天然海水中碳钢缓蚀剂吸附和阳极脱附行为的研究

以锌盐、葡萄糖酸盐为主要缓蚀成分复配的适用于天然海水中碳钢的高效缓蚀剂,采用极化曲线、循环伏安曲线和交流阻抗谱图分析了该缓蚀剂的阳极脱附行为.结果表明,碳钢在海水中的零电荷电位约为-0.6 V;缓蚀剂的吸附电位区间为-0.5～-0.8 V,缓蚀剂在该区间内存在特性吸附.当阳极极化电位超过-0.45 V时,极化电流迅速增大,缓蚀剂因发生大量脱附而失去对阳极过程的控制.     

电增强活性炭纤维吸附有机污染物的动力学研究

研究了在电极化条件下,几种具有代表性污染物质在活性炭纤维上的电吸附动力学特性.结果表明,各种污染物的电吸附动力学比较好地符合Lagergren一级吸附动力学,其平衡吸附量在电极化下的增加量各不相同.在400mV的极化电位下,苯酚钠的吸附量从开路时的0.008 3mmol·g^-1增加到0.18 mmol·g^-1,增加了17倍;而对硝基苯酚的吸附量从开路时的2.93mmol·g^-1降到2.65 mmol·g^-1.在-400mV的极化电位下,苯胺的吸附量从开路时的3.60 mmol·g^-1增加到3.88 mmol·g^-1;而十二烷基苯磺酸钠的吸附量从开路时的2.20 mmol·g^-1降到1.59 mmol·g^-1.说明不同取代基的苯衍生物,电吸附改变量不相同,供电子基团的单取代苯,正极化都能明显增强其吸附量;但是吸电子基团的单取代,正负极化对吸附量的影响都很小;供体-共轭桥键-受体型结构的苯衍生物,正负极化都使其吸附减弱但吸附速率加快.静电作用在离子型污染物的电吸附中表现明显.     

活性炭处理皂素废水及其再生的实验研究

采用活性炭对皂素废水进行吸附处理,研究了活性炭投加量、吸附时间及吸附次数对皂素废水色度去除率的影响.同时,研究了在微波辐照条件下,微波功率和辐照时间对吸附皂素废水后的活性炭脱附的影响.结果表明,当活性炭投加量为0.13g·mL-1时,吸附12h后皂素废水的色度去除率为96.17%.此条件下活性炭可以重复吸附皂素废水3次(按照色度去除率70%为限).当微波功率为500W、辐照时间为30min时,活性炭可被有效地再生,活性炭的再生率可达79.75%.     

电增强环氧树脂基聚合物膜萃取水样中的硝基苯

以环氧树脂基聚合物膜为萃取相,在电场作用下富集目标物,与高效液相色谱(HPLC)联用,应用于环境水样中硝基苯污染物的测定.考察了电压大小、萃取时间、洗脱时间、离子强度和溶液pH值对电增强萃取效率的影响.实验结果表明,环氧树脂基聚合物膜的萃取量与膜上所施加的控制电位相关,阴极极化时,膜对硝基苯的萃取量增大;在阳极极化时,膜萃取量减小.在电压为-0.3kV,硝基苯溶液pH=4的条件下,萃取20min,得到该方法的检出限为0.015μg·mL-1,在0.05～3.0μg·mL-1范围内具有良好的线性关系,可决系数为0.9929,变异系数小于5%.用上述方法分析鱼塘水,硝基苯3种不同加标水平的回收率为79.8%～108.2%.结果表明,该方法既可用于环境水样品中的硝基苯去除又可用于检测.     

电场辅助活性炭吸附法去除水中的Cu2+

通过电场辅助活性炭吸附水中的Cu²⁺,分析吸附机理,pH值对Cu²⁺吸附的影响以及活性炭电极的再生性.结果表明,活性炭电极添加电场后,Cu²⁺的去除率明显提高,当活性炭电极间施加1.0V电压时,Cu²⁺的去除率提高了223.5%.通过Langmuir和Freundlich吸附等温线模型分析,添加电场后,活性炭电吸附Cu²⁺主要是带电活性炭表面形成的双电层作用,而不仅仅是活性炭表面化学吸附点位.pH值对电场辅助活性炭吸附水中Cu²⁺的影响极大,pH值太低时,水中H⁺会与Cu²⁺竞争活性炭表面化学吸附点位以及双电层点位.研究发现采用电极短接方式可提高Cu²⁺后的脱附率及脱附速率,脱附率达到79.1%.通过FTIR图谱可知,表面官能团-COOH和-C=O吸附的Cu²⁺难以脱附出来,但得益于此,再循环吸附-脱附2~4次时,主要以双电层静电吸附为主,脱附效率提高,电极的再生性良好.     

KOH活化微孔活性炭对对硝基苯胺的吸附动力学

以互花米草为原料,经过碳化、KOH活化两步法制备了低成本、高比表面的微孔活性炭SAAC.通过静态实验研究了活性炭SAAC对水溶液中对硝基苯胺的吸附特性,并从动力学角度探讨了吸附机理.结果表明,微孔活性炭SAAC对对硝基苯胺吸附动力学数据符合准二级方程,吸附速率在前25min由内扩散控制,而后由膜扩散与内扩散共同控制.Freundlich方程能更好地描述对硝基苯胺在活性炭SAAC上的等温吸附行为;在15℃时,活性炭SAAC对对硝基苯胺的Langmuir最大吸附量为719mg/g.     

载溴活性炭去除烟气中的单质汞

为提高活性炭对烟气中单质汞的吸附作用,利用溴对活性炭进行处理.通过对吸附容量和吸附动力学的测试,研究了载溴活性炭对气体中的单质汞的去除行为.结果表明,载溴可使活性炭对单质汞的吸附量显著增加,并加快对单质汞的吸附速率.实验条件下,当载溴量为0.33%时,活性炭对汞的饱合吸附量可增加约80倍,吸附容量达0.2mg/g;相对吸附系数增加了约40倍.溴负载量越高,吸附强化作用越显著.温度升高,载溴活性炭的吸附能力略有下降,烟气中的二氧化硫对单质汞的吸附速率略有抑制作用.     

高比表面积活性炭(HSAAC)对水中镉(Ⅱ)吸附性能的研究

以石油焦基为原料,采用KOH活化法制取高比表面积活性炭.考察了高比表面积活性炭吸附水中Cd(Ⅱ)时,pH值、Cd(Ⅱ)浓度、吸附时间和活性炭用量等因素对Cd(Ⅱ)吸附量和水中Cd(Ⅱ)残余浓度的影响.实验结果表明高比表面积活性炭在适宜条件下对Cd(Ⅱ)具有较大的吸附量和良好的再生效果.为HSAAC在废水中的实际应用提供了理论依据.     

海洋工程用新型牺牲阳极设计与性能研究(Ⅲ)——中尺寸阳极实海试验研究

目的通过构型优化设计一种新型牺牲阳极,使其在与常规阳极质量相当的前提下,增加初期发生电流,使被保护体较快极化到保护电位,后期发生电流降低,满足平均和末期保护电流需要,达到节约牺牲阳极用量的目的。方法通过在传统梯形阳极两侧增加两个翼翅优化设计出新型牺牲阳极,并针对中等规格尺寸的新型阳极与常规阳极进行实海试验。结果质量与常规阳极相近的新型阳极,初期发生电流增加11%,而后逐渐增加到18%,被保护体优先极化到保护电位。翼翅消耗完全后,新型阳极与常规阳极均呈圆柱形,发生电流亦与常规阳极相当。结论所设计的新型牺牲阳极在与常规阳极质量相当的前提下,可使被保护体较快极化到保护电位,节约了牺牲阳极用量。     

一种两步联合控制吸附动力学模型的研究

以酸性染料为对象 ,进行了粒状活性炭吸附扩散过程的动力学研究 .实验结果表明活性炭对酸性红B的吸附反应速度主要受吸附物质向活性炭表面的迁移速度和活性炭颗粒内的扩散速度的影响 ,由此建立了一种新的活性炭吸附过程的复合动态吸附模型 ,并使模型符合在较低浓度时受一级扩散反应控制为主 ,在较高浓度时受Boyd扩散控制为主 .该模型能将不同浓度下的扩散动力学过程统一起来     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.