Main Chemical Species Research Articles

Exploring the Interplay between Tribocorrosion and Surface Chemistry of the ASTM F139 Surgical Stainless Steel in Phosphate-Buffered Saline Solution.

Surgical ASTM F139 stainless steel is used for temporary fixtures in the biomedical field. Tribocorrosion is a major concern in this application. The aim of the present work was to study the interplay between tribocorrosion behavior and the surface chemistry of the ASTM F139 stainless steel in phosphate-buffered saline solution (PBS). Sliding wear tests were conducted against alumina balls at different electrochemical potentials: open circuit potential (OCP), cathodic potential (-100 mV versus the OCP), and anodic potentials (+200 mVAg/AgCl and +700 mVAg/AgCl). The normal load was 20 N. The wear volume was estimated based on micrographs obtained from the wear tracks using confocal laser scanning microscopy. Moreover, the wear tracks were also examined by scanning electron microscopy (SEM). The surface chemistry of the ASTM F139 specimens was analyzed by X-ray photoelectron spectroscopy (XPS). The wear volume was dependent on the electrochemical potential, being maximized at +700 mVAg/AgCl. Delamination areas and grooves were observed in the wear tracks. Detailed assessment of the surface chemistry inside the wear tracks allowed identification of the main chemical species and their relative quantities, thus enabling correlation of the passive film composition with the observed tribocorrosion behavior.

Submicron aerosol pollution in Greater Cairo (Egypt): A new type of urban haze?

Greater Cairo, the largest megacity of the Middle East North Africa (MENA) region, is currently suffering from major aerosol pollution, posing a significant threat to public health. However, the main sources of pollution remain insufficiently characterized due to limited atmospheric observations. To bridge this knowledge gap, we conducted a continuous 2-month field study during the winter of 2019–2020 at an urban background site, documenting for the first time the chemical and physical properties of submicron (PM1) aerosols. Crustal material from both desert dust and road traffic dust resuspension contributed as much as 24 % of the total PM1 mass (rising to 66 % during desert dust events), a figure not commonly observed in urban environments. Our observations showed significant decreases in black carbon concentrations and ammonium sulfate compared to data from 15 years ago, indicating an important reduction in both local and regional emissions as a result of effective mitigation measures. The diurnal variability of carbonaceous aerosols was attributed to emissions emanating from local traffic at rush hours and nighttime open biomass burning. Surprisingly, semi-volatile ammonium chloride (NH4Cl) originating from local open biomass and waste burning was found to be the main chemical species in PM1 over Cairo. Its nighttime formation contributed to aerosol water uptake during morning hours, thereby playing a major role in the build-up of urban haze. While our results confirm the persistence of a significant dust reservoir over Cairo, they also unveil an additional source of highly hygroscopic (semi-volatile) inorganic salts, leading to a unique type of urban haze. This haze, with dominant contributors present in both submicron (primarily as NH4Cl) and supermicron (largely as dust) modes, underscores the potential implications of heterogeneous chemical transformation of air pollutants in urban environments.

Element distribution in electrochemically treated mine wastewater for efficient resource recovery and water treatment: A pilot study

The feasibility of recovering major and critical elements from acid mine drainage using a pilot-scale electrochemical reactor (ECR) was investigated by assessing elements concentration and species distribution in the liquid and solid phase (sludge) in multistage tests. These were carried out at different electrical currents (18–22 amps) and thus, pH (8–12). The results showed that major metals Al, Cu and Fe were removed from the liquid phase at pH 5.9 while remaining the majority of Zn (57.2 ppm). On the other hand, at pH 7, the effluent was mainly composed of Mn (7.3 ppm). These results were confirmed by the simulation results using the PHREEQC model, which also identified the main chemical species in solution and the precipitates formed after the treatment (oxyhydroxides/sulfates/oxides). The ECR treatment led to sludges with targeted critical elements, some up to 20 times (Co, Be and Sb) higher than their earth's crustal abundance. At pH 10, rare earth elements in the sludge targeted Ce, followed by Nd and La. This study is one of the few studies carrying a detailed analysis of the behavioural distribution pattern of these elements at each pH, which opens the door for the potential of recovering these elements.

A Multiphysics Co-Simulation Framework of a Gas Engine and Three-Way Catalyst toward a Complete Vehicle Design Model

In view of the increasingly stringent emission regulations, the automotive sector needs considerable support from the development of robust and reliable engine and aftertreatment models. Accurate reproduction of engine-out and tailpipe pollutants plays a crucial role in complying with these legislations. Given the difficulty in characterizing some critical phenomena, frequently caused by strong dynamics and related to experimental uncertainties, communication between several calibrated and reliable models is mandatory. This is certainly valid for powertrains that will be powered with alternative gas fuels such as natural gas, bio-methane and hydrogen in the future. This paper describes a methodology to co-simulate a 1D CNG HD 6-cyl engine model and a 1D quasi-steady Three-Way Catalyst model in a global framework for high-fidelity virtual prototyping of the vehicle system. Through the implementation of a dedicated control logic in MATLAB/Simulink, the modeling architecture allows for the reproduction of the engine performance parameters together with the evaluation of the TWC pollutants’ conversion efficiency. An extensive database of experimental tests was used to assess the model response. The latter was validated in multiple steady-state operating conditions of the engine workplan. Using a semi-predictive combustion model, the validation was carried out over a wide range of different air-to-fuel ratios and during fast rich/lean transitions to evaluate the formation and conversion phenomena of the main chemical species, both engine-out and tailpipe. Subsequently, the complete model was validated in dynamic conditions throughout a WHTC, accurately reproducing the cut-off phases and their sudden accelerations. The numerical–experimental agreement on pollutant reproduction is generally good and globally below 3%. Larger deviations occur in extremely rich conditions and in CH4 emission evaluation due to the lack of information related to the combustion process and chemical mechanisms involving the Pd surface.

The Influence of pH on the Lipase Digestion of Nanosized Triolein, Diolein and Monoolein Films

Herein we studied the processes at the liquid aqueous interface at pH 7 and 8.5 during Thermomyces lanuginosus lipase-catalyzed hydrolysis of nanosized tri-, di- and mono-olein films deposited on a planar substrate. By employing a combination of ellipsometry, QCM-D and ATR-FTIR, we were able to reveal the physical properties of the thin films at high time resolution throughout the initial hydration and subsequent digestion, as well as the main chemical species present before and after lipolysis. The ATR-FTIR results showed that the degree of digestion and protonated state of the oleic acid produced in the reaction are highly dependent on the pH of the aqueous solvent. Furthermore, the ellipsometry and QCM-D results reveal that the duration of the lag phase observed before lipolysis was detected and the magnitude and type of changes to the physical properties of the thin films throughout digestion was influenced by whether the initial substrate consisted of tri-, di- or mono-olein.

Multispectral Mid-Infrared Camera System for Accurate Stand-Off Temperature and Column Density Measurements on Flames.

Accurate measurement of temperature in flames is a challenging problem that has been successfully addressed by hyperspectral imaging. This technique is able to provide maps of not only temperature T (K) but also of column density Q (ppmm) of the main chemical species. Industrial applications, however, require cheaper instrumentation and faster and simpler data analysis. In this work, the feasibility and performance of multispectral imaging for the retrieval of T and Q in flames are studied. Both the hyperspectral and multispectral measurement methods are described and applied to a standard flame, with known T and Q, and to an ordinary Bunsen flame. Hyperspectral results, based on emission spectra with cm resolution, were found in previous works to be highly accurate, and are thus considered as the ground truth to compare with multispectral measurements of a mid-IR camera (3 to 5 m) with a six interference filter wheel. Maps of T and Q obtained by both methods show that, for regions with T K, the average of relative errors in multispectral measurements is ∼5% for T (and can be reduced to ∼2.5% with a correction based on a linear regression) and ∼20% for Q. Results obtained with four filters are very similar; results with two filters are also similar for T but worse for Q.

Assessment and validation of ICP-MS and IC-ICP-MS methods for the determination of total, extracted and speciated arsenic. Application to samples from a soil-rice system at varying the irrigation method

Food is the major route of arsenic (As) intake for humans, and rice is the staple food for more than half of the world's population. Unfortunately, rice bioaccumulates large amounts of As from the paddy field, and the toxicity of this element in the kernel is closely linked to its chemical form. Therefore, it is of the utmost importance to have access to an integrated set of analytical methods, capable of measuring the concentration of As in its various chemical forms in soil and rice. Hence, the principal aim of this study was to assess and validate a group of inductively coupled plasma – mass spectrometry (ICP-MS) and IC-ICP-MS (IC, Ionic Chromatography) methods designed to measure the amount of the total or extracted As and its main chemical species (As(III), As(V), monomethylarsonic acid, MMA, and dimethylarsinic acid, DMA) in flours of rice grain and in soils. Great attention has been given to the assessment and the optimization of extraction methods of As species from these matrices. No appreciable interconversion among As species has been observed using an aqueous solution 1 mol dm−3 of phosphoric acid and 0.5 mol dm−3 of L (+)-ascorbic acid for the extraction from soils, and an aqueous solution 0.2% (w/v) of nitric acid for the extraction from rice flour. Validation has been successfully accomplished in terms of limit of detection, limit of quantification, linearity and accuracy. In addition to many certified reference materials, these methods have been tested on real samples of soils and rice grains of the Aleramo genotype obtained through traditional or intermittent irrigation methods. Data obtained revealed the critical role of the intermittent irrigation methods in determining the nature and the amount of the As chemical species in rice grains as well as in soils. As(V) is the only species found in soil irrigated by sprinkling, while the most toxic As(III) dominates in soil irrigated by continuous flooding. On the other hand, the most abundant species found in continuously flooded Aleramo rice grains are As(III) and – mostly – DMA, whereas As(V), less toxic than As(III), represents 60% of the total inorganic compounds measured in sprinkler-irrigated rice. Lastly, the total amount of As measured in this rice is 3.8% of that measured in rice irrigated by continuous flooding.

Optimization of HS-SPME for GC-MS Analysis and Its Application in Characterization of Volatile Compounds in Sweet Potato.

Volatile compounds are the main chemical species determining the characteristic aroma of food. A procedure based on headspace solid-phase microextraction (HP-SPME) coupled to gas chromatography-mass spectrometry (GC-MS) was developed to investigate the volatile compounds of sweet potato. The experimental conditions (fiber coating, incubation temperature and time, extraction time) were optimized for the extraction of volatile compounds from sweet potato. The samples incubated at 80 °C for 30 min and extracted at 80 °C by the fiber with a divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) coating for 30 min gave the most effective extraction of the analytes. The optimized method was applied to study the volatile profile of four sweet potato cultivars (Anna, Jieshu95-16, Ayamursaki, and Shuangzai) with different aroma. In total, 68 compounds were identified and the dominants were aldehydes, followed by alcohols, ketones, and terpenes. Significant differences were observed among the volatile profile of four cultivars. Furthermore, each cultivar was characterized by different compounds with typical flavor. The results substantiated that the optimized HS-SPME GC-MS method could provide an efficient and convenient approach to study the flavor characteristics of sweet potato. This is the basis for studying the key aroma-active compounds and selecting odor-rich accessions, which will help in the targeted improvement of sweet potato flavor in breeding.

Chemical composition characteristics and source analysis of PM2.5 in Jiaxing, China: insights into the effect of COVID-19 outbreak

ABSTRACT Jiaxing is a medium-sized city in the Yangtze River Delta (YRD), which showed complex local and surrounding pollution sources. To study the COVID-19 impact on the ambient PM2.5 in Jiaxing, we collected the PM2.5 samples from 2 January to 25 April 2020 and analysed their chemical compositions (including carbon components, water-soluble ions (WSIs), and inorganic elements). The concentration of PM2.5 was 83.13 ± 30.93 μg/m3 before COVID-19 pandemic and then remarkably decreased with COVID-19 outbreak due to the suspension of mobility and industrial activities. Meanwhile, the concentrations of main chemical species (carbon components, water-soluble ions and inorganic elements) of PM2.5 all decreased from period A (2–20 January 2020) to period B (23 January to 10 February 2020). Moreover, Trajectory clustering analysis showed that close-range transport was one of the dominant factors throughout all the periods, except for period D (1–25 April 2020). In addition, the PSCF model indicated that the COVID-19 outbreak resulted in a significant decrease of WPSCF value. This study highlighted the differences in chemical compositions and sources of PM2.5 since COVID-19 pandemic was reported and provided a better understanding of its outbreak on PM2.5.

Computational Simulation of a Hot Filament Chemical Vapor Deposition Process for Depositing SRO Films

In the present report, a two dimensional (2D) model was developed to describe the fluid dynamics, heat and mass transfer of a Chemical Vapor Deposition activated by a Hot Filament (HFCVD) reactor, as well as the chemical generation of the precursor species which are present in the growth of non-stoichiometric silicon rich oxide (SRO) films. The SRO is known for have excellent photo luminescent properties which are useful in optoelectronic applications. This material can be obtained by the HFCVD technique which offers important advantages such as the easily to obtain thin films with diverse structural, compositional and optical characteristics. During deposition is a priority to control key parameters as inlet flow, substrate temperature and pressure so it compels to know previous theoretical information about these parameters which can be obtained by computational simulation. Therefore, by means of commercial Computational Fluid Dynamics (CFD) were solved the continuity, momentum and energy equations in steady state. Also, a thermodynamic equilibrium study of the SiO2(s) + H2 (g) reaction was carried out with the Factsage software. The thermodynamic equilibrium results provide the main chemical species which are present during the deposit process of the SRO films. The 2D model was used to simulate the temperature and velocity distribution of the hydrogen in the deposit process. The theoretical calculated temperatures were compared with those obtained experimentally by thermocouple measurements. From the simulation results, the temperature and gas velocity profiles were obtained at different hydrogen flow levels (50, 75, 100 sccm) and temperature source-substrate distances (5, 6 and 7mm) for a 50 sccm level. SEM micrographs and profilometry measurements disclose that the outlet configuration affects substantially both the thickness and surface uniformity of the SRO films. This parameter was modified to obtain a better quality (thickness and uniformity) and a large deposit area.

Formaldehyde Analysis in Non-Aqueous Methanol Solutions by Infrared Spectroscopy and Electrospray Ionization.

We present the analysis of formaldehyde (HCHO) in anhydrous methanol (CH3OH) as a case study to quantify HCHO in non-aqueous samples. At higher concentrations (C > 0.07 M), we detect a product of HCHO, methoxy methanol (MM, CH3OCH2OH), by Fourier transform infrared spectroscopy, FTIR. Formaldehyde reacts with CH3OH, CD3OH, and CD3OD as shown by FTIR with a characteristic spectral feature around 1,195 cm−1 for CH3OH used for the qualitative detection of MM, a formaldehyde derivative in neat methanol. Ab initio calculations support this assignment. The extinction coefficient for 1,195 cm−1 is in the order of 1.4 × 102 M−1cm−1, which makes the detection limit by FTIR in the order of 0.07 M. For lower concentrations, we performed the quantitative analysis of non-aqueous samples by derivatization with dinitrophenylhydrazine (DNPH). The derivatization uses an aqueous H2SO4 solution to yield the formaldehyde derivatized hydrazone. Ba(OH)2 removes sulfate ions from the derivatized samples and a final extraction with isobutyl acetate to yield a 1:1 methanol: isobutyl acetate solvent for injection for electrospray ionization (ESI). The ESI analysis gave a linear calibration curve for concentrations from 10 to 200 µM with a time-of-flight analyzer (TOF). The detection and quantification limits are 7.8 and 26 μM, respectively, for a linear correlation with R 2 > 0.99. We propose that the formaldehyde in CH3OH is in equilibrium with the MM species, without evidence of HCHO in solution. In the presence of water, the peaks for MM become less resolved, as expected from the well-known equilibria of HCHO that favors the formation of methylene glycol and polymeric species. Our results show that HCHO, in methanol does not exist in the aldehyde form as the main chemical species. Still, HCHO is in equilibrium between the production of MM and the formation of hydrated species in the presence of water. We demonstrate the ESI-MS analysis of HCHO from a non-aqueous TiO2 suspension in methanol. Detection of HCHO after illumination of the colloid indicates that methanol photooxidation yields formaldehyde in equilibrium with the solvent.

New approach for the dimensionless analysis of a unidirectional flow solar reactor based on Damköhler's number profiles

A methodology for the analysis of the behavior of complex reactors based on the construction of profiles of a dimensionless number (Damköhler) for each main chemical species (Dai) was proposed. A 4-chlorophenol mineralization reaction in a heterogeneous solar reactor with suspended TiO2 and addition of H2O2 with tubular geometry and radiation collectors, fluid flow and a recirculation system was selected as a complex model system in order to validate the approach. The dynamic behavior of the reactor in dimensionless variables was modeled as a function of Dai. Where Dai(z,t) is a local property and grouped the optical and surface's properties of the catalyst, catalyst load, radiation intensity, the photon absorption rate, rate of non-photochemical reactions, the H2O2 effect, the reaction rate of different stages like adsorption, attack of radicals, surface reactions, plus design and operation variables like reactor volume and volumetric flow.A coupling of orthogonal collocation and Runge-Kutta methods were used to solve the PDEs and carry out the simulations to the different experimental conditions, resulting in profiles of Dai, Ci, and conversion in function of time and space. The Dai profiles proposed in the new methodology are capable of describing the disturbances in solar reactors, to indicate consumption and generation rates, instantaneous changes of reaction rate, to describe competitive reactions and quenching effects and to determine equilibrium concentrations, all of the above at each time and space. Therefore, this approach is a analysis tool of reactors which complements the concentration profile. This methodology can be extended to other reactive systems, adapting the intrinsic reaction rates.

Hydrogen Production via Pd-TiO2 Photocatalytic Water Splitting under Near-UV and Visible Light: Analysis of the Reaction Mechanism

Photocatalytic hydrogen production via water splitting using a noble metal on a TiO2 is a technology that has developed rapidly over the past few years. Specifically, palladium doped TiO2 irradiated with near-UV or alternatively with visible light has shown promising results. With this end in mind, strategically designed experiments were developed in the Photo-CREC Water-II (PCW-II) Reactor using a 0.25 wt.% Pd-TiO2 under near-UV and visible light, and ethanol as an organic scavenger. Acetaldehyde, carbon monoxide, carbon dioxide, methane, ethane, ethylene, and hydrogen peroxide together with hydrogen were the main chemical species observed. A Langmuir adsorption isotherm was also established for hydrogen peroxide. On this basis, it is shown that pH variations, hydrogen peroxide formation/adsorption, and the production of various redox chemical species provide an excellent carbon element balance, as well as OH• and H• radicals balances. Under near-UV irradiation, 113 cm3 STP of H2 is produced after 6 h, reaching an 99.8% elemental carbon balance and 99.2% OH• and H• and radical balance. It is also proven that a similar reaction network can be considered adequate for the photoreduced Pd-TiO2 photocatalyst yielding 29 cm3 STP of H2 with 95.4% carbon and the 97.5% OH•–H• radical balance closures. It is shown on this basis that a proposed “series-parallel” reaction network describes the water splitting reaction using the mesoporous Pd-TiO2 and ethanol as organic scavenger.

Arsenic Removal and Recovery of Germanium and Tungsten in Toxic Coal Fly Ash from Lignite by Vacuum Distillation with a Sulfurizing Reagent.

Every year, billions of tons of lignite are burnt to generate electricity, meanwhile generating large amounts of coal fly ash (CFA) that is regarded as an industrial waste. During lignite combustion, arsenic and scarce metals are simultaneously volatilized in the form of oxide into CFA. This study proposed an effective vacuum distillation method to remove As and recover Ge and W from CFA. The feasibility of separating As and recycling Ge and W from CFA was verified by the theoretical analysis. The experimental result indicated that the removal ratio of As was 96 ± 1% and the contents of Ge and W reached 0.75 ± 0.023 and 0.24 ± 0.016 wt % in the residue, which were enriched 17.2 and 1.2 times, respectively, at a temperature of 550 °C, with 50 wt % sulfurizing agent added under pressure of 1 Pa and 240 min of heating. For the condensed product, chemical species As2S3 and As4S4 were detected by X-ray photoelectron spectroscopy analysis. For Ge and W in the residue, GeOx (x < 2), GeS, WOx (x < 3), and WS2 were the main chemical species. The potential mechanism involved in the release of arsenic from CFA, vacuum sulfurization, evaporation, and condensation was proposed. The kinetic analysis indicated that the apparent activation energy (Eα) was 31.24 kJ mol-1. Those results encourage further exploration of vacuum separation technology to environmentally friendly recycle CFA.

New Insights into Health Risk Assessments for Inhalational Exposure to Metal(loid)s: The Application of Aqueous Chemistry Modelling in Understanding Bioaccessibility from Airborne Particulate Matter

Aqueous modelling of chemical speciation in simulated lung fluid (SLF) enables a better understanding of the underlying chemical factors that influence metal(loid) inhalation bioaccessibility from airborne particulate matter. Such an approach can be used to supplement experimental techniques that are integral to the health risk assessment of metal(loid) exposure by inhalational routes. In this paper, we modelled the aqueous chemistry of airborne particulate-bound metal(loid)s (As, Cu, Mn, Pb and Zn) in a SLF based on Gamble’s solution (neutral pH). The modelling was performed using two software packages (Geochemist’s Workbench 14 and OLI Studio 9.5) and a total of five thermochemical databases (GWB Thermo, MINTEQ, PHREEQC, WATEQ4F and the default database for OLI Studio). Modelled results were compared with experimentally determined bioaccessibilities for the NIST 2710a standard reference material (SRM) and with literature-reported bioaccessibilities for NIST 1648a and BCR 038 SRMs. Whilst the models correctly describe the observed increase in bioaccessibility for more dilute solid/liquid extraction ratios, the performance of the models against the fractional bias of the mean (FBmean) and the normalised mean square error (NMSE) statistical metrics was generally outside the acceptance criteria. Findings from an analysis of the main aqueous chemical species predicted to be present in SLF indicate that carbonate and chloride complexes of Cu, Mn, Pb and Zn predominate, whilst free cations (for Cu, Mn and Zn) and hydroxides (for Cu) also play a role in solubilisation. Arsenic is not predicted to form significant complexes with the SLF components and is present in solution mainly as the HAsO42− ion and its conjugate acid, H2AsO4−. For modelled runs where glycine and citrate were present, significant increases in the bioavailability of Cu and Zn were predicted as a result of complexation with these ligands. An additional finding from our experimental bioaccessibility results for NIST 2710a was that the inclusion of the lung fluid surfactant dipalmitoylphosphatidylcholine (DPPC) in the SLF did not significantly affect the bioaccessibility. Our study provides useful insights into the likely aqueous- and solid-phase speciation of metal(loid)s in SLF and highlights that future developments in this area should consider the role of mineralogy and surface interactions.

Digital twin of a combustion furnace operating in flameless conditions: reduced-order model development from CFD simulations

The present paper presents the first-of-its-kind digital twin for a furnace operating in flameless combustion conditions. A methodology combining data compression, by means of Proper Orthogonal Decomposition (POD), and interpolation, using Kriging, was developed to design physics-based, reduced-order models (ROMs) for the prediction of combustion data at unexplored operating conditions. Three-dimensional simulations with detailed chemistry were carried out, spanning a wide range of operating conditions in terms of fuel composition (methane-hydrogen mixtures from pure methane to pure hydrogen), equivalence ratio (from 0.7 to 1) and air injector diameter (to adjust the air jet entrainment). Based on the available simulations, a ROM was developed, to predict both spatial fields, local and integral values of thermochemical variables at working conditions not included in the ROM development. Results showed that the developed ROM could reliably predict the temperature and main chemical species distribution in the furnace with an overall error below 10%, proving the effectiveness of the approach for the development of digital twins of combustion systems. A remarkable accuracy was observed for the prediction of specific quantities, including wall temperatures, OH decay length, OH peak value and location and exhaust gas composition, including pollutants, with prediction errors always below 5%, showing the potential of the approach to develop soft sensors.

Significant changes in the chemical compositions and sources of PM2.5 in Wuhan since the city lockdown as COVID-19

Wuhan was the first city to adopt the lockdown measures to prevent COVID-19 spreading, which improved the air quality accordingly. This study investigated the variations in chemical compositions, source contributions, and regional transport of fine particles (PM2.5) during January 23–February 22 of 2020, compared with the same period in 2019. The average mass concentration of PM2.5 decreased from 72.9 μg m−3 (2019) to 45.9 μg m−3 (2020), by 27.0 μg m−3. It was predominantly contributed by the emission reduction (92.0%), retrieved from a random forest tree approach. The main chemical species of PM2.5 all decreased with the reductions ranging from 0.85 μg m−3 (chloride) to 9.86 μg m−3 (nitrate) (p < 0.01). Positive matrix factorization model indicated that the mass contributions of seven PM2.5 sources all decreased. However, their contribution percentages varied from −11.0% (industrial processes) to 8.70% (secondary inorganic aerosol). Source contributions of PM2.5 transported from potential geographical regions showed reductions with mean values ranging from 0.22 to 4.36 μg m−3. However, increased contributions of firework burning, secondary inorganic aerosol, road dust, and vehicle emissions from transboundary transport were observed. This study highlighted the complex and nonlinear response of chemical compositions and sources of PM2.5 to air pollution control measures, suggesting the importance of regional-joint control.

Construction of immobilized 0D/1D heterostructure photocatalyst Au/CuS/CdS/TiO2 NBs with enhanced photocatalytic activity towards moxifloxacin degradation

Strong absorption in a wide wavelength range and effective charge separation are main factors for improving photocatalytic activity of semiconductor photocatalysts. Herein, immobilized zero-dimensional/one-dimensional (0D/1D) Au/CuS/CdS/TiO2 nanobelts (Au/CuS/CdS/TiO2 NBs) heterostructure photocatalyst with innovative morphology and appropriate band-gap configuration was synthesized for the first time. For this construction, TiO2 NBs provide the 1D structure for a large superficial area and fast electron mobility, 0D CdS and CuS nanoparticles are the visible-light responsive nanomaterials, and Au nanoparticles serve as the surface plasmon resonance effect and electron transfer. The Au/CuS/CdS/TiO2 NBs showed improved photocatalytic performance towards moxifloxacin (MOX) degradation, which can be attributed to the promoted photoabsorption contribution and enhanced separation and transfer of photoexcited electrons and holes. The morphology, constitution, optical and electrochemical properties of the prepared photocatalyst were investigated comprehensively. Moreover, the photocatalytic degradation mechanism and degradation by-products of moxifloxacin were studied. Results showed that the OH, O2− and h+ are the main chemical oxidation species responsible for the degradation of MOX. Eight different photocatalytic degradation products were detected. The stability assessment showed that photodissolution plays the primary role in the photocatalytic performance decrease of Au/CuS/CdS/TiO2 NBs. This work gives a promising strategy to rational design efficient hybrid metal-semiconductor photocatalysts for solar energy conversion.

Influence of Metallic Copper Vapors on the Chemical Composition of a Mixture of Air and Water Vapor Thermal Plasmas in the Temperature Range 1000 K to 20000K

This paper concern the calculation of equilibrium composition of plasma mixture Air-Water vapor and copper vapor in temperatures range 1000K to 20000 K. The plasma is suposed to be in local thermodynamic equilibrium. We used Gibbs free energy minimization method to access the different numerical densities of chemical species as a function of temperature. This data are very important to calculate thermodynamic properties, transport coefficients and modeling electrical arc in circuit breakers. The result shows that the influence of metallic copper vapor is important on equilibrium composition of plasma. In particular the densities of electron in the plasma increase with the percentage of copper vapor for the temperature inferior to 17000K. The increasing of electron densities increase electrical conductivity of plasma and limit the performance of circuit breakers. Also the electrical neutrality is made mainly between electron (e^-) and Cu⁺ in low temperature (T < 12000K). We are studying in particular the evolution of the densities of the main chemical species created in this plasma as a function of pressure. We choose four values of pressure (1 atm, 5 atm, 10 atm and 15 atm). The results obtained shows an increasing of chemical densities with the pressure in the mixture in conformity at Dalton's Law. the increasing of the pressure in the plasma retard chemical reactions because it disadvantages the dislocations that constitute dissociation and ionization reactions in the plasma.

Modelling of the Elementary Steps Involved in the Aluminum Electrochemical Deposition from Ionic Liquid Based Solution: The BMImCl/AlCl3 System

The energy hierarchy, of the main chemical species involved in the reaction mechanism relevant to the electrodeposition of aluminum in 1-Butyl-3-methylimidazolium chloride/aluminum trichloride solution (BMImCl/AlCl3), is studied by using ab-initio based theoretical calculations. Eventually, a reasonable theoretical estimate of energies, involved in the principal reactions ruling the aluminum electrodeposition from BMImCl ionic liquid solutions, is obtained. For screening purposes (geometry optimization and Hessian calculations) the CAMB3LYP density functional, DFT, has been used. Then single point (exploiting CAMB3LYP optimized geometries) energy data are obtained at the Møller-Plesset (MP2) level of the theory. They are used to cross-check DFT results. A reaction mechanism emerges in which, although the species AlCl−4 is formed with very high efficiency from the neutral species AlCl3, the competing reaction points to an almost complete conversion of aluminum to the dimeric form into bulk solution. This is observed in the absence and, most importantly, in the presence of a coordinating BMIm+ cation. In this respect, the presence of BMIm+ does not seem to affect significantly the equilibrium between the monomeric and dimeric forms of aluminum. This outcome is very interesting because the dimeric species is directly reduced to yield the metal aluminum. Indeed, a larger concentration of Al2Cl−7 gives due reason for a more effective electrodeposition process, as it is experimentally observed in the ionic liquid medium.