Abstract: Hydroxyapatite (HAP) is frequently used as biocompatible coating on Ti-based implants. In this context, the HAP-Ti adhesion is of crucial importance. Here, we report ab initio calculations to investigate the influence of Si incorporation into the amorphous calcium-phosphate (a-HAP) structure on the interfacial bonding mechanism between the a-HAP coating and an amorphous titanium dioxide (a-TiO2) substrate, contrasting two different density functionals: PBE-GGA, and DFT-D3, which are capable of describing the influence of the van der Waals (vdW) interactions. In particular, we discuss the effect of dispersion on the work of adhesion (W-ad), equilibrium geometries, and charge density difference (CDD). We find that replacement of P by Si in a-HAP (a-Si-HAP) with the creation of OH vacancies as charge compensation results in a significant increase in the bond strength between the coating and substrate in the case of using the PBE-GGA functional. However, including the vdW interactions shows that these forces considerably contribute to the W-ad. We show that the difference (W-ad – W-ad(vdW)) is on average more than 1.1 J m(-2) and 0.5 J m(-2) for a-HAP/a-TiO2 and a-Si-HAP/a-TiO2, respectively. These results reveal that including vdW interactions is essential for accurately describing the chemical bonding at the a-HAP/a-TiO2 interface.

Abstract: The investigation of thermal transport properties of novel two-dimensional materials is crucially important in order to assess their potential to be used in future technological applications, such as thermoelectric power generation. In this respect, the lattice thermal transport properties of the monolayer structures of group VA elements (P, As, Sb, Bi, PAs, PSb, PBi, AsSb, AsBi, SbBi, P3As1, P3Sb1, P1As3, and As3Sb1) with a black phosphorus like puckered structure were systematically investigated by first-principles calculations and an iterative solution of the phonon Boltzmann transport equation. Phosphorene was found to have the highest lattice thermal conductivity, , due to its low average atomic mass and strong interatomic bonding character. As a matter of course, anisotropic was obtained for all the considered materials, owing to anisotropy in frequency values and phonon group velocities calculated for these structures. However, the determined linear correlation between the anisotropy in the values of P, As, and Sb is significant. The results corresponding to the studied compound structures clearly point out that thermal (electronic) conductivity of pristine monolayers might be suppressed (improved) by alloying them with the same group elements. For instance, the room temperature of PBi along the armchair direction was predicted to be as low as 1.5 W m(-1) K-1, whereas that of P was predicted to be 21 W m(-1) K-1. In spite of the apparent differences in structural and vibrational properties, we peculiarly revealed an intriguing correlation between the values of all the considered materials as = c(1) + c(2)/m(2), in particular along the zigzag direction. Furthermore, our calculations on compound structures clearly showed that the thermoelectric potential of these materials can be improved by suppressing their thermal properties. The presence of ultra-low values and high electrical conductivity (especially along the armchair direction) makes this class of monolayers promising candidates for thermoelectric applications.

Abstract: Maritime transport of benzene is regulated by the International Maritime Organisation (IMO). Two important guidelines for a ships crew in this matter are IMO circulars 1095 and 1220. The first one describes the minimum safety standards for ships carrying liquids in bulk containing benzene while circular 1220 deals with structural guidelines for new ships carrying liquids in bulk containing benzene, but also technical developments could help in improving safety and health protection on board chemical tankers carrying benzene in bulk. The aim of the present paper is to determine the benzene concentration in the working and living environment on board a modern chemical tanker carrying benzene in bulk, where all safety, technical and operational procedures described by IMO in the above-mentioned circulars are followed. During specific cargo operations, we measured the benzene concentrations on different locations on board by means of Radiello® passive diffusive samplers. Despite all measures taken, we found an important difference in benzene concentration between operations with a benzene cargo compared to operations without benzene on board, as well as inside and outside the accommodation. Moreover, even during discharge operations, where the emission is theoretically zero, we found an important increase in the benzene concentration. In addition, we found less favourable results for the engine room.

Abstract: Porous limestone and mortar are able to absorb large quantities of water. This phenomenon will accelerate the deterioration of the material. In such cases, the material might be treated with a hydrophobic product, which creates a superficial layer that hampers the penetration of water. In order to decide if such a treatment should be applied or not, the water absorbing behaviour of the material should be measured. With the same measuring technique the efficiency of the hydrophobic barrier can be evaluated. Moreover, it allows the monitoring of such barriers as a function of time. At the same time, the water absorption of porous stone material is an indication of the degree of deterioration and its sensitivity to future deterioration. Up to now, two different measuring techniques exist, but one can only be used in laboratory and the other, which can be operated in laboratory as well as in situ, is not always reliable for in situ analyses. This article proposes an alternative method: the contact sponge method. This recently developed method was tested on non-treated porous stone materials in a laboratory environment in order to evaluate its performance in comparison with the two existing methods.

Abstract: Proton Induced X-ray Emission, (PIXE), is capable of high precision analysis for trace element components of aerosol particle size fractions sampled by cascade impactor. A statistical evaluation of data quality has been carried out in order to distinguish between analytical uncertainties in the PIXE procedure, errors caused by cascade impactor performance and by other factors in the sampling procedure, and geophysical causes of differences in composition and particle size distributions of the elements in aerosols. Replicate analyses and simultaneous samplings taken in north Florida and St. Louis have been used for the data evaluation. In addition to the analytical error the sampling procedure contributes an error of ~ 10% to be added quadratically. The resulting precision is sufficient to evaluate the data in geophysical terms. This is illustrated by means of sample sets taken simultaneously in an urban, forest and coastal environment of the same region.

Abstract: Mass, major ionic components (MICs) of PM2.5, and related gaseous pollutants (SO2, NOx, NH3, HNO2, and HNO3) were monitored over six locations of different anthropogenic influence (industrial, urban, suburban, and rural) in Belgium. SO42-, NO3-, NH4+, and Na+ were the primary ions of PM2.5 with averages diurnal concentrations ranging from 0.44.5, 0.37.6, 0.94.9, and 0.41.2 µg m-3, respectively. MICs formed 39% of PM2.5 on an average, but it could reach up to 8098%. The SO2, NO, NO2, HNO2, and HNO3 levels showed high seasonal and site-specific fluctuations. The NH3 levels were similar over all the sites (26 µg m-3), indicating its relation to the evenly distributed animal husbandry activities. The sulfur and nitrogen oxidation ratios for PM2.5 point towards a low-to-moderate formation of secondary sulfate and nitrate aerosols over five cities/towns, but their fairly intensive formation over the rural Wingene. Cluster analysis revealed the association of three groups of compounds in PM2.5: (i) NH4NO3, KNO3; (ii) Na2SO4; and (iii) MgCl2, CaCl2, MgF2, CaF2, corresponding to anthropogenic, sea-salt, and mixed (sea-salt + anthropogenic) aerosols, respectively. The neutralization and cation-to-anion ratios indicate that MICs of PM2.5 appeared mostly as (NH4)2SO4 and NH4NO3 salts. Sea-salt input was maximal during winter reaching up to 12% of PM2.5. The overall average Cl-loss for sea-salt particles of PM2.5 at the six sites varied between 69 and 96% with an average of 87%. Principal component analysis revealed vehicular emission, coal/wood burning and animal farming as the dominating sources for the ionic components of PM2.5.

Abstract: The leaf area, as an important leaf functional trait, is thought to be related to leaf length and width. Our recent study showed that the Montgomery equation, which assumes that leaf area is proportional to the product of leaf length and width, applied to different leaf shapes, and the coefficient of proportionality (namely the Montgomery parameter) range from 1/2 to π/4. However, no relevant geometrical evidence has previously been provided to support the above findings. Here, four types of representative leaf shapes (the elliptical, sectorial, linear, and triangular shapes) were studied. We derived the range of the estimate of the Montgomery parameter for every type. For the elliptical and triangular leaf shapes, the estimates are π/4 and 1/2, respectively; for the linear leaf shape, especially for the plants of Poaceae that can be described by the simplified Gielis equation, the estimate ranges from 0.6795 to π/4; for the sectorial leaf shape, the estimate ranges from 1/2 to π/4. The estimates based on the observations of actual leaves support the above theoretical results. The results obtained here show that the coefficient of proportionality of leaf area versus the product of leaf length and width only varies in a small range, maintaining the allometric relationship for leaf area and thereby suggesting that the proportional relationship between leaf area and the product of leaf length and width broadly remains stable during leaf evolution.

Abstract: The smuggling of illicit drugs urges the development of new tools for rapid on-site identification in cargos. Current methods rely on presumptive color tests and portable spectroscopic techniques. However, these methods sometimes exhibit inaccurate results due to commonly used cutting agents, the colorful nature of the sample or because the drugs are smuggled in common goods. Interestingly, electrochemical sensors can deal with these specific problems. Herein, an electrochemical device is presented that uses affordable screen-printed electrodes for the electrochemical profiling of several illicit drugs by square-wave voltammetry (SWV). The identification of the illicit compound is based on the oxidation potential of the analyte. Hence, a library of electrochemical profiles is built upon the analysis of illicit drugs and common cutting agents. This library allows the design of a tailor-made script that enables the identification of each drug through a user-friendly interface (laptop or mobile phone). Importantly, the electrochemical test is compared by analyzing 48 confiscated samples with other portable devices based on Raman and FTIR spectroscopy as well as a laboratory standard method (i.e., gas chromatography-mass spectrometry). Overall, the electrochemical results, obtained through the analysis of different samples from confiscated cargos at an end-user site, present a promising alternative to current methods, offering low-cost and rapid testing in the field.

Abstract: The ongoing rapid expansions of human activities and population dynamics have potential impact on the environmental quality of the Pangani river basin, one of the largest water resources in Tanzania, including possible loadings of different kinds of micro-contaminants. However, specific extents of the impacts are rather not well investigated. In this work, we assessed the environmental quality of the basin, based on seasonal characterisation of physicochemical water and sediments parameters, dissolved inorganic ions and nutrient loads. The contributions of geochemical processes and land-use practices were evaluated by multivariate correlations and principal component analysis (PCA). Hierarchical cluster analysis was used to classify similar water quality stations and identify the most and least enriched ones. Surface waters were slightly alkaline, characterised by low total dissolved solids (48652 mg/L). Extremely low oxygen concentration (2.0 mg/L) was also a cause of concern at one station. The Na+ and HCO3 − ions provided the dominant cation and anion, respectively. PCA identified weathering of carbonate and Na+ bearing rocks, gypsum dissolution and atmospheric deposition of sea-salt as the major factors controlling the ionic composition, contributing more than 60% of the spatial variance. Concentration profiles of the chemical species showed a generally low level of anthropogenic inputs, except at a few locations where nitrate and nitrite were significantly enriched above the limits of safe exposure, with patterns indicating influences of farming and livestock keeping. A seasonal difference was observed, with lower ion concentrations during the rainy season, likely due to the dilution effect of increased water discharge. The study provides new insights into the environmental quality of the basin, and indicates the need for continuous monitoring and assessment of the chemical species in the area.