Theoretical assessment of phosphate amendments for stabilization of (Pb + Zn) in polluted soil

Contamination of the environment with toxic metals, such as lead (Pb), represents a serious concern for human health. Most of the studies on Pb stabilization were performed using various phosphorus-containing amendments that can reduce Pb mobility and bioavailability by the sorption and precipitation of new, stable pyromorphite-type minerals, presenting very low solubility and bioaccessibility. However, the presence of competing ions, such as zinc (Zn), can reduce stabilization efficacy. The role of chemical composition on the stability of immobilization products of Pb and Zn by the addition of hydroxyapatite (HAP) or fluoroapatite (FAP) has been examined in this paper. In this analysis we used a theoretical criterion which is based on calculation of the ion–ion interaction potential, representing the main term of the cohesive energy of the matrix/pollutant system. It has been demonstrated that the stability of the HAP matrix decreases and that the stability of the FAP matrix increases with the Pb immobilization in the presence of Zn. The results of this analysis point out FAP as an advantageous amendment for the immobilization of Pb in the presence of Zn.     

新型负载型光催化剂的制备及其光催化活性研究

以硝酸钙和磷酸为原料,采用均匀沉淀法制备了羟基磷灰石(HAP);以HAP为载体,采用浸渍-提拉法制得负载型光催化剂TiO2／HAP,并用其对酸性媒介红B进行光催化氧化实验;探讨了HAP煅烧温度和TiO2负载量对TiO2／HAP光催化活性的影响,并利用XRD、FT—IR和TEM对载体及TiO2／HAP催化剂进行了表征。实验结果表明,煅烧温度、TiO2负载量对HAP吸附性能及催化活性有较大的影响;TiO2／HAP的催化活性明显优于TiO2／玻片的催化活性。     

纳米MnO_2/Fe_3O_4对镉离子的静态吸附

采用水热合成法将Mn O_2包覆于纳米Fe_3O_4的表面,制备出纳米Mn O_2/Fe_3O_4,并将其用于含镉溶液的吸附。考察了吸附效果的影响因素,并研究了纳米Mn O_2/Fe_3O_4的重复使用性能。实验结果表明:在初始镉离子质量浓度为10 mg/L、吸附剂投加量为4 g/L、吸附温度为20℃、溶液p H为6.0、吸附时间为12 h的条件下,镉离子去除率由使用纳米Fe_3O_4时的3%增至使用纳米Mn O_2/Fe_3O_4时的96%;在初始镉离子质量浓度为50 mg/L、纳米Mn O_2/Fe_3O_4投加量为4 g/L、吸附温度为20℃、溶液p H为6.0、吸附时间为1 h的条件下,镉离子去除率达78%,吸附量为9.7 mg/g;经5次重复使用后,纳米Mn O_2/Fe_3O_4对镉离子的去除率仅比首次使用时降低了10百分点,具有良好的重复使用性能。     

鞘细菌对镉离子的吸附性能及机理研究

研究了鞘细菌对镉离子的吸附性能及机理。实验结果表明：鞘细菌对镉离子吸附的最佳条件组合为镉离子初始质量浓度25 mg/L、吸附时间30 min、反应温度30 ℃;在此条件下,鞘细菌对镉离子的吸附量和吸附率均达最大值,分别为1 778 mg/g和84.65%;SEM照片显示,与吸附前相比,吸附后的鞘细菌菌体形态发生明显变化,菌体表面变得粗糙,并有大量絮状物沉积;吸附前后鞘细菌的红外光谱谱图显示,羟基、酰胺基、羧基等活性基团参与了镉离子的吸附过程。     

腐殖酸-海泡石复合钝化剂的制备及其对Cd污染土壤的修复

对海泡石进行热改性,以腐殖酸和海泡石为原料,制备了腐殖酸-海泡石复合钝化剂。采用BCR形态分析法研究了复合钝化剂对镉污染土壤的钝化效果。结果表明,制备复合钝化剂的最佳工艺条件为：腐殖酸与海泡石质量比2∶1,氢氧化钠质量浓度0.04 g/mL,热反应时间40 min,热反应温度80 ℃。复合钝化剂的最佳添加量为7%（w）,培养3 d后,钝化效率达46.87%,土壤pH升高至7.02,活稳比降低为0.65,土壤中镉的释放风险显著降低。复合钝化剂修复镉污染土壤时,会促使活性态镉向稳定态镉转化,使镉在土壤中的稳定性提高。     

An examination of the exothermic nature of fluidized bed combustion (FBC) residues

Circulating fluidized bed combustion (CFBC) ashes from nine operational periods at the 183 MWe CFBC boiler at Point Aconi were examined for exothermic behaviour. Bed ashes and fly ashes were investigated using a Parr 1455 solution calorimeter. Limited tests were also carried out with additional samples from Point Aconi and from the 160 MWe TVA Bubbling Fluidized Bed Combustion boiler to evaluate the effects of particle size and aging on exothermic behaviour. For the Point Aconi ashes, heat release from the bed ash ranged from 11 to 52 J/g, and the maximum heat release rates ranged from 0.06 to 0.17 J/g/s. For the fly ash heat release varied from 114 to 187 J/g and the maximum heat release rates ranged from 0.8 to 1.9 J/g/s. In the fly ash samples, 50% or more of available CaO was converted to Ca(OH)₂, while for the bed ash a third or less of the CaO was converted to Ca(OH)₂. The exothermicity of the bed ash is directly proportional to the CaO content of the ash. However, this is not true for the fly ash. The exothermic behaviour of fresh FBC ash appeared to be greatly reduced by exposure in air over a 48-h period. Another conclusion of this work is that particle size effects the exothermic behaviour.     

碳酸盐对化学沉淀法回收废水中磷的影响

研究了溶液中CO_3~(2-)对磷酸铵镁(MAP)法和羟基磷酸钙(HAP)法磷回收率的影响,并对回收磷所得产物进行了傅立叶变换红外光谱和X射线衍射分析.实验结果表明:为使磷回收率达80%以上,MAP法回收磷时n(CO_3~(2-)):n(Mg~(2+))必须小于0.5,HAP法回收磷时n(CO_3~(2-)):n(Ca~(2+))必须小于0.2;溶液中的CO_3~(2-)浓度对MAP法回收产物没有明显影响,但HAP法回收磷产物中会出现大量碳酸钙.     

Synthesis,Characterization and Application of α, β, and γ Cyclodextrin-Conjugated Graphene Oxide for Removing Cadmium Ions from Aqueous Media

In this study, a novel and facile route for the synthesis of cyclodextrin-conjugated graphene oxide (CDs–GO) nanocomposites by esterification reaction in the presence of EDC/DMAP as catalyst, was developed. The formation of CDs–GO was successfully approved by FT-IR, SEM, TEM, TGA and BET analyses. Then competitive adsorption capacity of cadmium ion by CDs–GO composites and the impact of different empirical parameters like contact time, initial metal ion concentration, and initial pH on the adsorption process were studied. The results showed that β-CD–GO at pH 7 is suitable for removing Cd(II) with 90?% removal efficiency. Also, the adsorption capacity experiment at constant concentration of 50 ppm of Cd(II) showed that more than 50?% of Cd(II) ions could be adsorbed by γ-CD–GO reaching an equilibrium within 2 h. Therefore, the γ-CD–GO and α-CD–GO showed high adsorption capacity toward Cd²⁺ (222.22 mg/g) which were pointedly more than that of β-CD–GO (208.33 mg/g). Furthermore, adsorption kinetics, isotherm studies, and thermodynamic analyses were evaluated. The adsorption data exhibited excellent fit to the pseudo-second-order (R²?>?0.99) and Freundlich isotherm models.

     

羟基磷灰石去除废水中的Fe3+

以天然磷矿粉制备的羟基磷灰石(HAP)作为吸附剂,处理模拟含Fe3+废水。实验结果表明,在HAP加入量为1.0g/L、初始模拟废水pH为3.00、反应温度为室温的最佳条件下,处理初始Fe3+质量浓度为150mg/L的模拟废水,反应90min后Fe3+去除率为99.89%,处理后模拟废水中Fe3+质量浓度为0.15mg/L,低于0.30mg/L,达到GB5749—2006《生活饮用水卫生标准》的要求。     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

Adsorption of Pb2+ and Cd2+ on the l-cysteine-functionalized graphene oxide/chitosan/polyvinyl alcohol hydrogel: Kinetic,isotherm, and thermodynamic study

In this study, polyvinyl alcohol-chitosan-cysteine-functionalized graphene oxide (PCCFG) hydrogel was synthesized from l -cysteine-functionalized graphene oxide (CFG), chitosan (CS), and polyvinyl alcohol (PVA). The hydrogel was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy and employed for removing lead ion (Pb²⁺) and cadmium ion (Cd²⁺) from aqueous solution. The effects of initial metal ion concentration, hydrogel dose, pH, time, and temperature were studied. The experimental data were well described by a pseudo-second-order kinetic model and Langmuir isotherm with maximum adsorption capacities of 250 and 192 mg g⁻¹ at 25°C for Pb²⁺ and Cd²⁺, respectively. The adsorption capacity of the PCCFG hydrogel increased with an increase in temperature. The value of ∆G° was negative, which shows the spontaneity of the reaction (electron exchange or ion exchange) between the metal ion and electron-rich atoms (–N, –S, –O). The positive ∆H° shows that the adsorption reaction consumes energy and the positive ∆S° shows the strong affinity of PCCFG toward the Pb²⁺ and Cd²⁺ ions. Pb²⁺ had better affinity and less spontaneity than Cd²⁺. The results show that the coexistence of Pb²⁺, Cd²⁺, and Cu²⁺ in the solution inhibits the adsorption capacity of PCCFG.     

The influence of pH on the leaching behaviour of inorganic components from municipal solid waste APC residues

The influence of pH on the leaching behaviour of air pollution control (APC) residues produced in municipal solid waste incineration (MSWI) is addressed in this study. The residue is considered hazardous waste, and in accordance with their chemical properties, the leaching of contaminants into the environment is the main concern. Several leaching tests can be used for research studies or regulatory purposes, where a wide variety of conditions may be tested. Our work deals mainly with the leaching behaviour of toxic heavy metals (Pb, Cd, Zn, Cr, Ni, Cu) and inorganics associated with soluble salts (Na, K, Ca, Cl). The main goal is to obtain an overview of the leachability of APC residues produced in a Portuguese MSWI process. Among the different variables that may have influence on the leaching behaviour, pH of the leachant solution is the most important one, and was evaluated through pH static tests. The acid neutralization capacity (ANC) of the residue was also determined, which is in the range of 6.2–6.8 meq g^?1 (for pH = 7) and 10.1–11.6 meq g^?1 (for pH = 4). The analysis of the leaching behaviour is particularly important when the leaching is solubility controlled. The amphoteric behaviour of some elements was observed, namely for Pb and Zn, which is characterized through high solubilization at low and high pH and moderate or low solubility at neutral or moderate high pH. The solubility curves for Pb, Cd, Zn, Cr, Ni and Cu as a function of pH were obtained, which are very useful for predicting the leaching behaviour in different scenarios. The solubility of K and Na reveals to be nearly independent of the solution pH and the released amount is mainly availability-controlled. Moreover, the pH static test showed that Cl^? is the most pH-independent species. The APC residue turns out to be a hazardous waste because of the high leaching of lead and chloride. On the other hand, leaching of elements like cadmium, nickel and copper is limited by the high pH of the residue, and as long as the waste keeps its ANC, the risk of mobilization of these elements is low.     

Understanding the chemical and mineralogical properties of the inorganic portion of MSWI bottom ash

This paper investigates the changes of mineralogical composition of bottom ash in the environment. The chemical and mineralogical bulk composition was determined by X-ray fluorescence (XRF) and X-ray powder diffraction (XRPD) Rietveld method. Single bottom ash particles were investigated by optical microscopy, scanning electron microscopy with quantitative energy-dispersive X-ray microanalysis (SEM/EDX) and electron probe micro analysis (EPMA). SEM/EDX and EPMA are valuable complement to bulk analysis and provide means for rapid and sensitive multi-elemental analysis of ash particles. The fresh bottom ash consists of amorphous (>30 wt.%) and major crystalline phases (>1 wt.%) such as silicates, oxides and carbonates. The mineral assemblage of the fresh bottom ash is clearly unstable and an aging process occurs by reaction towards an equilibrium mineral phase composition in the environmental conditions. The significant decrease of anhydrite and amorphous contents was observed in the aged bottom ash, leading to the formation of ettringite, hydrocalumite and rosenhahnite under atmospheric conditions. In the water-treated sample, the calcite contents increased significantly, but ettringite was altered by the dissolution and precipitation processes in part, to produce gypsum, while the remaining part reacted with chloride to form hydrocalumite. Gypsum and other Ca based minerals may take up substantial amounts of heavy metals and subsequently control leaching behaviour of bottom ash.     

Microbial influenced degradation of solidified waste binder

Ordinary cement pastes with water/cement (w/c) ratios of 0.2, 0.4 and 0.5 were used to examine the chemical and physical effects of microbial influenced degradation (MID). Samples were exposed to an active culture of Thiobacillus thiooxidans or to sterile media containing sulphuric acid using an intermittent immersion technique. Acid consumption and Ca, Al and Fe releases are presented for an exposure period of 90 days. Exposed samples were also sectioned and analysed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDX). All cement paste samples were subject to significant degradation in either sterile acid media or the T. thiooxidans lixiviant. Corrosion depths observed from SEM examination of exposed samples were affected by the w/c ratio of the cement. The extent and rate of degradation were not apparent from the calculated rate of hydrogen ion consumption, or the leaching rates of Ca, Al and Fe. It was not possible to distinguish differences in corrosion due to the chemical and microbial influenced degradation from the results obtained to date and further work is focusing on modified procedures to address this.     

Percolation and batch leaching tests to assess release of inorganic pollutants from municipal solid waste incinerator residues

In this study, percolation and batch leaching tests were considered in order to characterize the behaviour of air pollution control (APC) residues produced in a municipal solid waste incinerator (MSWI) as a function of the liquid to solid ratio (L/S). This waste is hazardous, and taking into account their physical and chemical properties, leaching of contaminants into the environment is the main concern. In our work the leaching behaviour of toxic heavy metals (Pb, Zn, Cr, Ni and Cu) and inorganics associated with soluble salts (Na, K, Ca and Cl) was addressed. Although pH of the leaching solution is the most important variable, L/S may also play an important role in leaching processes. In our work, results from column and batch tests were compared in terms of concentration (mg/L) and releasing (mg/kg). The APC residues revealed to be hazardous according to both tests, and both Pb and Cl⁻ far exceeded the regulatory thresholds. The material exhibits high solubility, and when the liquid to solid ratio was high, more than 50% can be solubilised. The patterns of release may be in some cases availability or solubility controlled, and the former was easier to identify. When the results from column and batch experiments were compared by representing the cumulative released amounts (in mg/kg) as a function of L/S, both curves match for Zn, Ni, Cu, K, Na, Cl and Ca, but for Cr and Pb a significant difference was observed. In fact, the column experiments revealed that under percolation conditions it should be expected slow releasing of Pb along time. From this study, it can be concluded that the released amounts obtained in batch experiments for a certain L/S should be considered as the worst case for medium term. Some simple models proposed on the literature and based on local equilibrium assumption showed good fitting to experimental data for soluble species (non-reactive solutes).     

次氯酸钙溶液的脱硫脱硝特性

采用Ca(ClO)2溶液在高效反应瓶中与模拟烟气进行脱硫脱硝实验,考察了模拟烟气中SO2和NOx的去除效果,以动力学为理论基础研究了Ca(ClO)2的脱硫脱硝性能。实验结果表明:在模拟烟气中SO2,NO,NO2的质量浓度分别为3700,1300,820 mg/m^3及Ca(ClO)2溶液浓度为0.35 mol/L的条件下,SO2去除率达到100%,NOx去除率达到67%。脱硫过程中吸收液中的ClO-是100%脱硫率的保障。Ca^2+吸收SO2的反应速率呈现一级反应的特征。得到的脱硫产物CaSO4·2H2O达到了工业石膏的品质要求。同时脱硫脱硝时NOx和SO2具有协同作用。     

Carbon dioxide utilization with carbonation using industrial waste-desulfurization gypsum and waste concrete

In this study, we propose a process making calcium carbonate and calcium sulfate and recovering absorbent using ammonia absorbent, carbon dioxide, and industrial waste. The main objective of this study is to confirm the possibility of carbon capture and utilization based on waste materials. We assumed desulfurization gypsum and construction waste (ready mixed concrete washing water, waste concrete, etc.) are CaSO₄, Ca(OH)₂, respectively. And concentration of simulated carbon dioxide gas was 15 vol% similar to flue gas. Calcium carbonate was produced by combination reaction between ionic CO₂ in absorbent and metal ion in the solid waste. Experiments were conducted at normal temperature and pressure. Furthermore, the generated products were characterized by X-ray diffraction, and scanning electron microscope.     

Eco-Friendly, Vascular Shape and Interpenetrating Poly (Acrylic Acid) Grafted Pectin Hydrogels; Biosorption and Desorption Investigations

The synthesis and characterization of poly (acrylic acid) grafted pectin hydrogel followed by biosorption and desorption characteristics of cadmium, as a model heavy metal, have been studied. The grafted eco-friendly pectin based interpenetrating hydrogel was prepared in the presence of gluteraldehyde crosslinker under N₂ atmosphere and characterized using ¹H-NMR, FTIR, TGA and SEM techniques. Gluteraldehyde was found to form one-arm and two-arm crosslinks in the copolymer. Upon grafting, two-dimensional sheet structures bounded to tubular and vascular cylindrical rods were observed. The biosorption and desorption data, determined experimentally, were fitted to pseudo-second order reaction kinetics. At higher ionic strength values, the maximum metal uptake value (q _max) was lowered and pseudo-second order rate constant (k ₂) was increased. Whereas, at higher pH values the maximum metal uptake value (q _max) was increased and Pseudo-second order rate constant (k ₂) was decreased. 0.1?M HCl solution was a suitable eluent to regenerate the hydrogel surface and recover the adsorbed cadmium metal ions. Pectin based copolymer could be used as an efficient candidature biosorbent for the recovery of cadmium metal ions from aqueous solutions.     

Sensitivity of Water Quality Model Results for the Dutch Coastal Zone to the Distribution Coefficient of Cadmium

Results of a water quality model of the Dutch coastal zone appeared to be highly sensitive for the distribution coefficient particulate/dissolved (K_d) of cadmium.Field data of the Dutch coastal zone were used to calculate the annual and seasonal trend in the distribution coefficient of cadmium over the years 1983–88. A strong seasonal and spatial gradient in the distribution coefficient was found with relatively high values in summer and lower values in winter (K_d=3.0–7.0 log l/kg). Near the coast (2 km) the K_d was lower than more offshore (70 km from the coast). In addition, values for the distribution coefficient for cadmium were extracted from the literature (K_d=2.9–4.7 log l/kg).The range of K_d values obtained from the field data was used to perform model simulations for cadmium, in order to determine the sensitivity of the model to the distribution coefficient. The modelled yearly averaged concentrations of dissolved cadmium at one location 10 km from the coast, ranged from 0.005–0.035 μg/l, depending on the magnitude of the K_d used in the simulation. These concentrations are low compared to measured values (0.053 μg/l) due to an underestimation of the cadmium input to the North Sea, or possibly the occurrence of bottom-water exchange processes which the model does not include.     

Photochemical oxidation of p-chlorophenol by UV/H2O2 and photo-Fenton process. A comparative study

In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV/H2O2 and the photo-Fenton reaction (UV + classical Fenton reaction) were investigated in lab-scale experiments for the degradation of p-chlorophenol. The study showed that the photo-Fenton process, (a mixture of hydrogen peroxide and ferrous or ferric ion), was the most effective treatment process under acidic conditions and produced a higher rate of degradation of p-chlorophenol at a very short radiation time. It accelerated the oxidation rate by 5-9 times the rate for the UV/H2O2 process. The reaction was found to follow the first order, the reaction was influenced by the pH, the input concentration of H2O2 and the amount of the iron catalyst and the type of iron salt. The experimental results showed that the optimum conditions were obtained at a pH value of 3, with 0.03 mol/l H2O2, and 1 mmol/l Fe(II) for the UV/H2O2/Fe(II) system and 0.01 mol/l H2O2 and, 0.4 mmol/l Fe(III) for the UV/H2O2/Fe(III) system. The reactions were accompanied by the generation of Cl- which reached its maximum value at a short reaction time when using the photo-Fenton process. Finally a rough comparison of the specific energy consumption shows that photo-Fenton process reduced the energy consumption by at least 73 to 83% compared with the UV/H2O2 process.