Metal-Organic Frameworks against Toxic Chemicals.

Materials capable of the safe and efficient capture or degradation of toxic chemicals, including chemical warfare agents (CWAs) and toxic industrial chemicals (TICs), are critically important in the modern age due to continuous threats of these chemicals to human life, both directly and indirectly. Metal-organic frameworks (MOFs), atomically precise hybrid materials that are synthesized via the self-assembly of metal cations or clusters and organic linkers, offer a unique solid adsorbent design platform due to their great synthetic versatility. This review will focus on recent advancements in MOF-based adsorbent design for protection against chemical warfare agents (organophosphorus nerve agents, blistering agents, and their simulants) and toxic industrial chemicals such as H2S, NH3, SO2, CO, NO2, and NO.

An experimental study on the simultaneous removal of NO and SO2 with a new wet recycling process based on the micro-nano bubble water system.

The micronano bubble water system (MNBW) generated by a micronano bubble generator (MNBG) has the superior oxidation properties and can improve gas solubility. In the study, a new wet recycling process based on MNBW is proposed to simultaneously remove nitric oxide (NO) and sulfur dioxide (SO2). The important experimental parameters such as initial water pH, initial water temperature, NO and SO2 concentrations, and the presence of oxygen (O2) were investigated to explore the feasibility of desulfurization and denitration with MNBW. The experimental results showed that decreasing initial water pH or increasing initial water temperature and NO and SO2 concentrations were not conducive to the removal of NO or SO2. O2 could promote the removal of NO, but it had no effect on SO2 removal. In addition, SO2 removal efficiency always remained high and did not change obviously during the experimental period. However, NO removal efficiency gradually decreased in the first 50 min and then became stable.

A pursuit to design highly sensitive fullerene-based sensors: adsorption and dissociation phenomenon of toxic sulfur gases on B40 fullerene.

The adsorption phenomenon of toxic sulfur gases namely H2S and SO2 on B40 fullerene is scrutinized utilizing density functional theory-non-equilibrium Green's function (DFT-NEGF) regime. Adsorption of gas molecules is considered at both the hexagonal and heptagonal rings of the fullerene and adsorption energies, charge transfer, electron charge densities, density of states, transmission spectra, molecular energy spectra; Eigen states, HOMO-LUMO gap, current voltage curve, and differential conductance are premeditated. It is inferred that H2S molecule is physisorbed on the heptagonal ring of the fullerene while it is dissociative-chemisorbed on the hexagonal ring. SO2 dissociates into SO and O species on adsorption on both the hexagonal and heptagonal rings. From the transmission spectra and DOS analysis, LUMO dominant transmission is noticed in all the devices except the one formed with heptagonal ring adsorption of H2S which favors HOMO-dominated transmission. From the I-V curve and differential conductance investigation, different conductance values are noticed for all the junctions, thus proving that B40 is an efficient material to be engaged in sensing toxic sulfur gases.

Recent progress in the small-molecule fluorescent probes for the detection of sulfur dioxide derivatives (HSO3-/SO32-).

Sulfur dioxide (SO2) had been recognized as an environmental pollutant produced from industrial processes. SO2 is water soluble and forms hydrated SO2 (SO2·H2O), bisulfite ion (HSO3-), and sulfite ion (SO32-) upon dissolution in water. SO2 could be also produced endogenously from sulfur-containing amino acids l-cysteine in mammals. Endogenous SO2 can maintain the balance of biological sulfur and redox equilibrium in vivo, regulate blood insulin levels and reduce blood pressure. Excess intake of exogenous SO2 can result in respiratory diseases, cardiovascular diseases and neurological disorders. As a result, fluorescent probes to detect HSO3-/SO32- have attracted great attention in recent years. Herein, a general overview was provided with the aim to highlight the typical examples of the HSO3-/SO32- fluorescent probes reported since 2010, especially those in the past five years. We have classified HSO3-/SO32- fluorescent probes through different chemical reaction mechanisms and wish this review will give some help to the researchers in this field.

Simultaneous removal of SO2 and NO by FeII(EDTA) solution: promotion of Mn powder and mechanism of reduction.

The effect of Mn powder addition on the simultaneous removal of SO2 and NO coupled with FeII(EDTA) absorption was investigated in this work. In the NO absorption system with FeII(EDTA), SO2 reduced FeII(EDTA)-NO to FeII(EDTA) with a reduction efficiency reaching 88.5% under the conditions of 4000 mg/m3 SO2, pH 8.0, 44 °C, and the flow rate of 1.2 L/min within 60 min. Introducing 0.1 M Mn powder with SO2 increased the FeII(EDTA)-NO reduction efficiency to 96.8% within 5 min. SO2 was also removed by reducing FeII(EDTA)-NO and converted into SO42- at a removal efficiency of 100%. After adding Mn powder, NO was removed through the following reaction: [Formula: see text]. Mn powder functioned as a reductant to regenerate the absorption of solution, and the coordinated NO in FeII(EDTA)-NO was reduced to NH4+. The resource utilization rate of N reached approximately 77.2%. The integrated technology is a potential solution for flue gas treatment in industrial sectors with coal-fired power plants and industrial boiler. Graphical abstract.

Integrated lipid production, CO2 fixation, and removal of SO2 and NO from simulated flue gas by oleaginous Chlorella pyrenoidosa.

CO2, SO2, and NO are the main components of flue gas and can cause serious environmental issues. Utilization of these compounds in oleaginous microalgae cultivation not only could reduce air pollution but could also produce feedstock for biodiesel production. However, the continuous input of SO2 and NO inhibits microalgal growth. In this study, the toxicity of simulated flue gas (15% CO2, 0.03% SO2, and 0.03% NO, balanced with N2) was reduced through automatic pH feedback control. Integrated lipid production and CO2 fixation with the removal of SO2 and NO was achieved. Using this technique, a lipid content of 38.0% DW was achieved in Chlorella pyrenoidosa XQ-20044. The lipid composition and fatty acid profile indicated that lipid production by C. pyrenoidosa XQ-20044 cultured with flue gas is suitable as a biodiesel feedstock; 81.2% of the total lipids were neutral lipids and 99.5% of the total fatty acids were C16 and C18. The ratio of saturated fatty acids to monounsaturated fatty acids in the microalgal lipid content was 74.5%. In addition, CO2, SO2, and NO from the simulated flue gas were fixed and converted to biomass and lipids with a removal efficiency of 95.9%, 100%, and 84.2%, respectively. Furthermore, the utilization efficiencies of CO2, SO2, and NO were equal to or very close to their removal efficiencies. These results provide a novel strategy for combining biodiesel production with biofixation of flue gas.

Simultaneous removal of NO and SO2 from flue gas using vaporized H2O2 catalyzed by nanoscale zero-valent iron.

To remove NO and SO2 from flue gas simultaneously, a heterogeneous catalytic oxidation system was developed with the nanoscale zero-valent iron (nZVI), vaporized H2O2, and sodium humate (HA-Na) acting as the catalyst, oxidant, and absorbent, respectively. The experimental results indicated that the desulfurization was mainly influenced by the absorption, and the denitrification was significantly affected by the catalytic oxidation parameters. Under the optimal conditions, the simultaneous removal efficiencies of SO2 and NO were 100 and 88.4%, respectively. The presence of ·OH during the removal process was proved by the scavenger tests, and the production of ·OH with and without nZVI was indirectly evaluated by the electron paramagnetic resonance (EPR) and methylene blue experiments. Moreover, the fresh and aged nZVI were characterized by a series of techniques and the results suggested that the redox pair Fe2+/Fe3+ released by nZVI could react with H2O2 to provide the sustainable ·OH, which was important for the oxidation from NO and SO2 to NO3- and SO42-. The removal mechanism was proposed preliminarily based on the correlative experiments, characterizations, and references.

Determination of free and total sulfur(IV) compounds in coconut water using high-resolution continuum source molecular absorption spectrometry in gas phase.

This work proposes a method for the determination of free and total sulfur(IV) compounds in coconut water samples, using the high-resolution continuum source molecular absorption spectrometry. It is based on the measurement of the absorbance signal of the SO2 gas generate, which is resultant of the addition of hydrochloric acid solution on the sample containing the sulfating agent. The sulfite bound to the organic compounds is released by the addition of sodium hydroxide solution, before the generation of the SO2 gas. The optimization step was performed using multivariate methodology involving volume, concentration and flow rate of hydrochloric acid. This method was established by the sum of the absorbances obtained in the three lines of molecular absorption of the SO2 gas. This strategy allowed a procedure for the determination of sulfite with limits of detection and quantification of 0.36 and 1.21mgL-1 (for a sample volume of 10mL) and precision expressed as relative standard deviation of 5.4% and 6.4% for a coconut water sample containing 38.13 and 54.58mgL-1 of free and total sulfite, respectively. The method was applied for analyzing five coconut water samples from Salvador city, Brazil. The average contents varied from 13.0 to 55.4mgL-1 for free sulfite and from 24.7 to 66.9mgL-1 for total sulfur(IV) compounds. The samples were also analyzed employing the Ripper´s procedure, which is a reference method for the quantification of this additive. A statistical test at 95% confidence level demonstrated that there is no significant difference between the results obtained by the two methods.

Simultaneous removal of NO and SO2 using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS).

Simultaneous removal process of SO2 and NO from flue gas using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS) in a VUV spraying reactor was proposed. The key influencing factors, active species, reaction products and mechanism of SO2 and NO simultaneous removal were investigated. The results show that vacuum ultraviolet light (185 nm) achieves the highest NO removal efficiency and yield of and under the same test conditions. NO removal is enhanced at higher PMS concentration, light intensity and oxygen concentration, and is inhibited at higher NO concentration, SO2 concentration and solution pH. Solution temperature has a double impact on NO removal. CO2 concentration has no obvious effect on NO removal. and produced from VUV-activation of PMS play a leading role in NO removal. O3 and ·O produced from VUV-activation of O2 also play an important role in NO removal. SO2 achieves complete removal under all experimental conditions due to its very high solubility in water and good reactivity. The highest simultaneous removal efficiency of SO2 and NO reaches 100% and 91.3%, respectively.

Gas chromatography-mass spectrometry strategies for the accurate and sensitive speciation of sulfur dioxide in wine.

Understanding the chemistry of wine oxidation requires the accurate and sensitive quantitative determination of the most important molecular species which SO2 can form. An analytical strategy based in three independent static headspace GC-MS determinations is proposed in order to obtain information about the total, nominally free and truly free levels of SO2. Nominally free forms are directly determined after sample acidulation, total forms require the previous incubation at 100°C, and truly free forms are determined after preconcentration of the headspace of the undisturbed sample in an alkaline solution. The two first determinations provide results equivalent to those reported by the aeration-oxidation (A-O) method, with lower limits of detection (1mgL-1) and better repeatabilities (<4.0%). Results from the analysis of different wines revealed that levels of nominally free are systematically in excess than those of truly free SO2, which suggests that free SO2 determined by any method using previous acidulation includes at least two different species of SO2, which may have different antioxidant behavior.

Removal kinetics for gaseous NO and SO2 by an aqueous NaClO2 solution mist in a wet electrostatic precipitator.

Removal kinetics for NO and SO2 by NaClO2 solution mist were investigated in a wet electrostatic precipitator. By varying the molar concentrations of NO, SO2, and NaClO2, the removal rates of NO and SO2 confirmed to range from 34.8 to 72.9 mmol/m3 s and 36.6 to 84.7 mmol/m3 s, respectively, at a fixed gas residence time of 0.25 s. The rate coefficients of NO and SO2 were calculated to be 0.679 (mmol/m3)-0.33 s-1 and 1.401 (mmol/m3)-0.1 s-1 based on the rates of the individual removal of NO and SO2. Simultaneous removal of NO and SO2 investigated after the evaluation of removal rates for their individual treatment was performed. At a short gas residence time, SO2 gas removed more quickly by a mist of NaClO2 solution than NO gas in simultaneous removal experiments. This is because SO2 gas, which has a relatively high solubility in solution, was absorbed more rapidly at the gas-liquid interface than NO gas. NO and SO2 gases were absorbed as nitrite [Formula: see text] and sulfite [Formula: see text] ions, respectively, by the NaClO2 solution mist at the gas-liquid interface. Then, [Formula: see text] and [Formula: see text] were oxidized to nitrate [Formula: see text] and sulfate [Formula: see text], respectively, by reactions with [Formula: see text], ClO2, HClO, and ClO in the liquid phase.

Effects of slurry properties on simultaneous removal of SO2 and NO by ammonia-Fe(II)EDTA absorption in sintering plants.

Simultaneous removal of SO2 and NO by ammonia-Fe(II)EDTA absorption has become a research focus in recent years. In order to get useful data for further industrialization, in this work the practical operating conditions of the sintering plant were simulated in a pilot-scale reactor in order to explore the effects of slurry properties on simultaneous removal of SO2 and NO. It was not conducive to the absorption of NO when (NH4)2SO4 concentration and slurry temperature had been increased. The initial NO removal efficiency decreased from 90.63% to 44.12% as the (NH4)2SO4 concentration increased from zero to 3.5 mol/L. With the increasing of Fe(II)EDTA concentration, SO32- concentration and pH value of absorption liquid and the absorption capacity of NO by Fe(II)EDTA solution increased. Especially the existence of SO32- ions in slurry had significantly improved the service life of chelating agents. The NO removal efficiency only decreased by 16.46% with the SO32- concentration of 0.3 mol/L after 30-min of operation. The chloride ions had no effects on the absorption of SO2 and NO. The results indicated that changes of slurry properties had different effects on simultaneous removal of SO2 and NO by ammonia-Fe(II)EDTA solution. The basic data offered by the experiments could effectively contribute to further industrial applications.

Temporal variation of microbial population in a thermophilic biofilter for SO2 removal.

The performance of a biofilter relies on the activity of microorganisms during the gas contaminant treatment process. In this study, SO2 was treated using a laboratory-scale biofilter packed with polyurethane foam cubes (PUFC), on which thermophilic desulfurization bacteria were attached. The thermophilic biofilter effectively reduced SO2 within 10months of operation time, with a maximum elimination capacity of 48.29 g/m(3)/hr. Temporal shifts in the microbial population in the thermophilic biofilter were determined through polymerase chain reaction-denaturing gradient gel electrophoresis and deoxyribonucleic acid (DNA) sequence analysis. The substrate species and environmental conditions in the biofilter influenced the microbial population. Oxygen distribution in the PUFC was analyzed using a microelectrode. When the water-containing rate in PUFC was over 98%, the oxygen distribution presented aerobic-anoxic-aerobic states along the test route on the PUFC. The appearance of sulfate-reducing bacteria was caused by the anaerobic conditions and sulfate formation after 4months of operation.

Desulphurization performance of TiO2-modified activated carbon by a one-step carbonization-activation method.

In this study, TiO2 powder was used as the additive to directly blend with raw bituminous coal and coking coal for preparing modified activated carbon (Ti/AC) by one-step carbonization-activation method. The Ti/AC samples were prepared through blending with different ratios of TiO2 (0-12 wt%) and their desulphurization performance was evaluated. The results show that the desulphurization activity of all Ti/AC samples was higher than that of the blank one, and the highest breakthrough sulphur capacity was obtained at 200.55 mg/g C when the blending ratio of TiO2 was 6 wt%. The Brunauer-Emmett-Temer results show that the micropores were dominant in the Ti/AC samples, and their textual properties did not change evidently compared with the blank one. The X-ray photoelectron spectroscopy results show that the loaded TiO2 could influence the relative content of surface functional groups, with slightly higher content of π-π* transitions groups on the Ti/AC samples, and the relative contents of C=O and π-π* transitions groups decreased evidently after the desulphurization process. The X-ray diffraction results show that the anatase TiO2 and rutile TiO2 co-existed on the surface of the Ti/AC samples. After the desulphurization process, TiO2 phases did not change and Ti(SO4)2 was not observed on the Ti/AC samples, while sulphate was the main desulphurization product. It can be assumed that SO2 could be catalytically oxidized into SO3 by TiO2 indirectly, rather than TiO2 directly reacted with SO2 to Ti(SO4)2.

Continuous desulfurization and bacterial community structure of an integrated bioreactor developed to treat SO2 from a gas stream.

Sulfide dioxide (SO2) is often released during the combustion processes of fossil fuels. An integrated bioreactor with two sections, namely, a suspended zone (SZ) and immobilized zone (IZ), was applied to treat SO2 for 6months. Sampling ports were set in both sections to investigate the performance and microbial characteristics of the integrated bioreactor. SO2 was effectively removed by the synergistic effect of the SZ and IZ, and more than 85% removal efficiency was achieved at steady state. The average elimination capacity of SO2 in the bioreactor was 2.80g/(m(3)·hr) for the SZ and 1.50g/(m(3)·hr) for the IZ. Most SO2 was eliminated in the SZ. The liquid level of the SZ and the water content ratio of the packing material in the IZ affected SO2 removal efficiency. The SZ served a key function not only in SO2 elimination, but also in moisture maintenance for the IZ. The desired water content in IZ could be feasibly maintained without any additional pre-humidification facilities. Clone libraries of 16S rDNA directly amplified from the DNA of each sample were constructed and sequenced to analyze the community composition and diversity in the individual zones. The desulfurization bacteria dominated both zones. Paenibacillus sp. was present in both zones, whereas Ralstonia sp. existed only in the SZ. The transfer of SO2 to the SZ involved dissolution in the nutrient solution and biodegradation by the sulfur-oxidizing bacteria. This work presents a potential biological treatment method for waste gases containing hydrophilic compounds.

The State of Ambient Air Quality in Two Ugandan Cities: A Pilot Cross-Sectional Spatial Assessment.

Air pollution is one of the leading global public health risks but its magnitude in many developing countries' cities is not known. We aimed to measure the concentration of particulate matter with aerodynamic diameter <2.5 µm (PM2.5), nitrogen dioxide (NO2), sulfur dioxide (SO2), and ozone (O3) pollutants in two Ugandan cities (Kampala and Jinja). PM2.5, O3, temperature and humidity were measured with real-time monitors, while NO2 and SO2 were measured with diffusion tubes. We found that the mean concentrations of the air pollutants PM2.5, NO2, SO2 and O3 were 132.1 µg/m3, 24.9 µg/m3, 3.7 µg/m3 and 11.4 µg/m3, respectively. The mean PM2.5 concentration is 5.3 times the World Health Organization (WHO) cut-off limits while the NO2, SO2 and O3 concentrations are below WHO cut-off limits. PM2.5 levels were higher in Kampala than in Jinja (138.6 µg/m3 vs. 99.3 µg/m3) and at industrial than residential sites (152.6 µg/m3 vs. 120.5 µg/m3) but residential sites with unpaved roads also had high PM2.5 concentrations (152.6 µg/m3). In conclusion, air pollutant concentrations in Kampala and Jinja in Uganda are dangerously high. Long-term studies are needed to characterize air pollution levels during all seasons, to assess related public health impacts, and explore mitigation approaches.

Adsorption of SOx and NOx in activated viscose fibers.

SOx and NOx are emissions resulting from combustion processes and are the main agents that contribute to the formation of acid rain, which causes harm to humans and the environment. Several techniques for removing these pollutants are applied in i.e. oil refineries, thermoelectric that use petroleum oils and vehicular pollution. Among these, highlight the adsorption of contaminants by the usage of activated carbon fibers and activated carbon, which are characterized by high surface area and uniform distribution of pores, providing appropriate conditions for application in processes of removing environmental contaminants. In the present work, activated viscose fibers (AVF) were prepared and applied in adsorption experiments of NO and SO2. The materials produced showed high values of surface area, with a predominance of micro pores with diameters in the range of 1.0 nm. The AVF had satisfactory performance in the removal of contaminants and are compatible with other synthetic fibers. Thus, the formation of active sites of carbon provides contaminants adsorption, demonstrating that carbon fibers cloth can be applied for the removal of pollutants.

Absorption and desorption of SO2 in aqueous solutions of diamine-based molten salts.

SO2 absorption and desorption behaviors were investigated in aqueous solutions of diamine-derived molten salts with a tertiary amine group on the cation and a chloride anion, including butyl-(2-dimethylaminoethyl)-dimethylammonium chloride ([BTMEDA]Cl, pKb=8.2), 1-butyl-1,4-dimethylpiperazinium chloride ([BDMP]Cl, pKb=9.8), and 1-butyl-4-aza-1-azoniabicyclo[2,2,2]octane chloride ([BDABCO]Cl, pKb=11.1). The SO2 absorption and desorption performance of the molten salt were greatly affected by the basicity of the molten salt. Spectroscopic, X-ray crystallographic, and computational results for the interactions of SO2 with molten salts suggest that two types of SO2-containg species could be generated depending on the basicity of the unquaternized amino group: a dicationic species comprising two different anions, HSO3(-) and Cl(-), and a monocationic species bearing Cl(-) interacting with neutral H2SO3.

Thermophilic biofilter for SO2 removal: performance and microbial characteristics.

A bench-scale thermophilic biofilter was applied to remove SO2 at 60°C in the present study. The SO2 concentration in the inlet stream ranged from 100mg/m(3) to 200mg/m(3). An average SO2 removal efficiency of 93.10% was achieved after developing acclimated organisms that can degrade SO2. The thermophilic biofilter effectively reduced SO2, with a maximum elimination capacity of 50.67g/m(3)/h at a loading rate of 51.44g/m(3)/h. Removal efficiency of the thermophilic biofilter was largely influenced by the water containing rate of the packing materials. The SO2 transfer in the biofilter included adsorption by the packing materials, dissolution in liquid, and microbial degradation. The main product of SO2 degradation was SO4(2-). The temporal shifts in the bacterial community that formed in the biofilter were determined through polymerase chain reaction-denaturing gradient gel electrophoresis and DNA sequence analysis. These shifts revealed a correlation between biofilter performance and bacterial community structure.

Simultaneous adsorption of SO2 and NO from flue gas over mesoporous alumina.

Mesoporous alumina (MA) with a higher ability to simultaneously remove SO2 and NO was prepared by the evaporation-induced self-assembly process. The adsorption capacities of MA are 1.79 and 0.702 mmol/g for SO2 and NO, respectively. The Brunauer-Emmett-Teller method was used to characterize the adsorbent. Simultaneous adsorption of SO2 and NO from flue gas over MA in different operating conditions had been studied in a fixed bed reactor. The effects of temperature, oxygen concentration and water vapour were investigated. The experimental results showed that the optimum temperature for MA to simultaneously remove SO2 and NO was 90°C. The simultaneous adsorption capacities of SO2 and NO could be enhanced by increasing O2 when its concentration was below 5%. The changes of simultaneous adsorption capacities were not obvious when O2 concentration was above 5%. The increase in relative humidity results in an increase after dropping of SO2 adsorption capacity, whereas the adsorption capacity of NO showed an opposite trend. The results suggest that MA is a great adsorbent for simultaneous removal of SO2 and NO from flue gas.