风淬钢渣对高炉渣基微晶玻璃性能的影响

以风淬钢渣和高炉渣为主要原料,采用一次烧结法制备微晶玻璃。结果表明,该方法制备的微晶玻璃主晶相为钙铝黄长石(Ca2Al2SiO7),还有少量的镁黄长石(Ca2MgSi2O7),钢渣最大用量达到50%;随着风淬钢渣含量的增加,样品的最佳烧结温度逐渐增加;烧结温度对样品析晶性能的影响明显大于风淬钢渣含量的影响;样品的抗折强度随风淬钢渣的增加呈现出先增大后减小的趋势;样品的密度随风淬钢渣的增加而逐渐减小;直接用风淬钢渣和高炉渣制备出的微晶玻璃具有良好的抗折强度和耐酸碱性,抗折强度最大可达90 MPa,该方法为综合治理冶金渣污染及其综合利用开辟了新的途径。     

Metal stabilization mechanism of incorporating lead-bearing sludge in kaolinite-based ceramics

The feasibility and mechanism of incorporating simulated lead-laden sludge into low-cost ceramic products was investigated by observing the reaction of lead with two kaolinite-based precursors under sintering conditions. To investigate the phase transformation process of lead, lead oxide (PbO) mixed with a kaolinite or mullite precursor were fired at 500-950 °C for 3 h. Detailed X-ray diffraction analysis of sintered products revealed that both precursors had crystallochemically incorporated lead into the lead feldspar (PbAl₂Si₂O₈) crystalline structure. By mixing lead oxide with kaolinite, lead feldspar begins to crystallize at 700 °C; maximum incorporation of lead into this structure occurred at 950 °C. However, two intermediate phases, Pb₄Al₄Si₃O₁₆ and a polymorph of lead feldspar, were detected at temperatures between 700 and 900 °C. By sintering lead oxide with the mullite precursor, lead feldspar was detected at temperatures above 750 °C, and an intermediate phase of Pb₄Al₄Si₃O₁₆ was observed in the temperature range of 750-900 °C. This study compared the lead leachabilities of PbO and lead feldspar using a prolonged leaching test (at pH 2.9 for 23 d) modified from the toxicity characteristic leaching procedure. The results indicate the superiority of lead feldspar in stabilizing lead and suggest a promising and reliable strategy to stabilize lead in ceramic products.     

Toxicity of nanoparticulate and bulk ZnO, Al2O3 and TiO2 to the nematode Caenorhabditis elegans

Limited information is available on the environmental behavior and associated potential risk of manufactured oxide nanoparticles (NPs). In this research, toxicity of nanoparticulate and bulk ZnO, Al₂O₃ and TiO₂ were examined to the nematode Caenorhabditis elegans with Escherichia coli as a food source. Parallel experiments with dissolved metal ions from NPs were also conducted. The 24-h median lethal concentration (LC₅₀) and sublethal endpoints were assessed. Both NPs and their bulk counterparts were toxic, inhibiting growth and especially the reproductive capability of the nematode. The 24-h LC₅₀ for ZnO NPs (2.3 mg L⁻¹) and bulk ZnO was not significantly different, but significantly different between Al₂O₃ NPs (82 mg L⁻¹) and bulk Al₂O₃ (153 mg L⁻¹), and between TiO₂ NPs (80 mg L⁻¹) and bulk TiO₂ (136 mg L⁻¹). Oxide solubility influenced the toxicity of ZnO and Al₂O₃ NPs, but nanoparticle-dependent toxicity was indeed observed for the investigated NPs.     

Ozone-enhanced catalytic oxidation of monochlorobenzene over iron oxide catalysts

In this study, we examined the experimental catalytic oxidation of gaseous monochlorobenzene (MCBz) with O₃ over Fe₂O₃ in a packed bed reactor to investigate the feasibility of economical low temperature decomposition at a high space velocity (SV). We investigated the effects of several reaction parameters (temperature, O₃ concentration, and SV) on the MCBz oxidation. At 150 °C, the conversion of MCBz over Fe₂O₃ in the absence of O₃ was only 3%; it increased to 91% over Fe₂O₃ in the presence of 1200 ppm of O₃ at a high SV of 83 s⁻¹. A long-term operation study revealed that the conversion of MCBz was stable for more than 96 h. In the steady state, the carbon and chlorine balances were 88% and 86%, respectively. Applying a Langmuir-Hinshelwood kinetic model, we estimated an activation energy of 16.7 kJ mol⁻¹ for MCBz oxidation over Fe₂O₃ in the presence of O₃.     

Evaluation of atmospheric sources of PCDD/Fs, PCBs and PBDEs around a steel industrial complex in northeast China using passive air samplers

The concern about emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from steel industrial parks has increased in the past decades. In this study, polyurethane foam (PUF)-disk based passive air samples were collected in and around a big steel industrial park of Anshan, Northeast China from June 2008 to March 2009. The levels, seasonal variations and potential sources of PCDD/Fs, PCBs and PBDEs in the atmosphere around the steel industrial complex were investigated, and potential contribution of these three groups of persistent organic pollutants (POPs) from iron and steel production was also assessed. The air concentrations of ∑₁₇PCDD/Fs (summer: 0.02-2.77 pg m⁻³; winter: 0.20-9.79 pg m⁻³), ∑₁₉PCBs (summer: 23.5-155.8 pg m⁻³; winter: 14.6-81.3 pg m⁻³) and ∑₁₃PBDEs (summer: 2.91-10.7 pg m⁻³; winter: 1.10-3.89 pg m⁻³) in this targeted industrial park were relatively low in comparison to other studies, which implied that the industrial activities of iron and steel had not resulted in serious contamination to the ambient air in this area. On the whole, the air concentrations of PCDD/Fs in winter were higher than those of summer, whereas the concentrations of PCBs and PBDEs showed opposite trends. The result from principal component analysis indicated that coal combustion might be the main contributor of PCDD/F sources in this area.     

Use of whole-body and subcellular Cu residues of Lumbriculus variegatus to predict waterborne Cu toxicity to both L. variegatus and Chironomus riparius in fresh water

We tested the use of whole-body and subcellular Cu residues (biologically-active (BAM) and inactive compartments (BIM)), of the oligochaete Lumbriculus variegatus to predict Cu toxicity in fresh water. The critical whole-body residue associated with 50% mortality (CBR₅₀) was constant (38.2-55.6 μg g⁻¹ fresh wt.) across water hardness (38-117 mg L⁻¹ as CaCO₃) and exposure times during the chronic exposure. The critical subcellular residue (CSR₅₀) in metal-rich granules (part of BIM) associated with 50% mortality was approximately 5 μg g⁻¹ fresh wt., indicating that Cu bioavailability is correlated with toxicity:subcellular residue is a better predictor of Cu toxicity than whole-body residue. There was a strong correlation between the whole-body residue of L. variegatus (biomonitor) and survival of Chironomus riparius (relatively sensitive species) in a hard water Cu co-exposure. The CBR₅₀ in L. variegatus for predicting mortality of C. riparius was 29.1-45.7 μg g⁻¹ fresh wt., which was consistent within the experimental period; therefore use of Cu residue in an accumulator species to predict bioavailability of Cu to a sensitive species is a promising approach.     

应用神经网络方法优化垃圾焚烧模拟灰渣熔点的预测

采用SiO₂、Al₂O₃、CaO、Na₂CO₃、NaCl和Fe₂O₃等物质来模拟垃圾焚烧的真实灰渣组成，通过实验测定模拟灰渣熔点，建立神经网络模型进行熔点预测，由预测结果来指导进一步实验，得到修正的模型，最终预测出的半球温度（HT）平均误差低于5%。     

Salting-out phenomenon and 1-octanol/water partition coefficient of metalaxyl pesticide

In this paper, we present the effect of inorganic cations such as Na⁺, K⁺, Ca²⁺, Mg²⁺ on the salting-out phenomenon of metalaxyl from pure water to aqueous salt solutions. Moreover the 1-octanol/water partition coefficient in pure water is presented. To accomplish this, aqueous solubility of metalaxyl was determined in pure water, in different salt solution (NaCl, KCl, CaCl₂ and MgCl₂), and at different concentration level ranging from 0.01 to 1.5 M. The 1-octanol/water partition coefficient was determined using the static shake-flask method. Solubility was determined using dynamic saturation method for pure water in the range of 298.15-325.15 K and at 298.15 K for different salt solutions. The solubility value in pure water for studied interval was found constant (m = 3.118 × 10⁻² mol kg⁻¹).Solubility values were used to calculate the standard molar Gibbs free energy of dissolution (Δ_solG°) and transfer (Δ_trG°) at 298.15 K. The values of Δ_trG° from pure to all studied aqueous salt solutions did not exceed 2 kJ mol⁻¹, the value of Δ_solG° of dissolution is 18.5 ±0.72 kJ mol⁻¹. The 1-octanol/water partition coefficient in pure water log K_o/w is equal to 1.69. The obtained results confirm the classification of the neutral metalaxyl as a slightly hydrophobic molecule.     

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved

The conventional hydrothermal reaction with iron powder, NaOH and H₂O as reactants was reported to occur at temperature above 423 K, and iron oxides (Fe₃O₄ and NaFeO₂) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H₂O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe₃O₄/NaFeO₂ and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100 mg L⁻¹ of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10 mL simulative transformer oil, almost complete dechlorination was achieved by 750 W microwave irradiation for 10 min, with 0.3 g iron powder, 0.3 g NaOH and 0.6 mL H₂O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H₂O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.     

Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

Characterization of eco-cement paste produced from waste sludges

In this study, marble sludge, sewage sludge, drinking water treatment plant sludge, and basic oxygen furnace sludge were used as replacements for limestone, sand, clay, and iron slag, respectively, as the raw materials for the production of cement in order to produce eco-cement. It was found that it is feasible to use marble sludge to replace up to 50% of the limestone and also that other materials can serve as total replacements for the raw materials typically used in the production of cement. The major components of Portland cement were all found in eco-cement clinkers. The eco-cement was confirmed to produce calcium hydroxide and calcium silicate hydrates during the hydration process, increasing densification with the curing age. The compressive strength (S_c) and microstructural evaluations conducted at 28 d revealed the usefulness of eco-cement. It was observed that the S_c data correlated linearly with the pore volume (P) data at 28 d. The proposed model equation could be represented as S_c = 178-461P (correlation coefficient, R² = 0.96). Two parameters, the large capillary pore volume and the medium capillary pore volume, were evaluated using multiple regression analysis.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

Mitigation effects of silicon rich amendments on heavy metal accumulation in rice (Oryza sativa L.) planted on multi-metal contaminated acidic soil

The mechanisms of stabilization by silicon-rich amendments of cadmium, zinc, copper and lead in a multi-metal contaminated acidic soil and the mitigation of metal accumulation in rice were investigated in this study. The results from a pot experiment indicated that the application of fly ash (20 and 40 g kg⁻¹) and steel slag (3 and 6 g kg⁻¹) increased soil pH from 4.0 to 5.0-6.4, decreased the phytoavailability of heavy metals by at least 60%, and further suppressed metal uptake by rice. Diffusion gradient in thin-film measurement showed the heavy metal diffusion fluxes from soil to solution decreased by greater than 84% after remediation. X-ray diffraction analysis indicated the mobile metals were mainly deposited as their silicates, phosphates and hydroxides in amended treatments. Moreover, it was found metal translocation from stem to leaf was dramatically restrained by adding amendments, which might be due to the increase of silicon concentration and co-precipitation with heavy metals in stem. Finally, a field experiment showed the trace element concentrations in polished rice treated with amendments complied with the food safety standards of China. These results demonstrated fly ash and steel slag could be effective in mitigating heavy metal accumulation in rice grown on multi-metal contaminated acidic soils.     

Removal of Rhodamine B under visible irradiation in the presence of Fe⁰, H₂O₂, citrate and aeration at circumneutral pH

A new Vis-Fe⁰-H₂O₂-citrate-O₂ system comprising zero-valent iron, hydrogen peroxide, citrate anion and aeration at circumneutral pH under visible irradiation was studied. 21 μmol L⁻¹ of Rhodamine B (RhB) was chosen as the substrate to be tested. Experiments were conducted under conditions of 2.9 mmol L⁻¹ of H₂O₂, 12.6 g of Fe⁰ and 1.0 mmol L⁻¹ of citrate at pH 7.5. Results showed that, in 1 h reaction, 54% of RhB was removed with corresponding 26% of COD reduced. Meanwhile, the amount of released dissolved irons from Fe⁰ surface was found to be at a very low level as <5.4 μmol L⁻¹. Extinguishing tests with isopropanol suggested that RhB oxidation by hydroxyl radicals was the main process taken place in Vis-Fe⁰-H₂O₂-citrate-O₂ system, which accounted for 75% of substrate removal in 3 h reaction. Control and factor influencing experiments showed that the prohibitive extents of individual factor importance on RhB removal followed a decreasing order of Fe⁰ > H₂O₂ > citrate > Vis > O₂. This study showed an excellent system that could remove refractory organic compounds from water in laboratory researches, and also provided a good idea to reduce secondary contamination by dissolved irons in future investigations.     

Degradation of paracetamol by advance oxidation processes using modified reticulated vitreous carbon electrodes with TiO2 and CuO/TiO2/Al2O3

The degradation of paracetamol in aqueous solutions in the presence of hydrogen peroxide was carried out by photochemistry, electrolysis and photoelectrolysis using modified 100 pores per inch reticulated vitreous carbon electrodes. The electrodes were coated with catalysts such as TiO₂ and CuO/TiO₂/Al₂O₃ by electrophoresis followed by heat treatment. The results of the electrolysis with bare reticulated vitreous carbon electrodes show that 90% paracetamol degradation occurs in 4 h at 1.3 V vs. SCE, forming intermediates such as benzoquinone and carboxylic acids followed by their complete mineralisation. When the electrolysis was carried out with the modified electrodes such as TiO₂/RVC, 90% degradation was achieved in 2 h while with CuO/TiO₂/Al₂O₃/RVC, 98% degradation took only 1 h. The degradation was also carried out in the presence of UV reaching 95% degradation with TiO₂/RVC/UV and 99% with CuO/TiO₂/Al₂O₃/RVC/UV in 1 h. The reactions were followed by spectroscopy UV-Vis, HPLC and total organic carbon analysis. These studies show that the degradation of paracetamol follows a pseudo-first order reaction kinetics.     

Trichloroethylene decomposition and in-situ dry sorption of Cl-products by calcium oxides prepared from hydrated limes

A comparison of CaOs produced by calcining two types of hydrated lime and calcium carbonate was made for decomposition of trichloroethylene and in-situ dry sorption of the decomposed Cl-products using a lab-scale gas flow type tubular packed bed reactor. About 20 mg of CaO sample was mixed with about 2 g of Al₂O₃ particles and packed in the reactor and allowed to react with a flowing standard gas containing 500 ppm of C₂HCl₃ (N₂ balance) at 673 and 873 K, under the condition that the reaction of CaO with C₂HCl₃ might be completed within a few hours.It was found that no thermal decomposition of C₂HCl₃ at or below 673 K was observed in a reactor packed only with Al₂O₃ particles. However, a considerable amount of decomposition of C₂HCl₃ was obtained in a reactor packed with CaO and Al₂O₃, even at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)₂ at 673 K, decomposition of 0.42 mol of C₂HCl₃ and in-situ absorption product of 0.53 mol of CaCl₂ were obtained. At 873 K, about 46% of C₂HCl₃ was thermally decomposed. The total amount of C₂HCl₃ decomposed in CaO-Al₂O₃ particle bed at 873 K became nearly twice larger than that at 673 K. For 1 mol of CaO prepared by calcining highly reactive Ca(OH)₂ at 873 K, decomposition of 0.59 mol of C₂HCl₃ and in-situ absorption product of 0.67 mol of CaCl₂ were obtained. Small amounts of C₂Cl₂, C₂Cl₄, CCl₄, etc. were detected during decomposition of C₂HCl₃ at 673 and 873 K.It was recognized that the data on decomposition of C₂HCl₃ as well as in-situ dry sorption of Cl-products in CaO particle bed were correlated with specific surface area of the CaO employed.     

Solvent tolerant marine bacterium Bacillus aquimaris secreting organic solvent stable alkaline cellulase

The organic solvent tolerant bacteria with their physiological abilities to decontaminate the organic pollutants have potentials to secrete extracellular enzymes of commercial importance. Of the 19 marine bacterial isolates examined for their solvent tolerance at 10 vol.% concentration, one had the significant tolerance and showed a relative growth yield of 86% for acetone, 71% for methanol, 52% for benzene, 35% for heptane, 24% for toluene and 19% for ethylacetate. The phylogenetic analysis of this strain using 16S rDNA sequence revealed 99% homology with Bacillus aquimaris. The cellulase enzyme secreted by this strain under normal conditions showed an optimum activity at pH 11 and 45 °C. The enzyme did show functional stability even at higher pH (12) and temperature (75 °C) with residual activity of 85% and 95% respectively. The enzyme activity in the presence of different additives were in the following order: Co⁺² > Fe⁺² > NaOCl₂ > CuSO₄ > KCl > NaCl. The enzyme stability in the presence of solvents at 20 vol.% concentration was highest in benzene with 122% followed by methanol (85%), acetone (75%), toluene (73%) and heptane (42%). The pre-incubation of enzyme in ionic liquids such as 1-ethyl-3-methylimidazolium methanesulfonate and 1-ethyl-3-methylimidazolium bromide increased its activity to 150% and 155% respectively. The change in fatty acid profile with different solvents further elucidated the physiological adaptations of the strain to tolerate such extreme conditions.