Phosphate recovery with granular acid-activated neutralized red mud: Fixed-bed column performance and breakthrough curve modelling

Granular acid-activated neutralized red mud (AaN-RM) has been successfully prepared with good chemical stability and physical strength. However, its potential for industrial application remains unknown. Therefore, the performance of granular AaN-RM for phosphate recovery in a fixed-bed column was investigated. The results demonstrated that the phosphate adsorption performance of granular AaN-RM in a fixed-bed column was affected by various operational parameters, such as the bed depth, flow rate, initial solution pH and initial phosphate concentration. With the optimal empty-bed contact time (EBCT) of 24.27 min, the number of processed bed volumes and the phosphate adsorption capacity reached 496.95 and 84.80 mg/g, respectively. Then, the saturated fixed-bed column could be effectively regenerated with a 0.5 mol/L HCl solution. The desorption efficiency remained as high as 83.45% with a low weight loss of 3.57% in the fifth regeneration cycle. In addition, breakthrough curve modelling showed that a 5-9-1 feed-forward artificial neural network (ANN) could be effectively applied for the optimization of the fixed-bed adsorption system; the coefficient of determination (R²) and the root mean square error (RMSE) evaluated on the validation-testing data were 0.9987 and 0.0183, respectively. Therefore, granular AaN-RM fixed-bed adsorption exhibits promising potential for phosphate removal and recovery from polluted water.     

Hygroscopicity measurement of sodium carbonate, β-alanine and internally mixed β-alanine/Na2CO3 particles by ATR-FTIR

Water-uptakes of pure sodium carbonate(Na_2CO_3),pure β-alanine and internally mixedβ-alanine/Na_2CO_3 aerosol particles with different mole ratios are first monitored using attenuated total reflectance Fourier transform infrared spectroscopy(ATR-FTIR) technique.For pure Na_2CO_3 aerosol particles,combining the absorptions at 877 and 1422 cm-1 with abrupt water loss shows the efflorescence relative humidity(ERH) of 62.9%–51.9%.Upon humidifying,solid Na_2CO_3 firstly absorbs water to from Na_2CO_3·H2 O crystal at 72.0% RH and then deliquesces at 84.5% RH(DRH).As for pure β-alanine particles,the crystallization takes place in the range of 42.4%–33.2% RH and becomes droplets at ～ 88.2% RH.When β-alanine is mixed with Na_2CO_3 at various mole ratios,it shows no efflorescence of Na_2CO_3 whenβ-alanine to Na_2CO_3 mole ratio(OIR) is 2:1.For 1:1 and 1:2 β-alanine/Na_2CO_3 aerosols,the ERHs of Na_2CO_3 are 51.8%–42.3% and 57.1%–42.3%,respectively.While β-alanine crystal appears from 62.7% RH for 2:1 and 59.4% RH for both 1:1 and 1:2 particles and lasts to driest state.On hydration,the DRH is 44.7%–75.2% for Na_2CO_3 with the OIR of 1:1 and 44.7%–69.0%for 1:2 mixture,and those of β-alanine are 74.8% for 2:1 mixture and 68.9% for two others.After the first dehumidification–humidification,all the water contents decrease despite of constituent fraction.And at ～ 92% RH,the remaining water contents are 92%,89% and 82%at ～ 92% RH,corresponding to OIR of 2:1,1:1 and 1:2 mixed system,respectively.     

Cytotoxicity of the soluble and insoluble fractions of atmospheric fine particulate matter

Inhaled atmospheric fine particulate matter(PM_(2.5)) includes soluble and insoluble fractions,and each fraction can interact with cells and cause adverse effects.PM_(2.5) samples were collected in Jinan,China,and the soluble and insoluble fractions were separated.According to physiochemical characterization,the soluble fraction mainly contains watersoluble ions and organic acids,and the insoluble fraction mainly contains kaolinite,calcium carbonate and some organic carbon.The interaction between PM_(2.5) and model cell membranes was examined with a quartz crystal microbalance with dissipation(QCM-D) to quantify PM_(2.5) attachment on membranes and membrane disruption.The cytotoxicity of the total PM_(2.5) and the soluble and insoluble fractions,was investigated.Negatively charged PM_(2.5) can adhere to the positively charged membranes and disrupt them.PM_(2.5)also adheres to negatively charged membranes but does not cause membrane rupture.Therefore,electrostatic repulsion does not prevent PM_(2.5) attachment,but electrostatic attraction induces remarkable membrane rupture.The human lung epithelial cell line A549 was used for cytotoxicity assessment.The detected membrane leakage,cellular swelling and blebbing indicated a cell necrosis process.Moreover,the insoluble PM_(2.5) fraction caused a higher cell mortality and more serious cell membrane damage than the soluble fraction.The levels of reactive oxygen species(ROS) enhanced by the two fractions were not significantly different.The findings provide more information to better understand the mechanism of PM_(2.5) cytotoxicity and the effect of PM_(2.5) solubility on cytotoxicity.     

Density functional theory (DFT) studies of vanadium-titanium based selective catalytic reduction (SCR) catalysts

Based on density functional theory (DFT) and basic structure models, the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction (SCR) denitrification catalysts were summarized. Reasonable structural models (non-periodic and periodic structural models) are the basis of density functional calculations. A periodic structure model was more appropriate to represent the catalyst surface, and its theoretical calculation results were more comparable with the experimental results than a non-periodic model. It is generally believed that the SCR mechanism where NH₃ and NO react to produce N₂ and H₂O follows an Eley-Rideal type mechanism. NH₂NO was found to be an important intermediate in the SCR reaction, with multiple production routes. Simultaneously, the effects of H₂O, SO₂ and metal on SCR catalysts were also summarized.     

Effect of NOx and SO2 on the photooxidation of methylglyoxal: Implications in secondary aerosol formation

Methylglyoxal(CH_3COCHO,MG),which is one of the most abundant α-dicarbonyl compounds in the atmosphere,has been reported as a major source of secondary organic aerosol(SOA).In this work,the reaction of MG with hydroxyl radicals was studied in a 500 L smog chamber at(293±3) K,atmospheric pressure,(18±2)% relative humidity,and under different NOx and SO_2.Particle size distribution was measured by using a scanning mobility particle sizer(SMPS) and the results showed that the addition of SO_2 can promote SOA formation,while different NOx concentrations have different influences on SOA production.High NOx suppressed the SOA formation,whereas the particle mass concentration,particle number concentration and particle geometric mean diameter increased with the increasing NOx concentration at low NOx concentration in the presence of SO_2.In addition,the products of the OH-initiated oxidation of MG and the functional groups of the particle phase in the MG/OH/SO_2 and MG/OH/NOx/SO_2 reaction systems were detected by gas chromatography mass spectrometry(GC-MS) and attenuated total reflection fourier transformed infrared spectroscopy(ATR-FTIR) analysis.Two products,glyoxylic acid and oxalic acid,were detected by GC-MS.The mechanism of the reaction of MG and OH radicals that follows two main pathways,H atom abstraction and hydration,is proposed.Evidence is provided for the formation of organic nitrates and organic sulfate in particle phase from IR spectra.Incorporation of NOx and SO_2 influence suggested that SOA formation from anthropogenic hydrocarbons may be more efficient in polluted environment.     

Plasmonic silver/silver oxide nanoparticles anchored bismuth vanadate as a novel visible-light ternary photocatalyst for degrading pharmaceutical micropollutants

The degradation of pharmaceutical micropollutants is an intensifying environmental problem and synthesis of efficient photocatalysts for this purpose is one of the foremost challenges worldwide. Therefore, this study was conducted to develop novel plasmonic Ag/Ag₂O/BiVO₄ nanocomposite photocatalysts by simple precipitation and thermal decomposition methods, which could exhibit higher photocatalytic activity for mineralized pharmaceutical micropollutants. Among the different treatments, the best performance was observed for the Ag/Ag₂O/BiVO₄ nanocomposites (5 wt.%; 10 min's visible light irradiation) which exhibited 6.57 times higher photodegradation rate than the pure BiVO₄. Further, the effects of different influencing factors on the photodegradation system of tetracycline hydrochloride (TC-HCl) were investigated and the feasibility for its practical application was explored through the specific light sources, water source and cycle experiments. The mechanistic study demonstrated that the photogenerated holes (h⁺), superoxide radicals (?O₂^?) and hydroxyl radicals (?OH) participated in TC-HCl removal process, which is different from the pure BiVO₄ reaction system. Hence, the present work can provide a new approach for the formation of novel plasmonic photocatalysts with high photoactivity and can act as effective practical application for environmental remediation.     

Algal toxicity induced by effluents from textile-dyeing wastewater treatment plants

This research aimed to evaluate the alga Scenedesmus obliquus toxicity induced by textiledyeing effluents(TDE).The toxicity indicator of TDE in alga at the physiological(algal growyth),biochemical(chlorophyll-a(Chl-a) synthesis and superoxide dismutase(SOD) activity) and structural(cell membrane integrity) level were investigated.Then we further study the relationship among toxicity indicators at physiological and biochemical level,and supplemented by research on algal biomacromolecules.According to the analysis of various endpoints of the alga,the general sensitivity sequence of toxicity endpoints of Scenedesmus obliquus was:SOD activity Chl-a synthesis algal growth.The stimulation rate of SOD activity increased from day 3(57.25%～83.02%) to day 6(57.25%～103.81%),and then decreased on day 15(-4.23%～-32.96%),which indicated that the antioxidant balance system of the algal cells was destroyed.The rate of Chl-a synthesis inhibition increased gradually,reaching19.70%～79.39% on day 15,while the rate of growth inhibition increased from day 3(-12.90%～10.16%) to day 15(-21.27%～72.46%).Moreover,the algal growth inhibition rate was positively correlated with the inhibition rate of SOD activity or Chl-a synthesis,with the correlation coefficients were 0.6713 and 0.5217,respectively.Algal cells would be stimulating to produce excessive reactive oxygen species,which would cause peroxidation in the cells,thereby destroying chloroplasts,inhibiting chlorophyll synthesis and reducing photosynthesis.With increasing exposure time,irreversible damage to algae can lead to death.This study is expected to enhance our understanding of the ecological risks through algal tests caused by TDE.     

UV/H2O2 oxidation of tri(2-chloroethyl) phosphate: Intermediate products, degradation pathway and toxicity evaluation

Tri(2-chloroethyl) phosphate (TCEP) with the initial concentration of 5 mg/L was degraded by UV/H₂O₂ oxidation process. The removal rate of TCEP in the UV/H₂O₂ system was 89.1% with the production of Cl^? and PO₄^3? of 0.23 and 0.64 mg/L. The removal rate of total organic carbon of the reaction was 48.8% and the pH reached 3.3 after the reaction. The oxidative degradation process of TCEP in the UV/H₂O₂ system obeyed the first order kinetic reaction with the apparent rate constant of 0.0025 min^?1 (R²=0.9788). The intermediate products were isolated and identified by gas chromatography-mass spectrometer. The addition reaction of HO? and H₂O and the oxidation reaction with H₂O₂ were found during the degradation pathway of 5 mg/L TCEP in the UV/H₂O₂ system. For the first time, environment risk was estimated via the “ecological structure activity relationships” program and acute and chronic toxicity changes of intermediate products were pointed out. The luminescence inhibition rate of photobacterium was used to evaluate the acute toxicity of intermediate products. The results showed that the toxicity of the intermediate products increased with the increase of reaction time, which may be due to the production of chlorine compounds. Some measures should be introduced to the UV/H₂O₂ system to remove the highly toxic Cl-containing compounds, such as a nanofiltration or reverse osmosis unit.     

Coupling mechanism of activated carbon mixed with dust for flue gas desulfurization and denitrification

To clarify the effect of coking dust, sintering dust and fly ash on the activity of activated carbon for various industrial flue gas desulfurization and denitrification, the coupling mechanism of the mixed activated carbon and dust was investigated to provide theoretical reference for the stable operation. The results show that coking dust had 34% desulfurization efficiency and 10% denitrification efficiency; correspondingly, sintering dust and fly ash had no obvious desulfurization and denitrification activities. For the mixture of activated carbon and dust, the coking dust reduced the desulfurization and denitrification efficiencies by blocking the pores of activated carbon, and its inhibiting effect on activated carbon was larger than its own desulfurization and denitrification activity. The sintering dust also reduced the desulfurization efficiency on the activated carbon while enhancing the denitrification efficiency. Fly ash blocked the pores of activated carbon and reduced its reaction activity. The reaction activity of coking dust mainly came from the surface functional groups, similar to that of activated carbon. The reaction activity of sintering dust mainly came from the oxidative property of Fe₂O₃, which oxidized NO to NO₂ and promoted the fast selectively catalytic reduction (SCR) of NO to form N₂. Sintering dust was activated by the joint action of activated carbon, and both had a coupling function. Sintering dust enhanced the adsorption and oxidation of NO, and activated carbon further promoted the reduction of NO_x by NH₃; thus, the denitrification efficiency increased by 5%-7% on the activated carbon.     

Chemical characteristics of road dust PM2.5 fraction in oasis cities at the margin of Tarim Basin

In order to understand the compositions characteristics of particulate matter with aerodynamic diameter less than 2.5 μm (PM_2.5) fraction in road dust (RD_2.5) of oasis cities on the edge of Tarim Basin, 30 road dust (RD) samples were collected in Kashi, Cele, and Yutian in the spring, 2018, and RD_2.5 was collected using the resuspension approach. Eight water-soluble ions, 39 trace elements and 8 fractions of carbon-containing species in PM_2.5 were analyzed. Ca²⁺ and Ca were the most abundant ions and elements in RD_2.5 (7.1% and 9.5%). Cl^- in RD_2.5 was affected not only by attributed to saline-alkali soils in oasis cities of the Tarim Basin and dust from Taklimakan Desert but also by human activities. Moreover, the organic carbon/elemental carbon (OC/EC) ratio indicated that carbon components in RD_2.5 in Cele town mainly come from fossil fuel combustion, while those in Yutian and Kashi mainly come from biomass combustion. It is noteworthy that high Ca in RD_2.5 was seriously affected by anthropogenic emissions, and high Na and K contents in RD_2.5 could be derived from soil and desert dust. It was estimated that Cd, Tl, Sn and Cr were emitted from anthropogenic emissions using the enrichment factor. The coefficients of divergence (COD) result indicated that the influence of local emission on road dust emission is greater than that of long-distance transmission. This study is the first time to comprehensively analyze the chemical characteristics of road dust in oasis cities, and the results provides the sources of road dust at the margin of Tarim Basin.