PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known “chlorine pattern” of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.     

Supercritical water gasification of sewage sludge using bench-scale batch reactor: advantages and drawbacks

Sewage sludge, a byproduct of municipal wastewater treatment, was gasified by supercritical water using a bench-scale batch reactor. Configuration of bench-scale batch reactor and operation procedures are discussed in detail. Experience and challenges that arose during the experiment are also shared. Using the bench-scale reactor under the condition of 600 °C, 23 MPa, and a reaction time of 60 min without catalyst presence, a total gas yield of 9.8 mol/(kg-sewage sludge) was obtained. Furthermore, investigations on operational parameters were conducted. Extension of reaction time up to 60 min increased the gasification, reaching a plateau thereafter. Investigation on pressure indicated the superiority of supercritical pressure. The addition of Ni as a catalyst also promoted gasification, although inorganic salts and char seemed to cover the catalyst surface. With regard to the prospect of future operation at a municipal waste water treatment plant, the effect of operational parameters on heavy metal concentration in the liquid phase is also discussed.     

二价铜离子与抗坏血酸共存下的杀菌效果及其机理

考察了二价铜离子与抗坏血酸的组合对大肠杆菌的杀菌效果。实验证明:高浓度的铜离子与抗坏血酸的组合有非常好的杀菌效果,不论是酸性还是中性条件下都能在0.5 h杀灭所有的大肠杆菌;低浓度的铜离子与抗坏血酸的组合也有不错的杀菌效果,且随着pH值的升高,杀菌效果增强,pH=4的条件下24 h后杀灭大肠杆菌,pH=7的条件下0.5 h便能杀灭所有杆菌。实验运用ESR检测羟基自由基,并结合杀菌实验结果推断二价铜离子与抗坏血酸反生了类Fenton反应。     

Decomposition of poly(amide-imide) film enameled on solid copper wire using atmospheric pressure non-equilibrium plasma

The decomposition of a poly(amide-imide) thin film coated on a solid copper wire was attempted using atmospheric pressure non-equilibrium plasma. The plasma was produced by applying microwave power to an electrically conductive material in a gas mixture of argon, oxygen, and hydrogen. The poly(amide-imide) thin film was easily decomposed by argon-oxygen mixed gas plasma and an oxidized copper surface was obtained. The reduction of the oxidized surface with argon-hydrogen mixed gas plasma rapidly yielded a metallic copper surface. A continuous plasma heat-treatment process using a combination of both the argon-oxygen plasma and argon-hydrogen plasma was found to be suitable for the decomposition of the poly(amide-imide) thin film coated on the solid copper wire.     

Finite element analysis of knee injury risks in car-to-pedestrian impacts

In vehicle-pedestrian collisions, lower extremities of pedestrians are frequently injured by vehicle front structures. In this study, a finite element (FE) model of THUMS (total human model for safety) was modified in order to assess injuries to a pedestrian lower extremity. Dynamic impact responses of the knee joint of the FE model were validated on the basis of data from the literature. Since in real-world accidents, the vehicle bumper can impact the lower extremities in various situations, the relations between lower extremity injury risk and impact conditions, such as between impact location, angle, and impactor stiffness, were analyzed. The FE simulation demonstrated that the motion of the lower extremity may be classified into a contact effect of the impactor and an inertia effect from a thigh or leg. In the contact phase, the stress of the bone is high in the area contacted by the impactor, which can cause fracture. Thus, in this phase the impactor stiffness affects the fracture risk of bone. In the inertia phase, the behavior of the lower extremity depends on the impact locations and angles, and the knee ligament forces become high according to the lower extremity behavior. The force of the collateral ligament is high compared with other knee ligaments, due to knee valgus motions in vehicle-pedestrian collisions.     

Effectiveness of resistivity monitoring for interpreting temporal changes in landfill properties

It is always possible for impermeable layers to exist in landfills. When they do, the properties of the solution at the exit of the leachate-collection system might not accurately reflect the overall properties of the landfill. This study examines whether resistivity monitoring is effective for determining the influence of impermeable layers on the leachate. The test cell used in this study was filled with waste made up mainly of incinerator ash and shredded incombustible material. Three lines of resistivity sensors were laid in the uppermost layer of the fill. A resistivity profile was recorded periodically from each of these lines. The water-table level and leachate properties were measured concurrently. Leachate conductivity was mainly controlled by concentrations of the main ions, and it correlated inversely to variations in resistivity. Temporal changes in the resistivity of the fills are an excellent means of assessing the leaching in fills. Monitoring the properties of leachate, combined with resistivity profiling, is extremely useful for interpreting the temporal changes of properties in landfills containing impermeable layers.     

土壤和沉积物中痕量元素的ICP质谱法测定

人们对环境中污染物 (特别是重金属 )的“安全”水平的关注与日俱增 ,要分析的元素更多 ,浓度更低 ,从而暴露出当前所用分析技术的局限性 ,需要进一步提高分析方法的灵敏度和可分析的元素数量 .尽管ＧＦＡＡＳ (石墨炉原子吸收光谱 )和ＩＣＰ ＯＥＳ (感耦等离子体发射光谱 )仍是环境元素分析中最常用的技术 ,但ＩＣＰ ＭＳ (等离子体质谱 )是具有更高灵敏度的分析技术 ,不久肯定会被普遍接受 .ＨＰ 4 50 0台式ＩＣＰ质谱仪具有实际惯常分析应用所必需的可靠性和易于操作 ,可进行亚ｎｇ·ｍｌ- 1级 (ｐｐｂ)浓度水平的多元素快速分析 .本篇…     

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol in supercritical water

Effects of potassium alkalis and sodium alkalis on the dechlorination of o-chlorophenol (o-CP) in supercritical water (SCW) were studied in this paper under the conditions of 450 degrees C and 25 MPa. Experimental results indicated that the dechlorination of o-CP can be accelerated significantly by all alkalis investigated. The dechlorination of o-CP proceeded mainly via two pathways: hydrodechlorination and hydrolysis. Both of the two pathways can be promoted by alkalis, and the dechlorination of o-CP can be accelerated by both the cations and hydroxide ion dissociated from alkalis. The overall dechlorination of o-CP can be accelerated by cations via promoting the hydrodechlorination pathway, while, hydroxide ion via promoting the hydrolysis pathway. In addition, the hydrodechlorination can be accelerated faster by sodium alkalis than that by potassium ones, while, the hydrolysis can be promoted faster by potassium alkalis. This difference may be caused by the different charge density between potassium ion and sodium ion, and the different solubility and dissociation constant between potassium alkalis and sodium alkalis in SCW. Dechlorination of o-CP with addition of alkalis prior to supercritical water oxidation (SCWO) process not only can avoid the reactor corrosion caused by the generated hydrochloric acid in direct SCWO of o-CP, but also can reduce the formation of toxic chlorinated byproducts compared with direct SCWO process or SCWO of o-CP with addition of alkali.     

土壤酸化及天然土壤溶液中铝的形态

采用真空式土壤溶液采样器收集了宜昌、巫山松树林中天然土壤溶液,采用高效液相色谱法Al－Lumogallion柱后荧光检测,分析测试了土壤溶液中可溶性铝的形态,研究了由于土壤酸化引起天然土壤溶液中不同形态铝的迁移转化结果表明,天然土壤溶液中含有不同形态的铝,主要是有机铝、 AISO₄⁺、AIF₂⁺、Al（OH）²⁺、Al³⁺等．宜昌、巫山地区土壤溶液中活性铝（Al³⁺、AlOH^2+F）的含量比较低．土壤的酸化使得天然土壤溶液中总铝含量增加、铝形态的优势态发生变化,即土壤的酸化使得天然土壤溶液中活性铝－Al³⁺、AlOHF²⁺含量和比例增加．土壤酸化还降低了大然土壤溶液中的BC/Al比值,这些变化的结果都增加了对森林潜在的危害．