Removal of elemental mercury with Mn/Mo/Ru/Al2O3 membrane catalytic system

In this work, a catalytic membrane using Mn/Mo/Ru/Al₂O₃ as the catalyst was employed to remove elemental mercury (Hg⁰) from flue gas at low temperature. Compared with traditional catalytic oxidation (TCO) mode, Mn/Al₂O₃ membrane catalytic system had much higher removal efficiency of Hg⁰. After the incorporation of Mo and Ru, the production of Cl₂ from the Deacon reaction and the retainability for oxidants over Mn/Al₂O₃ membrane were greatly enhanced. As a result, the oxidization of Hg⁰ over Mn/Al₂O₃ membrane was obviously promoted due to incorporation of Mo and Ru. In the presence of 8 ppmv HCl, the removal efficiency of Hg⁰ by Mn/Mo/Ru/Al₂O₃ membrane reached 95% at 423 K. The influence of NO and SO₂ on Hg⁰ removal were insignificant even if 200 ppmv NO and 1000 ppmv SO₂ were used. Moreover, compared with the TCO mode, the Mn/Mo/Ru/Al₂O₃ membrane catalytic system could remarkably reduce the demanded amount of oxidants for Hg⁰ removal. Therefore, the Mn/Mo/Ru/Al₂O₃ membrane catalytic system may be a promising technology for the control of Hg⁰ emission.     

中国地区大气汞的数值模拟研究

结合中国地区的汞排放,利用引入大气汞化学反应机制和干沉降模型的区域大气环境模式系统(Regional Atmospheric Environment Model System,Reg AEMS),对中国地区大气汞化物浓度和干沉降通量的时空分布特征进行模拟研究。研究结果表明,中国地区年均气态零价汞Hg0、氧化汞Hg O、氢氧化汞Hg(OH)2、氯化汞Hg Cl2和颗粒态汞HgP的沉降量分布类似。除西部、西北部地区Hg0的浓度较低外(0.5 ng·m-3),其他地区均高于全球背景浓度。各类汞化物浓度的季节变化明显,8月最低,2、3月最高。一次汞源区附近汞浓度随高度递减,在离源较远的地区,高层汞浓度较高。气态零价汞的干沉降速度的季节变化最明显,其干沉降通量在夏季最高。模拟区域中气态零价汞、氧化汞和颗粒态汞的年干沉降量分别为163.9、7.43和32.2 t。     

New insights into mercury removal mechanism on CeO<Subscript>2</Subscript>-based catalysts: A first-principles study

First-principles calculations were performed to investigate the mechanism of Hg⁰ adsorption and oxidation on CeO₂(111). Surface oxygen activated by the reduction of Ce⁴⁺ to Ce³⁺ was vital to Hg⁰ adsorption and oxidation processes. Hg0 was fully oxidized by the surface lattice oxygen on CeO₂(111), without using any other oxidizing agents. HCl could dissociate and react with the Hg adatom on CeO₂(111) to form adsorbed Hg–Cl or Cl–Hg–Cl groups, which promoted the desorption of oxidized Hg and prevented CeO₂ catalyst deactivation. In contrast, O–H and H–O–H groups formed during HCl adsorption consumed the active surface oxygen and prohibited Hg oxidation. The consumed surface oxygen was replenished by adding O₂ into the flue gas. We proposed that oxidized Hg desorption and maintenance of sufficient active surface oxygen were the rate-determining steps of Hg⁰ removal on CeO₂-based catalysts. We believe that our thorough understanding and new insights into the mechanism of the Hg⁰ removal process will help provide guidelines for developing novel CeO₂-based catalysts and enhance the Hg⁰ removal efficiency.

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Spectroscopic studies and biological evaluation of some transition metal complexes of a novel Schiff base ligands derived from 5-arylazo-salicyladehyde and o-amino phenol

Synthesis and characterization of Cu(II), Ni(II), and Zn(II) Schiff bases complexes resulted from the condensation of salicylaldehyde derivatives with o-amino phenol were discussed using elemental analysis (carbon, hydrogen, and nitrogen), molar conductance, magnetic measurements, mass spectra, and electronic spectra. The essential bands of infrared, ¹HNMR, and UV-Vis spectra as well as thermogravimetric analysis corresponding to the active groups within the three ligands and their complexes were interpreted. The dehydration and decomposition processes of the [Cu(H₂L₁)(H₂O)](OAc)₂, [Ni(H₂L₁)(H₂O)]SO₄ · H₂O, [Zn(H₂L₁)(H₂O)]SO₄ · H₂O, [Cu(H₂L₂)(H₂O)](OAc)₂, [Ni(H₂L₂)(H₂O)]SO₄ · H₂O, [Zn(H₂L₂)(H₂O)]SO₄ · 2H₂O, [Cu(H₂L₃)(H₂O)](OAc)₂ · H₂O, [Ni(H₂L₃)(H₂O)]SO₄ · 2H₂O, [Zn(H₂L₃)(H₂O)]SO₄ complexes were studied thermodynamically using the integral method applying the Coats–Redfern and Horowitz–Metzger equations and the thermodynamic parameters were calculated. It was found from the elemental analysis and the thermal studies, that the ligand behaves as tridentate ligand forming chelates with 1 : 1 (metal : ligand) stoichiometrically. The molar conductance measurements of the complexes in dimethyl sulfoxide solvent indicate that the complexes have an electrolytic nature. The biological activities of the three ligands in comparison with metal(II) complexes were studied against different Gram positive and Gram negative bacteria.     

Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl^? formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH? radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH? radicals together. With the inhibition of OH? radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH? were proposed in this study.     

Static and dynamic characteristics of SO<Subscript>2</Subscript>-O<Subscript>2</Subscript> aqueous solution in the microstructure of porous carbon materials

Porous carbon material facilitates the reaction SO₂ + O₂ + H₂O → H₂SO₄ in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H₂O, SO₂ and O₂) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO₂ and O₂ by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H₂O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.

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Bioreduction of nitrate in groundwater using a pilot-scale hydrogen-based membrane biofilm reactor

A long-term pilot-scale H₂-based membrane biofilm reactor (MBfR) was tested for removal of nitrate from actual groundwater. A key feature of this second-generation pilot MBfR is that it employed lower cost polyester hollow fibers and still achieved high loading rate. The steady-state maximum nitrate surface loading at which the effluent nitrate and nitrite concentrations were below the Maximum Contaminant Level (MCL) was at least 5.9 g·N·(m²·d)^?1, which corresponds to a maximum volumetric loading of at least 7.7 kg·N·(m³·d) ^?1. The steady-state maximum nitrate surface area loading was higher than the highest nitrate surface loading reported in the first-generation MBfRs using composite fibers (2.6 g·N·(m²·d)^?1). This work also evaluated the H₂-utilization efficiency in MBfR. The measured H₂ supply rate was only slightly higher than the stoichiometric H₂-utilization rate. Thus, H₂ utilization was controlled by diffusion and was close to 100% efficiency, as long as biofilm accumulated on the polyester-fiber surface and the fibers had no leaks.     

Speciation of mercury in South African coals

Total mercury (Hg_TOT) concentrations were determined by inductively coupled plasma mass spectrometry (ICP MS) for South African Highveld coals. The distribution of Hg in coals was investigated using a four-stage sequential leaching protocol and isotope dilution/gas chromatography coupled to ICP MS (ID-GC-ICP MS). The results show that Hg_TOT ranged from 144 to 303?µg?kg^?1 with a mean of 199?±?26?µg?kg^?1, while Hg_TOT leached from coals using different solvents ranged between 103 and 310?µg?kg^?1 (mean: 218?±?60?µg?kg^?1). Hg leaching rates of 53–78% were achieved in crushed coals. Hg⁰, Hg²⁺, and CH₃Hg⁺ were identified in all coals. CH₃Hg⁺ in studied coals ranged between 0.1 and 0.4 (mean: 0.2) µg?kg^?1. GC ICP MS chromatograms also showed unknown Hg peaks which were identified as other organomercury species such as ethylmercury. Modes of occurrence of Hg in coals were variable with the organic-bound (37–40%) and the sulfide-bound (37–39%) being the dominant mercury forms. Increasing the HCl concentration in the used protocol increased the amount of Hg leached (16%) during this step.     

Removal of cyanide in aqueous solution by oxidation with hydrogen peroxide in presence of activated alumina

This work is dedicated to the removal of free cyanide from aqueous solution by oxidation with hydrogen peroxide H₂O₂ catalyzed by neutral activated alumina. Effects of initial molar ratio [H₂O₂]₀/[CN^?]₀, catalyst amount, pH, and temperature on cyanide removal have been examined. The presence of activated alumina has increased the reaction rate showing thus, a catalytic activity. The rate of removal of cyanides increases with rising initial molar ratio [H₂O₂]₀/[CN^?]₀ but decreases at pH 10 to 12. Increasing the alumina amount from 1.0 to 30 g/L has a beneficial effect, and increasing the temperature from 20 °C to 35 °C improves cyanide removal. The kinetics of cyanide removal has been found to be of pseudo-first-order with respect to cyanide and the rate constants have been determined.     

五氧化二钒类Fenton降解邻苯二甲酸二乙酯的机制研究

发展了基于五氧化二钒(V_2O_5)和过氧化氢(H_2O_2)的新型类Fenton体系,探索了此体系产生羟基(·OH)的机制及降解邻苯二甲酸二乙酯(DEP)的效率;并考察了V_2O_5投加量、H_2O_2浓度,以及草酸对DEP降解的影响。结果表明,当V_2O_5投加量为0.1 g·L-1,H_2O_2浓度为2.0 mmol·L-1,反应24 h后,对DEP(25 mg·L-1)的降解率可达61.1%,增加或降低V_2O_5投加量和H_2O_2浓度均不利于DEP的降解。利用电子顺磁共振技术(Electron Paramagnetic Resonance,EPR)耦合5,5-二甲基-1-吡咯啉氮氧化物(DMPO)为捕获剂对反应体系中的主导自由基进行鉴定,发现·OH是体系降解DEP的主要活性物种,利用苯甲酸作为探针分子实现了·OH的间接定量,并初步推测了V_2O_5活化H_2O_2的过程。     

中国地区大气汞的干沉降速度

借助箱模式对汞的干沉降过程进行敏感性分析,并利用区域大气环境模式系统RegAEMS计算中国地区汞干沉降速度的时空分布特征。结果表明,森林下垫面下三类汞（气态零价汞、活性气态汞和颗粒态汞）的干沉降速度较大( 0.13、4.5和0.45 cm·s^-1),水体表面上的相对较小（0.0012,0.5和0.11 cm·s^-1）。敏感性分析发现,三类汞的干沉降速度随着近地层风速增加;降水或者地表湿度降低会导致零价汞和活性气态汞干沉降速度增加;雪盖厚度会减小气态零价汞的干沉降速度而增加活性气态汞的干沉降速度。三类汞的干沉降速度在区域上分布类似,东北以及南部地区最高,华东地区最小。季节变化上,气态零价汞、活性气态汞的干沉降速度在多数下垫面都夏季最大,冬季最小;颗粒态汞季节变化不明显。     

Low-cost and efficient adsorbent derived from pyrolysis of Jatropha curcas seeds for the removal of Cu2+ from aqueous solutions

Biochar, is a low-cost material that can be used as an alternative adsorbent for the removal of heavy metals. In this study, a low-cost and efficient adsorbent synthesised from Jatropha curcas seeds was used for the uptake of Cu²⁺ from aqueous solutions. The as-prepared adsorbent was characterised by scanning electron microscopy and Brunauer–Emmett–Teller analysis post calcination at 500 °C, its BET surface area and total pore volume were 39.62?m²?g^?1 and 0.049?m³?g^?1, respectively. Subsequently, the effects of initial pH of the solution, contact time, and adsorbent material dosage on the adsorption of Cu²⁺ by the prepared adsorbent were investigated. The as-prepared adsorbent exhibited a high performance, with a maximum adsorption amount of 32.895?mg?g^?1 for Cu²⁺ at pH 5.0 and 25 °C, owing to the presence of ?OH, C=O, C–O, Si-O-Si, and O-Si-O on its surface. The predominant Cu²⁺ adsorption mechanism was assumed to be ion exchange. Notably, the Cu²⁺ adsorption could attain equilibrium within 90?min. In addition, the fact that the Langmuir model was a better fit than the Freundlich model for the isotherm data of Cu²⁺ adsorption by the as-prepared adsorbent suggested that the adsorption of Cu²⁺ was a monolayer adsorption process.     

Sonocatalytic degradation of tetracycline antibiotic in aqueous solution by sonocatalysis

Tetracycline (TC), one of the most common antibiotics, is often poorly bio-degraded in conventional wastewater treatment plants. In this study, the sonocatalytic degradation of TC was investigated using TiO₂ nano-particles as catalyst. The effect of pH, initial TC concentrations, reaction times, and H₂O₂ concentrations were evaluated. The efficacy of ultrasonic irradiation alone in the removal of this pollutant was negligible but removal efficiency increased upon addition of TiO₂ up to 250 mg L^?1; increase of pH and initial TC concentration attenuated TC degradation. Addition of H₂O₂ raised the removal efficiency so that complete removal of TC was achieved within 75 min.     

Inorganic mercury and methylmercury in surface sediments and mussel tissues from a microtidal lagoon (Bizerte, Tunisia)

The aim of this study was to investigate the distribution of mercury compounds in marine sediments and mussel tissues collected in the lagoon of Bizerte, Tunisia, during two seasons (summer and winter). Inorganic mercury (Hg²⁺) concentrations in sediments were found to be highly variable, ranging from 0.04 nmol.g¹ to 3.22 nmol.g⁻¹ (dry weight) with a mean value of 0.52 nmol.g⁻¹. Anthropogenic sources of Hg²⁺, most probably metallurgy or tire production industries, have been evidenced. The mean concentration of monomethylmercury (MeHg⁺) in the surface sediments is 2.32 pmol g⁻¹ ranging from below the detection limit (0.45 pmol.g⁻¹) to 14.6 pmol.g⁻¹. No significant variation was observed between winter and summer seasons for both mercury species concentration in the sediments. The Hg²⁺ concentrations in mussel tissues are also variable, ranging from 0.007 to 1.347 nmol.g⁻¹ (dry weight). The mean concentration is 0.70 nmol.g⁻¹. In these tisssues, Hg²⁺ is generally the major compound, making up ca. 88% of total mercury concentrations. However, methylmercury concentrations are significant and homogeneous, ranging from 62 to 121 pmol.g⁻¹ (mean 96 pmol.g⁻¹). The results suggest that a fraction of the inorganic mercury load in the sediments of the lagoon undergoes methylation pathways. MeHg⁺ produced is assimilated in the mussels more readily than Hg²⁺.     

Inhibitory effect of the iron chelator desferrioxamine (Desferal) on the generation of activated oxygen species by Chattonella marina

Recent studies demonstrated that the toxic red tide phytoplankton Chattonella spp. produce activated oxygen species such as superoxide anion (O ₂ ^- ), hydrogen peroxide (H₂O₂), and hydroxyl radicals (·OH), which may be responsible for the toxicity of this flagellate. However, the mechanism behind the production of these oxygen radicals and H₂O₂ by Chattonella spp. is largely unknown, and the physiological significance of activated oxygen species for Chattonella spp. is also unclear. In the present study, we investigated the involvement of iron in the generation of O ₂ ^- and H₂O₂ by C. marina. The generation of O ₂ ^- by C. marina was related to the growth phase; the highest rate of O ₂ ^- production was observed during the exponential growth phase. However, no such increase during the exponential growth phase was observed in C. marina growing in an iron-deficient medium, even though the growth of C. marina was not significantly affected by iron-deficiency during the first 4 d. In addition, the iron chelator desferrioxamine (Desferal) strongly inhibited the generation of both O ₂ ^- and H₂O₂ by C. marina in a concentration-dependent manner. The growth of C. marina was also inhibited by Desferal. Furthermore, in the presence of 500 M Desferal, C. marina-induced growth inhibition of the marine bacteria Vibrio alginolyticus was almost completely abolished. These results suggest that iron is required for the generation of activated oxygen species by C. marina, as well as for its own growth.     

Principal Biogeochemical Factors Affecting the Speciation And Transport of Mercury through the terrestrial environment

It is increasingly becoming known that mercury transport and speciation in the terrestrial environment play major roles in methyl-mercury bioaccumulation potential in surface water. This review discusses the principal biogeochemical reactions affecting the transport and speciation of mercury in the terrestrial watershed. The issues presented are mercury-ligand formation, mercury adsorption/desorption, and elemental mercury reduction and volatilization. In terrestrial environments, OH^–, Cl^– and S^– ions have the largest influence on ligand formation. Under oxidized surface soil conditions Hg(OH)₂, HgCl₂, HgOH⁺, HgS, and Hg⁰ are the predominant inorganic mercury forms. In reduced environments, common mercury forms are HgSH⁺, HgOHSH, and HgClSH. Many of these mercury forms are further bound to organic and inorganic ligands. Mercury adsorption to mineral and organic surfaces is mainly dictated by two factors: pH and dissolved ions. An increase in Cl^– concentration and a decrease in pH can, together or separately, decrease mercury adsorption. Clay and organic soils have the highest capability of adsorbing mercury. Important parameters that increase abiotic inorganic mercury reduction are availability of electron donors, low redox potential, and sunlight intensity. Primary factors that increase volatilization are soil permeability and temperature. A decrease in mercury adsorption and an increase in soil moisture will also increase volatilization. The effect of climate on biogeochemical reactions in the terrestrial watershed indicates mercury speciation and transport to receiving water will vary on a regional basis.     

Characterization and performance of V2O5/CeO2 for NH3-SCR of NO at low temperatures

A series of CeO₂ supported V₂O₅ catalysts with various loadings were prepared with different calcination temperatures by the incipient impregnation. The catalysts were evaluated for low temperature selective catalytic reduction (SCR) of NO with ammonia (NH₃). The effects of O₂ and SO₂ on catalytic activity were also studied. The catalysts were characterized by specific surface areas (S_BET) and X-ray diffraction (XRD) methods. The experimental results showed that NO conversion changed significantly with the different V₂O₅ loading and calcination temperature. With the V₂O₅ loading increasing from 0 to 10 wt%, NO conversion increased significantly, but decreased at higher loading. The optimum calcination temperature was 400°C. The best catalyst yielded above 80% NO conversion in the reaction temperature range of 160°C–300°C. The formation of CeVO₄ on the surface of catalysts caused the decrease of redox ability.     

Synthetischer Crandallit

Crandallite (Ca,Sr) Al₃ (PO₄)₂ (OH)₅ · H₂O crystallizes in the alunitecrystal lattice. Because of its open structure, the cations Ca²⁺, Sr²⁺, and Al³⁺ can be replaced by various elements depending on their diadochial properties; the element entering into the crystal network thus becomes immobilized. Artificial amorphous crandallite has been shown to eliminate the heavy metal ions: Pb²⁺>>Cu²⁺>Hg²⁺>>Cd²⁺ from contamined water in the presence of lateritic phosphates. Pb²⁺ could be removed nearly quantitatively in all cases.     

Rate evaluation of marble damage by SO2-acidity in the vicinity of stacks

A laboratory modelling for the assessment of damage to marble by the SO₂-acidity in the vicinity of stacks has been devised. The modelling is based on the role of metal oxide particulates (also emitted by smoke-stacks) which catalytically convert SO₂ to SO₃ forming H₂SO₄ (in presence of water), which has an excessively high selectivity, compared with HNO₃, for corroding marble. The requisites of the modelling are: (1) determination of composition of the marble, (2) immersion of samples of marble blocks (after measurement of surface areas) in H₂SO₄ solutions of known concentrations, maintaining pH and temperature at their initial values, (3) determination of concentrations of Ca and Mg (major components of marble) in the leachate, and thereby evaluating the mass loss of the marble, in terms of mg marble cm^–2 day^–1, for each level of H₂S0₄ concentration, (4) application of derived data for evaluation of duration (in years) for the decay of 1 cm thickness of marble block by the process of surface corrosion. From the modelling, it was found that the duration for the damage of 1 cm thickness of the marble sample used here by SO₂ acidities of 1, 5, 10, 50 and 100 ppm are 83.01, 69.02, 31.24, 8.19 and 4.31 years respectively.