the metals risk in groundwater of the West Bokaro coalfield. The results show that 94 % of water samples were found as low class and 6 % of water samples were in medium class in the post-monsoon season. However, 79 % of water samples were found in low class, 18 % in medium class and 3 % in high class in the pre-monsoon season. The HPI values were below the critical pollution index value of 100. The concentrations of Al, Fe, Mn, and Ni are exceeding the desirable limits in many groundwater samples in both seasons.

Evaluation of Surface Water Quality by Using GIS and a Heavy Metal Pollution Index (HPI) Model in a Coal Mining Area, India.

Twenty eight surface water samples were collected from fourteen sites of the West Bokaro coalfield, India. The concentration of Mn, Cu, Zn, Ni, As, Se, Al, Cr, Ba, and Fe were analyzed using inductively coupled plasma mass spectrometry (ICP-MS) for determination of seasonal fluctuations and a heavy metal pollution index (HPI). The HPI values were below the critical pollution index value of 100. Metal concentrations were higher in the pre-monsoon season as compared to the post-monsoon season. The Zn, Ni, Mn, As, Se, Al, Ba, Cu, and Cr concentrations did not exceed the desirable limits for drinking water in either season. However, at many sites, concentrations of Fe were above the desirable limit of the WHO (2006) and Indian drinking water standard (BIS 2003) in both seasons. The water that contained higher concentrations of Fe would require treatment before domestic use.

Unique emission from norbornene derived terpyridine--a selective chemodosimeter for G-type nerve agent surrogates.

A new chemodosimeter for a G-type agent that exploits norbornene derived terpyridine (NDT)-lanthanide unique emission is reported. The unusual emission between terpyridine and norbornene motifs of NDT is attributed to the significant difference in the position of the HOMO and LUMO wave functions that prevents the non-radiative relaxation pathway. An interesting magenta emission from NDT along with Eu(III) is utilized as a new fluorometric chemodosimeter that selectively detects (by changing the observed magenta emission to blue) G-type agent surrogates. A detection limit of 40 ppb is obtained and the selectivity for reactive surrogates over a variety of other close chemical analogs is demonstrated.

The temperature dependence of methane dissociation on Ni(111) and Pt(111): mixed quantum-classical studies of the lattice response.

The barrier to the dissociative adsorption of methane on metal surfaces is generally large, and its height can vary with the motion of the lattice atoms. One fully quantum and three different mixed quantum-classical approaches are used to examine this reaction on Ni(111) and Pt(111) surfaces, using potential energy surfaces derived from density functional theory. The three approximate methods are benchmarked against the exact quantum studies, and two of them are shown to work reasonably well. The mixed models, which treat the lattice motion classically, are used to examine the lattice response during the reaction. It is found that the thermal motion of the lattice atoms strongly modifies the reactivity, but that their motion is not significantly perturbed. Based on these results, new models for methane reactions are proposed based on a sudden treatment of the lattice motion and shown to agree well with the exact results. In these new models, the reaction probability at different surface temperatures is computed from static surface reaction probabilities, allowing for a quantum calculation of the reaction probability without having to explicitly treat the motion of the heavy lattice atoms.

Methane dissociation and adsorption on Ni(111), Pt(111), Ni(100), Pt(100), and Pt(110)-(1 x 2): energetic study.

We use density functional theory to examine 24 transition states for methane dissociation on five different metal surfaces. In our calculations, the nonlocal exchange-correlation effects are treated within the generalized gradient approximation using the Perdew-Burke-Ernzerhof functional. In all cases, the minimum energy path for dissociation is over a top site. The barriers are large, 0.66-1.12 eV, and relatively insensitive to the rotational orientation of the (nonreacting) methyl group and the azimuthal orientation of the reactive C-H bond. There is a strong preference on the Pt surfaces for the methyl fragment to bond on the top site, while on the Ni surfaces there is a preference for the hollow or bridge sites. Thus, during the dissociation on Pt, only the low mass H atom needs to significantly move or tunnel, while on Ni, both the dissociating H and the methyl fragment move away from the top site. For all 24 configurations there is a strong force at the transition state to pucker the metal atom over which the reaction occurs. The resulting magnitude of the variation in the barrier height with the motion of this atom varies a bit from surface-to-surface, but is of the order of 1 eV/A. We derive a model for the effective reaction barrier height that includes the effects of lattice motion and substrate temperature and compare with recent experiments and other theoretical studies.

Importance of Coriolis Coupling in Isotopic Branching in (He, HD+) collisions.

A three-dimensional time-dependent quantum mechanical wave packet approach is used to calculate the reaction probability (P(R)) and integral reaction cross section values for both channels of the reaction He + HD(+)(v = 1; j = 0) --> HeH (D)(+) + D (H) over a range of translational energy (E(trans)) on the McLaughlin-Thompson-Joseph-Sathyamurthy potential energy surface including the Coriolis coupling (CC) term in the Hamiltonian. The reaction probability plots as a function of translational energy for different J values exhibit several oscillations, which are characteristic of the system. The sigma(R) values obtained by including CC and not including it are nearly the same over the range of E(trans) investigated for the HeD(+) channel. For the HeH(+) channel, on the other hand, sigma(R) values obtained from CC calculations are significantly smaller than those obtained from coupled state calculations. These results are compared with the available experimental results. The computed branching ratios (Gamma(sigma) = sigma(R) (HeH(+))/sigma(R) (HeD(+))) are also compared with the available experimental results.

Methane dissociation on Ni(111): a new understanding of the lattice effect.

The nature of the lattice motion during the dissociation of methane on Ni(111) is analyzed in great detail, and various models for including lattice effects are explored. It is shown that the thermal vibrations of the lattice strongly modify the reactivity, but that the lattice motion is relatively unperturbed by the incident molecule during the collision, in contrast with several earlier predictions. Based on these studies we propose a new model to describe the effects of lattice motion, which agrees well with exact quantum calculations.

Effect of reagent rotation on isotopic branching in (He, HD+) collisions.

A three-dimensional time-dependent quantum mechanical wave packet approach is used to calculate reaction probability (P(R)) and integral reaction cross section (sigma(R)) values for both the channels of the reaction He + HD(+) (v = 1; j = 0, 1, 2, 3) --> HeH(D)(+) + D(H), over a range of translational energy (E(trans)) on the McLaughlin-Thompson-Joseph-Sathyamurthy (MTJS) potential energy surface using centrifugal sudden approximation for nonzero total angular momentum (J) values. The reaction probability plots as a function of translational energy for different J values exhibit several oscillations, which are characteristic of the system. It is shown that HeH(+) is preferred over HeD(+) for large J values and that HeD(+) is preferred over HeH(+) for small J values for all the rotational (j) states studied. The integral reaction cross section for both the channels and therefore the isotopic branching ratio for the reaction depend strongly on j in contrast to the marginal dependence shown by earlier QCT calculations. The computed results are in overall agreement with the available experimental results.

Structure and stability of salicylic acid-water complexes and the effect of molecular hydration on the spectral properties of salicylic acid.

Density functional theory with B3LYP parametrization and 6-311++G(d,p) basis set has been used to investigate the structure and stability of salicylic acid-water complexes. The vertical excitation energies for these complexes have been computed using time-dependent density functional theory (with B3LYP parametrization and a 6-311++G(d,p) basis set). It is shown that the hydrogen bond between the carboxylic hydrogen and the oxygen of water is the strongest among all possible hydrogen bonds in the system. The hydrogen bond strength in salicylic acid-water complexes seems to be nearly additive. The change in absorption maximum (lambda(max)) corresponding to the vertical excitation energy for the first three excited singlet and triplet states of the complex with 1-3 water molecules is nominal (approximately 1-3 nm). But with the addition of the fourth water molecule, the lambda(max) for S(1) and T(1) decreases by approximately 17 nm and it increases for S(2) and S(3) by about the same amount. The decrease in lambda(max) for transition to the T(2) state on the addition of the fourth water molecule is only approximately 9 nm. There seems to be an intersystem crossing between the S(1) and T(3) states that could account for the observed fluorescence quenching of salicylic acid in water.

Isotopic branching in (He, HD+) collisions.

A three-dimensional time-dependent quantum mechanical approach is used to calculate the reaction probability (P(R)) and the integral reaction cross section (sigma(R)) for both channels of the reaction He + HD+(v = 0, 1, 2, 3; j = 0) --> HeH(D)+ + D(H), over a range of translational energy (E(trans)) on two different ab initio potential energy surfaces (McLaughlin-Thompson-Joseph-Sathyamurthy and Palmieri et al.). The reaction probability plots as a function of translational energy exhibit several oscillations, which are characteristic of the system. The vibrational enhancement of the reaction probability and the integral reaction cross section values are reproduced qualitatively by our calculations, in accordance with the experimental results. The isotopic branching ratio for the reaction decreases in going from v = 0 to v = 1 and then becomes nearly v-independent in going from v = 1 to v =3 on both the surfaces.