Enhanced debromination of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) by zero-valent zinc with ascorbic acid

• Highly efficient debromination of BDE-47 was achieved in the ZVZ/AA system. • BDE-47 debromination by the ZVZ/AA can be applied to a wide range of pH. • AA inhibits the formation of (hydr)oxide and accelerates the corrosion of ZVZ. • Reduction mechanism of BDE-47 debromination by the ZVZ/AA system was proposed. A new technique of zero-valent zinc coupled with ascorbic acid (ZVZ/AA) was developed and applied to debrominate the 2,2′,4,4′-Tetrabromodiphenyl ether (BDE-47), which achieved high conversion and rapid debromination of BDE-47 to less- or non-toxic forms. The reaction conditions were optimized by the addition of 100 mg/L ZVZ particles and 3 mmol/L AA at original solution pH= 4.00 using the solvent of methanol/H₂O (v:v= 4:6), which could convert approximately 94% of 5 mg/L BDE-47 into lower-brominated diphenyl ethers within a 90 min at the ZVZ/AA system. The high debromination of BDE-47 was mainly attributed to the effect of AA that inhibits the formation of Zn(II)(hydr)oxide passivation layers and promotes the corrosion of ZVZ, which leads to increase the reactivity of ZVZ. Additionally, ion chromatography and gas chromatography mass spectrometry analyses revealed that bromine ion and lower-debromination diphenyl ethers formed during the reduction of BDE-47. Furthermore, based on the generation of the intermediates products, and its concentration changes over time, it was proposed that the dominant pathway for conversion of BDE-47 was sequential debromination and the final products were diphenyl ethers. These results suggested that the ZVZ/AA system has the potential for highly efficient debromination of BDE-47 from wastewater.     

两种有机锌络合物处理棉花的霉变及热解行为研究

棉花是纺织业的重要原料,是人民群众生活不可或缺的必需品,同时也是我国进出口重要的商品。研究如何安全有效地进行棉花的储备具有十分重要的现实意义。棉纤维本身含有脂肪、蜡质和果胶等适合微生物生长繁殖的营养物质。在棉花储备中,高的回潮率会加速微生物的繁殖,进而产生热量。热量的累积会引起温度升高以及棉花霉变,不利于棉花的安全有效储存。因此,通过静电吸附法将安全无毒的有机锌络合物附着在棉纤维表面,研究表明,相同条件下,处理棉的霉变状况明显得到抑制。加速发霉条件下,未处理棉的相对于白纸的平均色差值为28.10,而双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别为5.16和5.86,下降了81.6%和79.1%。自然发霉条件下,双乙酸锌以及苯甲酸锌防霉处理棉的色差值分别下降了53.8%和50.7%。同时研究了纯棉以及处理棉氮气下的热分解动力学,相比于未处理棉,双乙酸锌防霉处理后活化能下降了15.8%,而苯甲酸锌防霉处理后活化能下降了10.9%。此外,利用实时红外和热重红外联用技术得到了样品在热解过程中固相以及气相的裂解产物的红外谱图,发现防霉处理能一定程度上抑制棉花热解。     

Zinc recovery from hazardous construction wastes via an integrated process of the air classification,alkaline leaching,and water washing

Zinc- and lead-containing wastes are often mixed with construction and demolition wastes in many factories, generating abundant of heavy metal-enriched hazardous waste. In the present study, a novel integrated process of air classification, alkaline leaching, and water washing dechlorination was proposed for the efficient recycling of Zinc (Zn) resources. The first air classification process was realized via venturi tube, wherein the content of Zn could increase by 20 wt.%. After that, the product underwent an alkaline leaching process. Results showed that Zn recovery rate increased with fine particle sizes, and a 65% recovery rate was obtained under the following conditions of 5 mol/L NaOH, liquid/solid 10:1, and leaching time 1 h. Finally, water washing associated with microwave and ultrasonic treatments could remove over 85% of Cl and other water-soluble salts. All the results indicated that the integrated method had an excellent recovery rate for Zn resources from construction and demolition wastes.     

我国典型铅锌选矿企业尾矿产生及综合利用分析

通过对我国6家典型铅锌选矿企业铅锌尾矿产生情况的调研及现场采样测试分析,掌握典型企业铅锌尾矿的产生、理化性质及综合利用情况,推算出不同品位铅锌原矿吨产品铅锌尾矿的产生系数,并结合我国铅锌选矿行业及铅锌尾矿综合利用现状,提出适合我国国情的对策建议。     

锌在辽宁红沿河核电站的大气腐蚀研究

通过锌在红沿河核电站的大气暴露试验,研究了锌在红沿河地区SO2,Cl-含量较高以及高湿的环境条件下的腐蚀规律。试验结果表明锌的腐蚀质量损失与暴露时间呈线性关系。利用扫描电子显微镜、Fourier变换红外光谱仪以及X射线衍射仪对锌表面腐蚀产物进行了分析,进一步分析了腐蚀质量损失与暴露时间呈线性关系的原因,并探讨了锌在SO2,Cl-含量较高以及高湿的环境条件下的腐蚀机理。     

一株Zn抗性菌株的筛选鉴定及吸附条件优化

采用浓度梯度法从铅锌尾矿区与污水灌溉区土壤中筛选了一株Zn抗性放线菌,并通过形态与培养特征、生理生化特性、细胞壁组分与16SrRNA基因序列分析对该菌株进行了鉴定.同时,综合运用单因素试验与正交试验法对该菌株吸附Zn2+的条件进行了优化.结果表明,菌株CCNWHX72-14经鉴定为高加索链霉菌(Streptomyces ciscaucasicus),其对Zn2+的抗性达到845mg·L-1.锌胁迫生长曲线表明,该菌株在130mg·L-1Zn2+胁迫时生长良好,且最适培养时间为7d.各个单因素条件对该菌株吸附Zn2+的影响顺序为:接种量初始Zn2+浓度初始pH转速温度.该菌株吸附Zn2+的最佳条件为:初始Zn2+浓度为150mg·L-1,初始pH=5,接种量为1%,转速为60r·min-1,温度为28℃.菌株CCNWHX72-14在最佳条件下对Zn2+的吸附较具有良好的重复性与稳定性,最高吸附量可达51.05mg·g-1,该研究为进一步探讨链霉菌的Zn2+吸附机制及其在生物修复中的应用奠定了基础.     

Heavy metal （Pb,Zn） uptake and chemical changes in rhizosphere soils of four wetland plants with different radial oxygen loss

Lead and Zn uptake and chemical changes in rhizosphere soils of four emergent-rooted wetland plants; Aneilema bracteatum, Cyperus alternifolius, Ludwigia hyssopifolia and Veronica serpyllifolia were investigated by two experiments: (1) rhizobag filled with “clean” or metal-contaminated soil for analysis of Pb and Zn in plants and rhizosphere soils; and (2) applied deoxygenated solution for analyzing their rates of radial oxygen loss (ROL). The results showed that the wetland plants with di erent ROL rates had significant e ects on the mobility and chemical forms of Pb and Zn in rhizosphere under flooded conditions. These e ects were varied with di erent metal elements and metal concentrations in the soils. Lead mobility in rhizosphere of the four plants both in the “clean” and contaminated soils was decreased, while Zn mobility was increased in the rhizosphere of the “clean” soil, but decreased in the contaminated soil. Among the four plants, V. serpyllifolia, with the highest ROL, formed the highest degree of Fe plaque on the root surface, immobilized more Zn in Fe plaque, and has the highest e ects on the changes of Zn form (EXC-Zn) in rhizosphere under both “clean” and contaminated soil conditions. These results suggested that ROL of wetland plants could play an important role in Fe plaque formation and mobility and chemical changes of metals in rhizosphere soil under flood conditions.     

种植密度对镉锌污染土壤伴矿景天植物修复效率的影响

田间微区试验研究了不同种植密度对伴矿景天生长和地上部重金属吸收量的影响.结果表明,适度增大种植密度可促进伴矿景天的生长,显著提高其地上部生物量,但过分密植对植物地上部增产无显著贡献.种植密度由11万株/hm2上升到44万株/hm2时,伴矿景天地上部Cd、Zn吸取量显著上升,分别由0.208 kg.hm-2上升至0.631 kg.hm-2、13.2 kg.hm-2上升至58.7kg.hm-2;但种植密度从44万株/hm2增大到100万株/hm2时,植物地上部重金属吸取量并无显著提高.伴矿景天种植密度为44万株/hm2时,在Cd、Zn分别为(3.04±0.11)mg.kg-1和(1 299±96)mg.kg-1的污染土壤上种植1 a,对镉锌的修复效率分别达21.1%和4.60%,表明选择适宜的密度种植伴矿景天有利于增大植物地上部Cd、Zn吸取量,从而缩短修复时限.     

Variation of grain Cd and Zn concentrations of 110 hybrid rice cultivars grown in a low-Cd paddy soil

Enhanced Cd uptake and Zn depletion in rice grains and high potential for food Cd exposure by the high-yielding hybrid cultivars of China had been addressed. A field experiment was conducted in 2006 to determine the di erence in grain Cd and Zn between cultivars. Total 110 cultivars including super rice and common hybrid rice cultivars were grown on a single paddy soil (Entic Haplaquept) with a neutral reaction and low total Cd content. Grain Cd and Zn concentrations were determined with graphite atomic adsorption spectrophotometer (GFAAS) and flame atomic adsorption spectrophotometer (AAS) respectively.Wide variation of Cd content in grain was found in a range of 0.004–0.057 mg/kg, while the Zn content in a range of 10.25–30.06 mg/kg among the cultivars. Higher Cd but lower Zn concentration in grains of super rice cultivars was observed compared to the common hybrid ones. A highly significant positive linear correlation of grain Cd/Zn with grain Cd was found for super rice and common hybrid cultivars, meanwhile much higher slope for these hybrid cultivars than the reported non-hybrid cultivars was also observed. Using the limit value of the Chinese chemical guidelines for foods (MOHC and SSC, 2005), calculated potential risk of food Cd exposure with “Zn hungry” through diet intake was prominent with all the studied 110 hybrid rice cultivars, possessing high potential health problems for rice production in South China using the super rice cultivars. Breeding of genotypes of rice cultivars with low grain Cd and low Cd/Zn ratio is needed for rice production in acidic red soils where Cd bioavailability is prevalently high.     

Photocatalytic degradation of methyl orange over ITO/CdS/ZnO interface composite films

ITO/CdS/ZnO interface composite films were successfully prepared by subsequent electrodeposition of CdS and ZnO onto indium tin oxide (ITO) glass substrates. The obtained ITO/CdS/ZnO composite films were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-Vis spectroscopy. The photocatalytic activity of ITO/CdS/ZnO composite films were investigated using methyl orange (MO) as a model organic compound under UV light irradiation. The influence of operating parameters on MO degradation including initial concentration of MO, pH value of solution, and inorganic anion species over the composite films were examined. A blue shift of absorption threshold was observed for the ITO/CdS/ZnO film in comparison with ITO/ZnO film. ITO/CdS/ZnO composite films prepared under specific conditions showed a higher photocatalytic activity than that of ITO/ZnO films. It was also found that the photocatalytic degradation of MO on the composite filing followed pseudo-first order kinetics.