AOAB工艺处理难降解混合化工污水的挂膜启动

采用AOAB(水解酸化A1+生物接触氧化O+深度水解酸化A2+曝气生物滤池BAF)工艺处理难降解混合化工污水,重点研究工艺挂膜方式和生物膜的驯化。结果表明,采用分段连续式挂膜法进行反应器挂膜,20 d即可完成快速挂膜启动;采用分阶段同步培养驯化法驯化生物膜,30 d内可完成高浓度多组分混合化工污水进水的驯化,最终进水COD 1 456 mg/L,出水COD 324 mg/L,总去除率76.85%,驯化效果显著;整个工艺对COD的降解主要集中在生物接触氧化池和曝气生物滤池,驯化期间生物接触氧化池去除率稳定在40%左右,曝气生物滤池去除率稳定在50%以上。同时,通过对比一段水解酸化和深度水解酸化的VFA(挥发性脂肪酸)产出,表明在高有机负荷进水时,一段水解酸化降解大分子有机物的能力有限,但这些有机物可通过二段水解酸化再次降解,由此体现了AOAB工艺在处理多组分混合型的难降解化工污水的优势。     

MBR净化受污染地表水的自然启动及稳定运行除污染特性

为了考察膜生物反应器(MBR)净化受污染地表水自然启动过程中功能菌群的成熟规律及碱度对MBR去除水中氨氮的影响,通过构建小试规模的MBR,考察了MBR处理受污染地表水的自然启动和稳定运行除污染特性。结果表明,MBR在自然启动过程中不会出现异养菌成熟的标志,系统对进水DOC、UV254和CODMn的平均去除率分别仅为(14.5±5.1)%、(12.6±5.6)%和(31.2±7.4)%,应考虑将其他工艺与MBR联用以提高系统的有机物去除能力。启动23天后,MBR中的亚硝化细菌成熟,NH3-N去除率达到80%以上;启动31 d后,MBR中的硝化细菌成熟,出水NO2--N稳定在0.05mg/L以下。碱度对MBR去除NH3-N效能影响较大,向进水中投加30 mg/L的NaHCO3能使MBR对NH3-N的去除率由(86.1±3.7)%提高至(98.0±1.6)%。在连续曝气、10 L/(m2.h)通量、每10 min反洗15 s运行模式下,MBR的膜污染较为严重,平均TMP增长速率为0.45 kPa/d,需进一步优化相关参数以实现MBR的长期稳定运行。     

Electrochemical oxidation of benzene on boron-doped diamond electrodes

This work presents an electrochemical investigation of the benzene oxidation process in aqueous solution on boron-doped diamond (BDD) electrodes. Additionally, in order to determine the main products generated during the oxidation process, electrolysis and high performance liquid chromatography experiments were carried out. The complete degradation of this compound was performed aiming to a further application in waste water treatment. The cyclic voltammetry studies indicate that benzene is irreversibly oxidized in acid medium (H₂SO₄ 0.5 M) on the BDD electrode surface at 2.0 V versus Ag/AgCl in a diffusion controlled process. During the cycling, other products are generated, and a pair of peaks was observed that can be associated with the oxi-reduction of anyone of the following species: hydroquinone, benzoquinone, resorcinol or catechol. The electrolysis experiments were carried out at 2.4 and 2.5 V on the BDD electrode surface in a solution containing 1 × 10⁻² M of benzene (below the saturation concentration in aqueous solution), for 3 and 5 h, respectively. The main products measured were: hydroquinone, resorcinol, p-benzoquinone, catechol and phenol. The complete electrochemical benzene degradation was performed in the electrolysis experiments using a rotating BDD disc electrode (2.5 V for 5 h) and the main products detected were all measured at concentrations lower than 10⁻⁵ M in this condition. The boron-doped diamond electrode had proved to be a valuable tool for the electrochemical degradation of the benzene, a very stable chemical compound.     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.     

Removal of phenolic estrogen pollutants from different sources of water using molecularly imprinted polymeric microspheres

The efficiency and effects of using Bisphenol A-molecularly imprinted polymeric microspheres (MIPMs) to remove phenolic estrogens from different sources of water were evaluated. MIPMs prepared by precipitation polymerization removed a group of phenolic estrogens from different kinds of water selectively and effectively. The highest removal efficiency was observed at pH=5. Fifty millimoles per litre ions or 10mg/L humid acid improved removal efficiency. MIPMs were more suitable to remove trace estrogens in large volume than high concentration of estrogens in small volume. The removal efficiency of spiked tap water, lake water and river water were better than that of distilled water. Hundred milligrams of MIPMs had higher removal selectivity and efficiency than those of 100mg or 300mg activated carbons. Moreover, MIPMs can be re-used for at least 30 times without losing any removal efficiency. MIPMs provided a selective, simple, reliable and practicable solution to remove trace phenolic estrogens from different sources of water.     

Persistent organic pollutants (POPs) in Caspian seals of unusual mortality event during 2000 and 2001

Persistent organic pollutants including organochlorine pesticides, PCBs, and PCDDs/DFs were determined in the blubber of Caspian seals, which died during an outbreak of canine distemper virus in 2000 and 2001. DDTs were the predominant contaminants that ranged from 3.1 to 560 microg/g lipid. A negative correlation was observed between concentration of contaminants and blubber thickness. During spring, as the blubber layer becomes thin after breeding and moulting, seals may face higher risk due to the increased concentration of organochlorines in their bodies. TEQs in the blubber of Caspian seals (10-340 pg TEQ/g) were lower than those in seals from other locations, suggesting that toxic effects of these contaminants are a deal less in the present population and they are unlikely to be linked to mass mortality. The levels of PCBs and pesticides in Caspian seals, however, comparable to those in other aquatic mammals that have suffered from epizootics, might pose a risk of immunosuppression.     

小氮肥生产装置火灾爆炸危险性分析与评价

结合小氮肥生产工艺的特点及企业实际情况,在分析小氮肥生产过程中火灾爆炸危险因素的基础上,应用道化学法对小氮肥生产工艺中的煤气发生炉、煤气柜、脱硫、变换、铜洗和合成等6个单元进行了固有危险指数和安全补偿措施后的危险指数的计算,同时对评价单元的火灾爆炸危险度进行了研讨。分析评价结果表明,合成单元和煤气发生炉的固有危险度最大,生产过程中极易发生火灾爆炸危险,小氮肥企业应特别重视。笔者建议,小氮肥企业应设法改进监控和操作手段,降低相应的工艺危险系数或加强安全防范,提高整个系统的安全性。     

The use of clays to sequestrate organic pollutants. Leaching experiments

Leaching experiments are performed from clay-pollutant systems in order to evaluate the capability of clays to sequestrate organic pollutants from wastewaters. Reference kaolinite KGa-1b, montmorrillonite SWy-2 and reference soil BCR^®-700 are the sorbent materials. 2,4,6-trichloroaniline (2,4,6-TCA) and 4-chlorophenol (4-CP) are the typical pollutants, sorbed at amounts of 10.0 mg g⁻¹ and 5.8 mg g⁻¹ on SWy-2 and 7.3 mg g⁻¹ and 2.2 mg g⁻¹ on KGa-1b, respectively.The leaching agents are ultrapure water and model solutions of acid rain and surface waters that simulate meteoric leaching. 1.0 mM HNO₃, 1.0 mM H₂SO₄ solutions and a methanol/water 50/50 (v/v) mixture simulate leaching agents of industrial source.The results are compared and the preferential capability of the clays to sequestrate the more lipophilic 2,4,6-TCA is evidenced.The bond interactions are discussed and explained through preferential adsorption reactions. For montmorrillonite also a simultaneous intercalation in the phyllosilicate interlayer is proposed.     

Diet shifts during egg laying: Implications for measuring contaminants in bird eggs

We combined stable isotope tracers of blood plasma, blood cells and egg contents with faecal analysis during pre-breeding and egg laying phases in two dipper species Cinclus cinclus and Cinclus mexicanus to determine the occurrence of dietary shifts during egg production and to assess consequences for egg contaminant loads. In both species, changes in δ¹³C (C. cinclus) or δ¹⁵N (C. mexicanus) in female plasma relative to red blood cells indicated a dietary shift during laying that was not observed in males. Eurasian dippers increased prey consumption as breeding approached, shifting from primarily trichopteran insect larvae to ephemeropterans and plecopterans. In American dippers, egg-laying females switched to feeding at a higher trophic level by consuming more fish. Eggs derived from higher trophic level diets contained more mercury (American dipper), polychlorinated biphenyls and some organochlorines, especially DDT metabolites. The results demonstrate how dietary changes during egg laying accompany the demands for egg production with consequences for contaminant deposition in avian eggs.     

微波催化氧化修复技术处理有机氯污染土壤

采用微波催化氧化修复技术处理常州某农药厂有机氯农药污染场地和南通某化工厂有机氯污染场地土壤,考察不同参数条件下实验装置对污染土壤的处理效能。结果表明,在微波功率18kW、微波辐射时间20min、土壤处理量400kg/h、土壤含水率15%、活性炭添加量0.03kg/kg的最佳条件下,实验装置运行稳定,有机氯农药污染土壤中氯丹去除率可达70%左右;有机氯污染土壤中邻二氯苯、石油烃总量、1,2-二氯乙烷、苯酚去除率分别可达到99.98%、91.29%、98.52%、74.74%。研发的污染土壤微波催化氧化修复技术及实验装置对有机氯污染土壤的修复具有一定的普适性。