Almond shell activated carbon: adsorbent and catalytic support in the phenol degradation

In this work, two technologies are studied for the removal of phenol from aqueous solution: dynamic adsorption onto activated carbon and photocatalysis. Almond shell activated carbon (ASAC) was used as adsorbent and catalytic support in the phenol degradation process. The prepared catalyst by deposition of anatase TiO₂ on the surface of activated carbon was characterized by scanning electron microscopy, sorption of nitrogen, X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, and pH_ZPC point of zero charge. In the continuous adsorption experiments, the effects of flow rate, bed height, and solution temperature on the breakthrough curves have been studied. The breakthrough curves were favorably described by the Yoon–Nelson model. The photocatalytic degradation of phenol has been investigated at room temperature using TiO₂-coated activated carbon as photocatalyst (TiO₂/ASAC). The degradation reaction was optimized with respect to the phenol concentration and catalyst amount. The kinetics of disappearance of the organic pollutant followed an apparent first-order rate. The findings demonstrated the applicability of ASAC for the adsorptive and catalytic treatment of phenol.     

Pathways and Kinetics on Photocatalytic Destruction of Aqueous Phenol

In this study, the TiO₂ photocatalytic decomposition process of aqueous phenol was investigated. The intermediate products generated in the elementary reaction steps in the mineralization process were experimentally identified as hydroquinone, catechol and hydroxyhydroquinone. The concentration variations of these intermediate products with time passage were traced by high performance liquid chromatograph. The pathways of the decomposition process were given. Based on Langmuir isothermal theory and Langmuir-Hinshelwood mechanism, the multi-compounds competition kinetic model was established. In this model, the observed time-dependent concentrations of phenol and the intermediate products were simulated.     

Toxicity assessment of textile effluents treated by advanced oxidative process (UV/TiO2 and UV/TiO2/H2O2) in the species Artemia salina L.

Textile industry wastes raise a great concern due to their strong coloration and toxicity. The objective of the present work was to characterize the degradation and mineralization of textile effluents by advanced oxidative processes using either TiO₂ or TiO₂/H₂O₂ and to monitor the toxicity of the products formed during 6-h irradiation in relation to that of the in natura effluent. The results demonstrated that the TiO₂/H₂O₂ association was more efficient in the mineralization of textile effluents than TiO₂, with high mineralized ion concentrations (NH ₄ ⁺ , NO ₃ ^? , and SO ₄ ^2? ) and significantly decreased organic matter ratios (represented by the chemical oxygen demand and total organic carbon). The toxicity of the degradation products after 4-h irradiation to Artemia salina L. was not significant (below 10 %). However, the TiO₂/H₂O₂ association produced more toxicity under irradiation than the TiO₂ system, which was attributed to the increased presence of oxidants in the first group. Comparatively, the photogenerated products of both TiO₂ and the TiO₂/H₂O₂ association were less toxic than the in natura effluent.     

Synthesis of magnetic carbon nanotube and photocatalytic dye degradation ability

In this paper, magnetic carbon nanotube (M-CNT) was synthesized. The photocatalytic dye degradation ability of M-CNT in the presence of hydrogen peroxide (H₂O₂) from colored wastewater was studied. Manganese ferrite (MnFe₂O₄) was synthesized in the presence of multiwalled carbon nanotube. Direct Red 23 (DR23), Direct Red 31 (DR31), and Direct Red 81 (DR81) were used as anionic dyes. The characteristics of M-CNT were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscope (SEM). The photocatalytic dye degradation using M-CNT was studied by UV–vis spectrophotometer and ion chromatography (IC). The effects of M-CNT dosage, initial dye concentration, and salt on the degradation of dye were evaluated. Formate, acetate, and oxalate anions were detected as dominant aliphatic intermediates. Inorganic anions (nitrate and sulfate anions) were detected and quantified as the mineralization products of dyes during the degradation process. The results indicated that the M-CNT could be used as a magnetic catalyst to degrade anionic dyes from colored wastewater.     

Photocatalytic degradation of NOx in a pilot street canyon configuration using TiO2-mortar panels

Titanium dioxide is the most important photocatalysts used for purifying applications. If a TiO₂- containing material is left outdoors as a form of flat panels, it is activated by sunlight to remove harmful NOx gases during the day. The photocatalytic efficiency of a TiO₂-treated mortar for removal of NOx was investigated in the frame of this work. For this purpose a fully equipped monitoring system was designed at a pilot site. This system allows the in situ evaluation of the de-polluting properties of a photocatalytic material by taking into account the climatologic phenomena in street canyons, accurate measurements of pollution level and full registration of meteorological data The pilot site involved three artificial canyon streets, a pollution source, continuous NOx measurements inside the canyons and the source as well as background and meteorological measurements. Significant differences on the NOx concentration level were observed between the TiO₂ treated and the reference canyon. NOx values in TiO₂ canyon were 36.7 to 82.0% lower than the ones observed in the reference one. Data arising from this study could be used to assess the impact of the photocatalytic material on the purification of the urban environment.     

Modeling photocatalytic destruction of the organic contaminants in continuous stir flow reactor

Thin-film technique is becoming an industry standard for the preparation of TiO₂-based photocatalyst for organic destruction. The catalyst provides several advantages over the conventional powder TiO₂ in the treatment of wastewater and groundwater. In this study, a continuous stir flow reactor model is developed capable of describing the photocatalytic process. The model incorporates the following fundamental mechanisms: adsorption, diffusion, liquid-film transfer, UV attenuation, and photocatalytic reaction. All of the simulation results indicate that there exists a highly nonlinear relation between each of these parameters and the destruction rate. Various incident light intensities also are incorporated to simulate the energy efficiency. The simulations illustrate that the photocatalytic model can be used to elucidate the effect of process variables. It is also possible to “custom-design” a catalyst for the treatment of a particular waste stream.     

31P-NMR evaluation of organophosphorus pesticides degradation through metal ion promoted hydrolysis

The degradation of some organophosphorus pesticides (OPPs) in the presence of metal ions was studied by ³¹P-NMR spectroscopy. Both ³¹P-NMR and gas chromatography/mass spectroscopy results were used in order to determine the nature of metabolites formed after degradation. The degraded organophosphorus pesticide were investigated for chlorpyrifos and phoxim in the presence of several metal ions including Hg²⁺, Cu²⁺, Cd²⁺, Ni²⁺, Pb²⁺, and Ag⁺. ³¹P-NMR results indicated Ag⁺ and Hg²⁺ ion promoted degradation of OPPs and other metal ions formed complex with OPPs and cannot degrade OPPs. We found that the degradation of chlorpyrifos and phoxim with Ag⁺ or Hg²⁺ led to the formation of O,O-diethyl-O-methyl phosphorothionate, (C₂H₅O)₂(CH₃O)PS, at metal ion/pesticide mole ratios ≤1.0 and completely decomposed at a higher mole ratio of 10. Finally, the method was successfully applied to the degradation study of a number of technical and formulated pesticides in the presence of Ag⁺ ion at a metal ion/pesticide mole ratio of 10.     

珠三角典型城市COVID-19疫情封闭期间臭氧污染的放大效应研究

珠三角地区臭氧(O₃)已经逐步取代颗粒物成为主要大气污染物。对新型冠状病毒肺炎(COVID-19)疫情封闭期间珠三角城市背景污染效应(特别是对O₃的放大效应)进行了量化研究,发现PM_2.5和NO₂质量浓度均为工作日高于节假日,非疫情期高于疫情期。O₃质量浓度节假日高于工作日,其中疫情期节假日浓度最高。减排会增加低温高湿背景下O₃质量浓度,但会降低其极大值,并导致 O₃随温度和相对湿度的变化梯度减弱。疫情封闭期间异地输送对于局地O₃质量浓度的变化贡献突出。叠加疫情封闭影响的春节假期O₃质量浓度比节前工作日增加20.4%~41.7%,与一般年份特征相反,而NO₂降低65.3%~75.6%,降低程度强于一般年份。疫情封闭期春节期间O₃质量浓度比一般年份上升14.0%~25.9%,而NO₂质量浓度降低37.0%~54.5%。低湿晴好的天气为光化学反应提供有利条件,并且疫情封闭扩大了假期人为源减排规模,导致NO_x质量浓度进一步下降,使其对O₃的滴定效应减弱,同时静稳天气有利于O₃浓度的累积,导致局地O₃污染被逐步放大。     

Application of the UAM-V and Use of Indicator Species to Assess Control Strategies for Ozone Reduction in the Lower Fraser Valley of British Columbia

Modelled and measured indicator species ratios of O₃/NOz, O₃/NOy, H₂O₂/HNO₃, HCNO/NOy for the Lower Fraser Valley were compared with VOC-NO_x-O₃ sensitivity threshold values reported in previous studies. Modelled region - specific indicator ratio thresholds derived from 50% NOx and 50% VOC reduction scenarios are provided. They show strongest agreement with the H₂O₂/HNO₃ ratio values found elsewhere. A clear transition region for the LFV from VOC to NOx sensitivity could not be identified, but there is evidence that O₃ concentrations in the western valley, dominated by metropolitan Vancouver, are VOC sensitive, and the more rural eastern valley O₃ concentrations exhibit greater NO_x sensitivity. The UAM-V Process Analysis utility was used to identify physical and chemical mechanisms which contributed to O₃ formation and destruction and indicate the key importance of entrainment from elevated layers generated by the highly complex meteorological conditions in determining near surface O₃ concentrations.     

Effects of aqueous suspensions of titanium dioxide nanoparticles on Artemia salina: assessment of nanoparticle aggregation, accumulation, and toxicity

Aquatic stability and impact of titanium dioxide nanoparticles (TiO₂ NPs, 10–30 nm) were investigated using Artemia salina. Acute exposure was conducted on nauplii (larvae) and adults in seawater in a concentration range from 10 to 100 mg/L TiO₂ NPs for 24 and 96 h. Rapid aggregation occurred in all suspensions of TiO₂ NPs to form micrometer size particles. Yet, both nauplii and adults accumulated the aggregates significantly. Average TiO₂ content in nauplii ranged from 0.47 to 3.19 and from 1.29 to 4.43 mg/g in 24 and 96 h, respectively. Accumulation in adults was higher ranging from 2.30 to 4.19 and from 4.38 to 6.20 mg/g in 24 and 96 h, respectively. Phase contrast microscopy images revealed that Artemia were unable to excrete the particles. Thus, the TiO₂ aggregates filled inside the guts. No significant mortality or toxicity occurred within 24 h at any dose. Lipid peroxidation levels characterized with malondialdehyde concentrations were not statistically different from those of the controls (p?>?0.05). These results suggested that suspensions of the TiO₂ NPs were nontoxic to Artemia, most likely due to the formation of benign TiO₂ aggregates in water. In contrast, both mortality and lipid peroxidation increased in extended exposure to 96 h. Highest mortality occurred in 100 mg/L TiO₂ NP suspensions; 18 % for nauplii and 14 % for adults (LC₅₀?>?100 mg/L). These effects were attributed to the particle loading inside the guts leading to oxidative stress as a result of impaired food uptake for a long period of time.     

2014—2018年洛阳市大气污染变化特征及影响因素研究

研究采用空气质量指数法对2014—2018年洛阳市大气污染变化特征进行了分析,构建了空气污染物浓度的影响指标体系,采用灰色关联法研究了空气污染物浓度与影响因子之间的关联度,得到了影响空气污染物浓度的主要指标因子,并提出了改善洛阳市空气质量的措施。结果表明:洛阳市空气质量指数类别主要为良和轻度污染。2014—2018年空气质量为优良的天数主要出现在春季、夏季和秋季,重度污染和严重污染主要出现在冬季。2018年PM₁₀、PM_2.5、NO₂、SO₂和CO这5项污染物浓度随时间变化呈"V"型,污染主要集中在1—5月和11—12月。O₃浓度随时间变化呈倒"V"型,污染主要集中在4—9月。研究期内PM_2.5、PM₁₀和O₃是主要污染物。市区总人口、工业(综合)能源消耗量、人均生产总值、城市机动车总数、城市房屋施工面积、人均公园绿地面积、建成区绿化覆盖率和一般工业固体废物产生量等8项指标因子与PM_2.5、PM₁₀和O₃的浓度表现出高关联度或较高关联度。     

Temporal evolution of the main processes that control indoor pollution in an office microenvironment: a case study

The aim of this study is to examine the relative contribution of the outdoor concentration, the ventilation rate, the geometric characteristics of the indoor environment (i.e., extent of indoor surfaces and indoor volume), the deposition, and chemical reactions to the indoor air quality of the office microenvironment. For this case study, the NO, NO₂, and O₃ concentrations indoors and outdoors and TVOCs and CO₂ concentrations indoors were measured in an office microenvironment in Athens, Greece, that was ventilated both naturally and mechanically. The calculated ventilation and loss rates and the measured outdoor concentrations of NO, NO₂, and O₃ were set as input to Multi-chamber Indoor Air Quality Model in order to study the temporal variation of the indoor NO, NO₂, and O₃ concentrations. Results showed that when the ventilation rate and outdoor concentration are high, the relative contribution of the transport process contributes significantly, while the chemical process depends on the contemporary interplay between the indoor O₃, NO, and NO₂ concentrations and lighting levels. The significance of each process was further examined by performing sensitivity tests, and it was found that the most important parameters were the deposition velocities, the UV infiltration rates (which determines the indoor chemical reaction rates), the ventilation rates, and the filtration (when a mechanical ventilation system is used). The effect of the hydrocarbon chemistry was not significant.     

Stress ethylene: A bioassay for rhizosphere-applied phytotoxicants

A bioassay for rhizosphere-applied phytotoxicants was developed and evaluated with a broad range of chemicals. Test substances were applied to the rhizosphere of whole, intact bush bean plants (Phaseolus vulgaris L. cv. Bush Blue Lake 290) grown in a solid support medium and the resultant ethylene production was measured to detect the presence of phytotoxic materials. The beans were encapsulated in plastic bags for 2 hr following treatment and then incubated for 24 hr in the dark. Ethylene and ethane accumulating within the bags were quantified via gas-solid chromatography. The application of various concentrations of inorganic and organic chemicals induced various responses. No single equation adequately described the dose-response curves; therefore, a critical value (a statistically significant increase in stress ethylene) was computed for each test substance. A phytotoxic-response threshold for each test substance was defined as the test-substance concentration that caused ethylene production to exceed its respective critical-value concentration. Based on threshold concentrations determined by analysis of stress ethylene production, the relative phytotoxicity rankings of the inorganic test substances were: CdCl₂>CuCl₂>Pb(C₂H₃O₂)₂>LiCl, while those of the organic test substances were 2,4-D esters>paraquat dichloride>1-butanol>2-propanone>2-propanol. Both stress ethylene and ethane production were nonresponsive to hydrogen-ion concentration (measured before application) over a broad pH range. However, significant ethane production was detected at pH 2 and stress ethylene was produced at pH 1. The measurement of stress-induced ethylene provides a rapid and simple means to determine the relative phytoxicity of rhizosphere-applied substances.     

2001—2020年合肥市空气质量变化趋势研究

为系统分析合肥市长时间序列空气质量变化特征,对合肥市2001—2020年SO₂、NO₂和PM₁₀,以及2013—2020年CO、O₃和PM_2.5的浓度特征开展研究。采用Mann-Kendall(M-K)时间趋势检验法分析了6项污染物的时间变化规律,同时考虑了人为活动对污染物小时浓度的影响。结果表明,PM_2.5和O₃是目前影响合肥市空气质量的首要污染物。2014年以来,合肥市PM₁₀、PM_2.5、CO和SO₂年均浓度均呈逐年下降趋势,但NO₂和O₃污染有加剧趋势。合肥市SO₂和颗粒物浓度表现为冬春季节高、夏秋季节低;O₃浓度变化趋势与之相反;NO₂和CO浓度呈秋冬季节高、春夏季节低。     

Monitoring of Fogwater Chemistry in the Gulf Coast Urban Industrial Corridor: Baton Rouge (Louisiana)

Seventeen fog events were sampled in Baton Rouge, Louisiana during 2002–2004 as part of characterizing wet deposition by fogwater in the heavily industrialized corridor along the Louisiana Gulf Coast in the United States. These samples were analyzed for chemical characteristics such as pH, conductivity, total organic and inorganic carbon, total metals and the principal ion concentrations. The dominant ionic species in all samples were NH₄⁺, NO₃⁻, Cl⁻ and SO₄²⁻. The pH of the fogwater sampled had a mean value of 6.7 with two cases of acidic pH of 4.7. Rainwater and fogwater pH were similar in this region. The acidity of fogwater was a result of NO₃⁻ but partly offset by high NH₄⁺. The measured gaseous SO₂ accounted for a small percentage of the observed sulfate concentration, indicating additional gas-to-particle conversion of SO₂ to sulfate in fogwater. The gaseous NO_x accounted for most of the dissolved nitrate and nitrite concentration in fogwater. The high chloride concentration was attributable to the degradation of chlorinated organics in the atmosphere. The metal composition was traced directly to soil-derived aerosol precursors in the air. The major metals observed in fogwater were Na, K, Ca, Fe, Al, Mg and Zn. Of these Na, K, Ca and Mg were predominant with mean concentrations > 100 μM. Al, Fe and Zn were present in the samples, at mean concentrations < 100 μM. Small concentrations of Mn (7.8 μM), Cu (2 μM), Pb (0.07 μM) and As (0.32 μM) were also observed in the fogwaters, and these were shown to result from particulates (PM_2.5) in the atmosphere. The contribution to both ions and metals from the marine sources in the Louisiana Gulf Coast was minimal. The concentrations of all principal ionic species and metals in fogwater were 1–2 orders of magnitude larger than in rainwater. Several linear alkane organic compounds were observed in the fogwater, representing the contributions from petroleum products at concentrations far exceeding their aqueous solubility. A pesticide (atrazine) was also observed in fogwater, representing the contribution from the agricultural activities nearby.     

Impact of ultrasonic treatment on dewaterability of sludge during Fenton oxidation

Fenton oxidation was compared with Fenton oxidation coupled with ultrasonication (Fenton?+?US) for sludge dewatering. Different Fenton reagent (H₂O₂, Fe²⁺) concentrations, pH, and reaction times were studied in different systems on the basis of the specific resistance to filtration (SRF) and capillary suction time (CST). It was found that Fenton?+?US can significantly reduce Fe²⁺ and H₂O₂ dosages and reaction times. After ultrasonication of the system at pH 3, with an ultrasonic frequency of 25 kHz and a sound energy density of 100 W/L, the Fe²⁺, H₂O₂ dosage, and reaction time were reduced by 66.7, 75.0, and 75.0 %, respectively, when compared with Fenton oxidation at the same dewaterability of sludge. The microstructure of sludge and hydroxyl radical (·OH) density in Fenton oxidation and Fenton?+?US was further examined. Fenton?+?US produced more?·?OH in a sludge system than did individual Fenton oxidation. The concentration of?·?OH in Fenton?+?US fell from 79.2 to 6 mg/L over 3.5 h, while the concentration of?·?OH in Fenton oxidation fell from 59.6 to 1 mg/L over 2 h, thus destroying the microstructure of sludge more effectively. Sludge treated using Fenton?+?US for 30 min showed a much thinner and looser microstructure.     

Case studies on summertime measurements of O3, NO2, and SO2 with a DOAS system in an urban semi-industrial region in Athens, Greece

The objective of this study is to analyze the concentrations of SO₂, NO₂, and O₃ measured by a Differential Optical Absorption Spectroscopy (DOAS) system that was operating at the campus of Technological Education Institute of Piraeus during 2008 and 2009 warm periods (July to September) in relation to the prevailing meteorological conditions. The DOAS system was operating in a particularly polluted area of the West part of Attica basin on a continuous basis, measuring the concentration levels of the main pollutants (O₃, NO₂, and SO₂) as well as aromatic hydrocarbon substances (benzene, toluene, and xylene). According to the analysis, the SO₂ concentration levels at this measuring site are rather high and this may be attributed to the characteristics of this measuring site. Proximity of roadways and local circulation are just some of the factors that can affect the concentration levels of monitoring of pollutant concentrations such as NO₂ and surface ozone. The results provide evidence for the occurrence of an atmospheric phenomenon that produces higher ozone concentrations during weekends despite lower concentrations of ozone precursors. This phenomenon is known as the weekend effect.     

Growth impact of O3, NO2 and/or SO2 on pinus taeda

Seedlings of two full-sib families of loblolly pine expressing different degrees of sensitivity to O₃ were exposed to 0.05 ppm O₃, 0.10 ppm NO₂, and/or 0.14 ppm SO₂ for 6 hr/day for 28 consecutive days. The treatments were O₃, NO₂, SO₂ (each used alone), O₃+SO₂, O₃+NO₂, and O₃+NO₂+SO₂. Significant growth suppressions were noted with the relatively sensitive family in all but the the NO₂ alone treatments. The O₃+SO₂ treatment had a more significant effect than O₃ alone, but adding NO₂ had an inconsistent effect. Significant growth suppressions were noted for the relatively non-sensitive family only in the O₃+SO₂ and O₃+SO₂+NO₂ combination treatments. Adding NO₂ to O₃+SO₂ had a slightly stimulatory effect. The relatively sensitive pine family suffered a 30% height growth suppression versus a 14% height growth suppression for the relatively insensitive family when exposed to the 3 pollutant combination. Symptoms were noted on less than 4% of the foliage in the most severe treatments. The pollutant concentrations used in this study were below the National Ambient Air Quality Standards (NAAQS) for each pollutant.     

Evaluation of the effectiveness of red mud-supported catalysts in combination with ozone and TiO<Subscript>2</Subscript> in the treatment of solution containing benzene,toluene, and xylene

Ozone and a Fe²⁺/TiO₂-based catalyst were examined in the degradation of a synthetic solution of benzene toluene and xylene (BTX) in an advanced oxidation process (AOP). The catalyst beads were made from the slurry waste of aluminum production process, by inserting the TiO₂ content and subsequent calcination. The reduction of the BTX concentration load was monitored by the reduction of chemical oxygen demand (COD) and BTX concentration. Different levels were used on factors: pH, time of treatment, initial concentration of BTX, and percentage of TiO₂. The process was conducted in a bubble column reactor with the insertion of catalyst beads. A response surface methodology technique (CCD) was used to build a model based on COD reduction results. The model was optimized using the normal-boundary intersection (NBI) algorithm to maximize COD reduction and minimize the variance attributed to the process. Optimization led to COD reductions of 80% in 2 h of experiment. Correlation analysis of coefficient models from experimental data R²_adj was 0.9966, showing a good fit of model data. In the optimized conditions, the possible increase of the biodegradability ratio of the BTX solution, through the biochemical oxygen demand (BOD) and COD, was also analyzed. Under pre-treatment conditions, the BOD/COD ratio was 0.13. After the treatment, it increased to 0.56.

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Comparison of Numerical and Experimental Results for the Evaluation of the Depollution Effectiveness of Photocatalytic Coverings in Street Canyons

Towards the aim of improving the air quality in the urban environment via the application of innovative TiO₂ based photocatalytic coverings, a field campaign took place within the frame of the EU PICADA project () to asses the expected depollution efficiency of such materials under realistic conditions. Furthermore, extensive numerical modeling was performed via the application of the RANS CFD code for microscale applications MIMO, in an effort to asses the sensitivity of the developing flow field and the corresponding dispersion mechanism and hence of the depollution efficiency of the PICADA products on a wide range of factors, with most notably the length of the street canyon, the thermal exchange between the heated street canyon walls and the air and the approaching wind direction. For the needs of the PICADA project a new, simple module had to be implemented into MIMO to be able to model the removal of NO_x from a street canyon whose walls have been treated with a photocatalytic product. The model simulations results presented in this paper, show that MIMO is indeed capable of predicting the effectiveness of the photocatalytic products in question. At the same time, they reveal a strong dependence of the developing flow and concentration fields inside the field site street canyon configuration on most of the aforementioned factors with most notably the direction of the approaching wind.