工业含钒废水处理工艺的研究进展

针对大量企业采用传统提钒法制备钒产品产生的工业含钒废水的处理问题,综述了工业含钒废水处理工艺的研究进展,分别详述了沉淀法、溶剂萃取法、离子交换法、电解法、吸附法和生物法的处理工艺,并对比分析了它们的优势与不足。指出:工业含钒废水的处理既是环保的要求,又可实现有价资源的回收利用;在实际应用时,可依据工业含钒废水的p H选择相应的处理工艺及处理试剂。     

旋流萃取分离技术处理石化电脱盐废水

采用旋流萃取分离技术处理某炼油厂常减压装置电脱盐废水(初始废水含油量约为5 000 mg/L),优化了废水除油的工艺条件。试验结果表明,废水除油的最佳工艺条件为:旋流萃取分离机中心转子的转速960 r/min、废水流量2 000 L/h、废水温度80℃。废水经旋流萃取分离后,废水的含油量小于200 mg/L,废水除油效果较好;分离后油相的含水量约为0.1%(w),盐质量浓度小于20 mg/L,可回注到常减压装置原料罐循环利用。对于2 Mt/a的常减压装置,采用旋流萃取分离技术后,每年可减少支出100.4万元。     

苯甲酸生产残液中锰、钴和镍的提取及分离

探讨了苯甲酸生产残液中锰、钴和镍的提取及分离方法。首先采用酸溶液提取残液中的金属元素;然后通过氨水沉淀法分离锰;最后使用p507萃取剂分离钴和镍。实验结果表明:当苯甲酸生产残液中锰、钴和镍的质量分数分别为0.085 0%,0.307 1%,0.015 5%时,在硫酸浓度为2.0 mol/L、过氧化氢溶液质量分数为25%的条件下,锰、钴和镍的提取率分别为88.59%,87.77%,86.50%;当氨水浓度为2 mol/L时,锰的沉淀率达94.24%;在平衡水相p H为4、p507萃取剂皂化率为60%、油相中p507萃取剂的体积分数为15%的条件下,钴萃取率达87.53%,镍萃取率仅为8.46%,钴镍分离系数为68.70。     

Simultaneous determination of eight metabolites of organophosphate and pyrethroid pesticides in urine

A simultaneous method for quantifying eight metabolites of organophosphate pesticides and pyrethroid pesticides in urine samples has been established. The analytes were extracted using liquid–liquid extraction coupled with WCX solid phase extraction (SPE) cartridges. Eight metabolites were chemically derivatized before analysis using gas chromatography–tandem mass spectrometry (GC–MS–MS). The separation was performed on a HP-5MS capillary column (30 m × 0.25 mm × 0.25 µm) with temperature programming. The detection was performed under electro-spray ionization (ESI) in multiple reaction monitoring (MRM) mode. An internal standard method was used. The extraction solvent, types of SPE cartridges and eluents were optimized by comparing the sample recoveries under different conditions. The results showed that the calibration curves of the five organophosphorus pesticides metabolites were linear in the range of 0.2–200 μg/L (r² ≥ 0.992) and that of the three pyrethroid pesticides metabolites were linear in the range of 0.025–250 μg/L (r² ≥ 0.991). The limits of detection (LODs, S/N ≥ 3) and the limits of quantification (LOQs, S/N ≥ 10) of the eight metabolites were 0.008–0.833 μg/L and 0.25–2.5 μg/L, respectively. The recoveries of the eight metabolites ranged from 54.08% to 82.49%. This efficient, stable, and cost-effective method is adequate to handle the large number of samples required for surveying the exposure level of organophosphorus and pyrethroid pesticides in the general population.     

Using sequential extraction techniques to assess the partitioning of plutonium and neptunium-237 from multiple sources in sediments from the Ob River (Siberia)

Sequential extraction techniques have been developed to assess partitioning of anthropogenic radionuclides (²⁴⁰Pu, ²³⁹Pu, and ²³⁷Np), originating from a variety of sources, as identified by using bulk sediment isotopic composition. Sediments were leached sequentially with a series of six chemical treatments designed to approximate different environmental processes that may occur or to selectively extract trace metals contained in different solid phases of the sediments (i.e., exchangeable, reducible, carbonate, organic, acid leachable, and refractory). Results indicate the majority of Pu and Np is similarly distributed within many of the extracted fractions, with the largest percentage (66–97%) of both elements being observed in sediments treated with buffered citrate dithionite (CDB), which targets easily reduced constituents such as Mn and Fe hydrous oxides. While these results do indicate an association of Pu and Np with redox sensitive elements, the environmental implications are unclear given that the CDB treatment is more extreme than naturally occurring conditions. Minor amounts of Np partition differently from Pu in sediments. The NH₄-acetate treatment, which is designed to liberate trace metals that are loosely adsorbed onto the surfaces of sedimentary materials such as hydrated iron oxides and humic substances, or present at exchangeable sites in clay minerals, mobilized ∼12% of the total Np while Pu levels were below detection. The H₂O₂ treatment, which is designed to liberate trace metals bound to organic matter, mobilized ∼8 and ∼1% of Np and Pu, respectively. These results indicate that a minor portion of the total Np may be affected by environmental conditions that have little or no effect on Pu. Between 7 and 24% of the Pu was observed in treatments designed to liberate Pu and Np that are tightly bound to lithogenic phases or refractory silicates. The ²⁴⁰Pu/²³⁹Pu observed in accessible and refractory fractions ranged between 0.11 and 0.18. With the exception of one sample, the ²⁴⁰Pu/²³⁹Pu isotope ratios measured in the refractory fractions are essentially identical having a mean ratio value of 0.123 ± 0.001 (1σ). The ²⁴⁰Pu/²³⁹Pu ratios provide isotopic evidence that suggests a portion of non-fallout contamination has a refractory nature. The presence of similarly low ²⁴⁰Pu/²³⁹Pu ratios in refractory fractions of sediments from the Ob and Irtysh Rivers suggests the existence of a source of refractory Pu which is consistent with refractory “hot particles” derived from surface tests at the Semipalitinsk test site.     

中温焙烧/钠化氧化法回收电镀污泥中的铬

采用中温焙烧/钠化氧化法从电镀污泥中回收铬.结果表明,影响铬浸出率的最主要因素为焙烧温度.电镀污泥与碳酸钠质量比、焙烧时间、水浸时间对铬浸出率的影响较接近,在水浸水固比为10.0 ; 1.0(质量比)、室温、焙烧温度为650℃、焙烧时间为2.0h、电镀污泥与碳酸钠质量比为1:1、水浸时间为60 min的最佳浸出条件下,铬浸出率为99.3%;去除氢氧化铝、氢氧化锌的最佳反应温度和pH分别为90～95℃和7.5;去除硫酸钠晶体的最佳pH为4.0,在最佳试验条件下,铬回收率为90.57%.     

咪唑类[PF6]^-型离子液体萃取胺类化合物

以眯唑类[PF6]^-型离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺、对氯苯胺等7种胺类化合物的萃取,考察了溶液初始浓度、相比、盐类、pH及离子液体眯唑基团上取代烷基对萃取平衡的影响,并研究了萃取过程的热效应。实验结果表明：溶液初始浓度对分配系数影响较小;相比10：1是离子液体对胺类化合物的溶解饱和临界点,当相比大于10：1时,分配系数降低;NaCl、K2SO4可以增大萃取分配系数,ZnSO4对分配系数几乎没有影响;pH增加,分配系数增大;离子液体对不同取代基的胺类萃取能力有较大的差异,咪唑基团上取代烷基的长度对不同胺类物质的分配系数影响较显著;萃取过程属于焓增大的吸热过程。     

Assessment of heavy metal pollutants accumulation in the Tisza river sediments

In this study we have worked on the evaluation of heavy metal contamination in the sediments taken from the Tisza River and its tributaries, and thereby used the sequential extraction method, geochemical normalization, the calculation of the enrichment factor (EF), and the methods of statistical analysis. The chemical fractionation of Ni, Cu, Zn, Cr, Pb, Fe, and Mn, carried out by using the modified Tessier method, points to different substrates and binding mechanisms of Cu, Zn and Pb in sediments of the tributaries and sediments of the Tisza River. The similarities in the distributions of Fe and Ni in all types of sediments are the result of geochemical similarity as well as of the fact that natural sources mainly affect the concentration levels of these elements. The calculated enrichment factors (EF, measured metal vs. background concentrations) indicated that metal contamination (Cu, Pb, Zn and Cr) was recorded in the sediments of the Tisza River, while no indications of pollution were detected in the tributaries of the Tisza River and the surrounding pools. The maximum values of the EF were close to 6 for Cu and Pb (moderately severe enrichment) and close to 4.5 for Zn (indicating moderate enrichment). It can be said that the Tisza River is slightly to moderately severely polluted with Cu, Zn, and Pb, and minorly polluted with Cr. It is concluded that sediments of the Tisza serve as a repository for heavy metal accumulation from adjacent urban and industrial areas.     

Copper and zinc bioavailabilities to ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) grown in biosolid treated Chilean soils

The purpose of this study was assessing Cu and Zn availabilities in soils amended with a biosolid through the determination of their sequentially extracted chemical forms and their relationship with the contents of these metals in ryegrass (Lolium perenne L.) and subterranean clover (Trifolium subterraneum L.) plant tissues cultivated in a greenhouse using four soils classified as Aquic Xerochrepts and Ultic Haploxeralfs representatives of potential areas for biosolids application in the central zone of Chile. The soils were treated with sewage sludge at a rate of 0 and 30 Mg ha⁻¹. The greenhouse experiment was carried out through a completely randomized block design in a 2 × 4 (biosolid rate × soil) arrangement, considering three repetitions per treatment. The soils used in the greenhouse experiment before and after cultivation, were sequentially extracted with specific reagents and conditions in order to obtain the following fractions: exchangeable, sodium acetate-soluble, soluble in moderately reducing condition, K₄P₂O₇-soluble, soluble in reducing condition, and soluble in strongly acid and oxidizing condition. It was established that Cu and Zn were predominantly found in soils in less available forms, associated to organic matter, oxides and clay minerals. Zinc concentration in ryegrass plants was higher than that found in subterranean clover plants in biosolid-amended soils. Zinc contents in ryegrass shoot and root correlated with the exchangeable, bound-to-carbonate, and bound-to-FeOx metal forms in control soil. Copper and Zn bioavailabilities were estimated through satisfactorily fitted multiple linear regression models, with determination coefficients from 0.77 to 0.99, which showed a positive contribution of the labile metal forms in soils, especially in relation to Zn in both plant species.     

二元有机酸的络合萃取研究

研究了磷酸三丁酯（ＴＢＰ）和甲基异丁基酮（ＭＩＢＫ）对乙二酸,丙二酸,丁二酸和己二酸等二元有机酸的萃取及其影响因素。结果表明,萃取反应为中性络合萃取机理,有机相中生成１：２的萃合物;空腔效应,偶极作用和氢键等是影响萃取性能的主要因素;稀释剂,无机盐,温度及二元有机酸结构等对萃取性能都有重要影响。