Electrochemical or UV-photochemical oxidation of industrial wastes containing polar aromatic sulphonates

BACKGROUND AND INTENTION: Aromatic sulphonates other than surfactants and their hydroxy and amino-derivatives are important intermediates for the production of azo dyes. Their production on a large scale can be detrimental for the environment, if the by-products of their synthesis are not disposed of appropriately. An industrial waste, the organic components of which were mainly amino and hydroxy-substituted aromatic sulphonates, seriously endangers the environment close to an dismissed Italian industrial site. Inorganic sulphates and chlorides contained in the waste seriously hinder its disposal by incineration, since they corrode furnace walls. In this work, preliminary exploration of aqueous-phase electrochemically and photochemically induced oxidation techniques have been performed as possible alternatives to incineration. METHODS: Electrochemically-induced oxidation was experimented on individual aromatic sulphonates and on an industrial waste by electrolysing them between smooth platinum electrodes at low temperature (5 degrees C) and high current densities (0.4 A/cm2) with aqueous 0.5 M NaHSO4 electrolyte. Photochemically-induced oxidation was performed by irradiating individual aromatic sulphonates or industrial waste with a 500 W mercury lamp in the presence of sodium peroxydisulphate. RESULTS AND DISCUSSION: After 200 min electrodegradation, 90% of the original compounds disappeared, while 50% Total Organic Carbon (TOC) of an industrial waste was removed from solution after 10 hours. After 180 min UV-photodegradation, 90% of two test aromatic sulphonates disappeared, while 65% of TOC of industrial waste was removed after 5 hours. CONCLUSIONS: Two methods, electrochemical and UV-persulphate oxidation of an industrial waste, were used in order to propose a disposal procedure alternative to incineration. Electrodegradation with smooth Pt anode in 0.5 M NaHSO4 at 5 degrees C halved TOC concentration within 10 hours, while persulphate-assisted UV-photochemical oxidation with a 500 W high pressure Hg lamp abated two-thirds of TOC concentration after 5 hours. Energetic consumption of electrodegradation was 0.33 kWh/g TOC, while that of photooxidation was larger than 2 kWh/g TOC. Although both techniques can be considered efficient from a purely chemical point of view, since both are capable of wet-oxidising the aromatic sulphonates and the industrial waste, electrodegradation seems more promising than a photochemical degradation if economical considerations are also taken into account. Considering also that neither cell design nor catalyst were optimised in this preliminary study, the energy yield of electrodegradation seems likely to be largely improved.     

Aniline degradation by electrocatalytic oxidation

The degradation of aniline solution in alkaline medium of pH 11.0 by electrocatalytic oxidation has been studied using an electrochemical reactor containing a SnO₂–Sb₂O₃–PtO anode and a Ti cathode, both of 54 cm² area. Hydroxyl radicals (HO^√) are produced at the anode, being tested with the trace catcher salicylic acid and phenol by spectrophotometery and high performance liquid chromatography. Intermediates dianiline, 4-anilino phenol and azobenzol were detected by gas chromatography–mass spectrometry. The existence of HO^√ produced in the aniline degradation was assayed with scavenger tertiary butanol. The results showed that electrocatalytic oxidation is an effective process for the degradation of aniline. A general reaction pathway that accounts for aniline degradation to CO₂ involving those intermediates is proposed.     

垃圾填埋场稳定化研究（Ⅰ）

通过填埋场的实验室规模的模拟实验，研究了负温和低温条件下城市生活垃圾的降解行为。经８个月的阵解，发现含水率、污泥的加入以及高温均有利于位圾降解。菜类垃圾的降解率为５０％以上：而含水率为６０％的混合垃圾，降解率为２０％以下。测定了单位垃圾产生的气体和浸取液量以及浸取液的化学耗氧量、含水率和无机残渣。讨论了本工作在寒区填埋场工艺设计的实践意义。     

诺卡氏菌属对对苯二甲酸降解的研究

从活性污泥中分离驯化出一株能降解对苯二甲酸(TA)的诺卡氏菌属(文中称细菌A)，经复壮后，接种于TA液体培养基中。研究证明，该细菌对TA废水CODCr的最大去除率可达49．46％。综合考虑不同氮源对细菌A的TA降解率和去除废水CODCr效率的影响，氯化铵是最佳的氮源。     

气相色谱法测定黄瓜和土壤中代森锰锌的残留及其消解动态分析

采用GC-FPD(S)法测代森锰锌在黄瓜和土壤中的残留,通过优化前处理和检测条件,使方法在0.007 6 mg/L~3.80 mg/L范围内线性良好,在黄瓜和土壤中的方法检出限分别为5.12μg/kg和2.35μg/kg。黄瓜和土壤3个质量比水平的空白加标回收率分别为91.1%~96.5%和82.4%~90.5%,7次测定结果的RSD为5.0%~6.5%和2.4%~4.1%。将该方法用于研究代森锰锌在黄瓜和土壤中的消解动态,得知代森锰锌在黄瓜中的半衰期为3.63 d~4.77 d,在土壤中的半衰期为4.19 d~7.33 d。     

潮汐河网可降解有机物降解系数研究

潮汐河网具有其独特的水物理及水化学特性。本文采用珠江三角洲河网区域20个水样的BOD降解实验数据,并用BOD反应一级动力学方程进行数据拟合,结果表明,潮汐河网水体BOD降解过程的延滞期消失,远离污染源河段河水的BOD降解过程两阶段区分不明显,降解过程符合BOD反应一级动力学方程。此外,潮汐河网河水的降解系数随时间的变化过程是随机的。      

Acute toxicity of 353-nonylphenol and its metabolites for zebrafish embryos

Background, aim and scope  Nonylphenol (NP) can be detected in the aquatic environment all over the world. It is applied as a technical mixture of isomers of which 353-NP is the most relevant both in terms of abundance (about 20% of total mass) and endocrine potential. 353-NP is metabolised in sewage sludge. The aims of the present study were to determine and to compare the acute toxicity of t-NP, 353-NP and its metabolites as well as to discuss if the toxicity of 353-NP changes during degradation. Materials and methods  353-NP and two of its metabolites were synthesised. The zebrafish embryo test was performed according to standard protocols. Several lethal and non-lethal endpoints during embryonal development were reported. NOEL, LOEL and EC₅₀ were calculated. Results  All tested compounds caused lethal as well as non-lethal malformations during embryo development. 353-NP showed a higher toxicity (EC₅₀ for lethal endpoints 6.7 mg/L) compared to its metabolites 4-(3.5-dimethyl-3-heptyl)-2-nitrophenol (EC₅₀ 13.3 mg/L) and 4-(3,5-dimethyl-3-heptyl)-2-bromophenol (EC₅₀ 27.1 mg/L). Discussion  In surface water, concentrations of NP are far below the NOEC identified by the zebrafish embryo test. However, in soils and sewage sludge, concentrations may reach or even exceed these concentrations. Therefore, sludge-treated sites close to surface waters should be analysed for NP and its metabolites in order to detect an unduly high contamination due to runoff events. Conclusions  The results of the present study point out that the toxicity of 353-NP probably declines during metabolisation in water, sediment and soil, but does not vanish since the major metabolites exhibit a clear toxic potential for zebrafish embryos. Recommendations and perspectives  Metabolites of environmental pollutants should be included in the ecotoxicological test strategy for a proper risk assessment. An erratum to this article can be found at     

Biodegradation of mono-alkyl phthalate esters in natural sediments

Mono-alkyl phthalate esters (MPEs) are primary metabolites of di-alkyl phthalate esters (DPEs), a family of industrial chemicals widely used in the production of soft polyvinyl chloride and a large range of other products. To better understand the long term fate of DPEs in the environment, we measured the biodegradation kinetics of eight MPEs (-ethyl, -n-butyl, -benzyl, -i-hexyl, -2-ethyl-hexyl, -n-octyl, -i-nonyl, and -i-decyl monoesters) in marine and freshwater sediments collected from three locations in the Greater Vancouver area. After a lag period in which no apparent biodegradation occurred, all MPEs tested showed degradation rates in both marine and freshwater sediments at 22 °C with half-lives ranging between 16 and 39 h. Half-lives increased approximately 8-fold in incubations performed at 5 °C. Biodegradation rates did not differ between marine and freshwater sediments. Half-lives did not show a relationship with increasing alkyl chain length. We conclude that MPEs can be quickly degraded in natural sediments and that the similarity in MPE degradation kinetics among sediment types suggests a wide occurrence of nonspecific esterases in microorganisms from various locations, as has been reported previously.     

环糊精在环境治理中的应用研究进展

环糊精及其衍生物由于具有一定大小的低极性空腔结构,能够包合多种低极性有机物,形成主客体包合物.这种包合物的形成可以增加有机物的水溶性和促进其被微生物的分解利用;可以改变有机物的物理化学特性,促进其在光化学和芬顿体系中的降解;可以在去除有机物的同时,去除Cd2 等无机物;此外,环糊精还可以用来制成环境友好材料,吸除空气和水中污染物.     

UV/微曝气联用工艺对内分泌干扰物BP的去除效果和影响因素

采用新型工艺UV/微曝气对水中内分泌干扰物4-叔丁基苯酚（BP）进行降解研究.结果表明,UV/微曝气是一种高级氧化法,可以有效去除水中BP;UV/微曝气联用工艺降解BP受本底TOC值、BP初始浓度值、UV光强以及溶液初始pH影响较大.随着TOC值的降低,BP降解速率k₁迅速增加;随着光强的增大,BP的降解速率呈线性增长;在189～410 μg/L浓度范围内,k₁随着BP浓度的增大而逐步增大,在410～971 μg/L浓度的范围内,k₁随着浓度的增大而逐步降低;pH 2.77～4.01范围内UV/微曝气对BP降解速率较大,pH 4.70～8.16范围内UV/微曝气对BP降解速率较低.