2A12铝合金在模拟溶液中的周浸腐蚀行为

采用干湿周浸实验、失重法和电化学阻抗谱研究了2A12铝合金在0.6mol/L NaCl和0.6mol/L NaCl 0.02mol/L NaHSO3两种溶液中的腐蚀行为与规律, 利用扫描电镜(SEM)、能谱(EDX)和红外光谱(FTIR) 观察分析腐蚀产物表面形貌、结构和组成,测试了材料的力学性能.研究表明,随腐蚀时间的延长,腐蚀产物不断增多,失重增加,力学性能下降,阻抗模值逐渐减小;腐蚀产物形貌以团状和块状为主,在0.6mol/L NaCl溶液中腐蚀产物主要为铝的氯化物和氧化铝,在0.6mol/L NaCl 0.02mol/L NaHSO3溶液中腐蚀产物主要为氧化铝、铝的硫酸盐水合物和铝的氯化物;由于NaCl和NaHSO3共同作用,2A12合金在0.6mol/L NaCl 0.02mol/L NaHSO3溶液中腐蚀电流密度高,阻抗模值相对较小,腐蚀速率较高,腐蚀后失重大,力学性能下降幅度较大,腐蚀更严重.     

T2铜在不同海水飞溅条件下的腐蚀性能差异

目的研究T2铜在不同飞溅条件下的腐蚀行为。方法通过对T2铜在三亚热带海水飞溅区进行0.5、1、2 a三个周期的环境试验,采用扫描电子显微镜、X射线衍射仪对其腐蚀产物形貌、物相进行分析,使用电化学工作站对带锈样品进行分析。结果 T2铜在堤岸飞溅区和堤岸内飞溅区腐蚀速率随时间的延长逐渐下降。在飞溅区,不同周期T2铜的腐蚀产物为表面较薄的氧化层,且存在分层现象,主要由外层疏松的绿色Cu2(OH)3Cl和内层致密的棕色Cu_2O组成。不同试验周期,两处飞溅区试样表面的腐蚀产物都较为平整,堤岸飞溅区腐蚀产物层的平均厚度大于堤岸内飞溅区,腐蚀形貌均为均匀腐蚀。两处飞溅区锈层均由Cu_2O和Cu2(OH)3Cl相构成,堤岸飞溅区锈层主要为Cu_2O和Cu2(OH)3Cl相,堤岸内飞溅区锈层主要为Cu_2O相,存在少量Cu2(OH)3Cl相。结论在同一试验地点进行飞溅试验,由于飞溅条件不同,2a内铜的腐蚀速率、腐蚀产物等会存在差异。     

氯化铵盐粒导致的铜初期大气腐蚀行为研究

目的研究在氯化铵存在条件下,铜的大气腐蚀行为。方法采用扫描电子显微镜(SEM)、能谱(EDS)、傅里叶红外光谱(FT-IR)、X射线衍射(XRD)、滴定法和电化学等方法来确定铜的大气腐蚀过程和腐蚀产物。结果随着暴露时间的延长,铜的腐蚀质量损失变大,平均腐蚀速率变小。在氯化铵存在条件下,铜表面生成了Cu_2O、Cu_2(OH)_3Cl和Cu_2(OH)_2CO_3,其中Cu_2O为主要腐蚀产物,其质量占腐蚀产物总质量的97%以上。结论氯化铵的存在会对铜造成很强的腐蚀,随着暴露时间的延长,铜的腐蚀变得严重,但是暴露后期腐蚀速率将会减缓。     

OH~-浓度对地下水中铁碳酸盐沉淀形成的影响

铁的碳酸盐沉淀是Fe~0-PRB运行过程中最为常见的铁腐蚀产物,其对Fe~0-PRB的长期运行有重要的影响.探究这类沉淀产物形成的环境条件,可为控制Fe表面碳酸盐沉淀的生成提供重要依据.本文以Fe Cl_2、Na OH、Na_2CO_3为反应物,考察了缺氧条件下不同[OH~-]=0.02,0.06,0.1mol/L及R=[Fe~(2+)]/[OH~-]、R′=[CO_3~(2-)]/[OH-]对铁的碳酸盐沉淀生成情况的影响.结果表明,不同实验条件下检测到了Fe CO_3、Fe_2(OH)_2CO_3及Fe_6(OH)_(12)CO_3三种铁的碳酸盐沉淀.Fe_6(OH)_(12)CO_3仅能在低浓度[OH~-]=0.02mol/L时生成,高浓度的OH~-条件下不能生成.Fe_2(OH)_2CO_3在较低的OH-浓度,较小的R条件下生成;较高的OH~-浓度,较大的R同样有利于Fe_2(OH)_2CO_3的生成.Fe CO_3仅在[OH~-]=0.02mol/L,[Fe~(2+)]、[CO_3~(2-)]均较低情况下与Fe_2(OH)_2CO_3共同生成.     

氮源对氧化亚铁硫杆菌浸提废旧印刷线路板覆层铜的影响研究

采用摇瓶实验,在170rpm、30℃下,以氧化亚铁硫杆菌(Thiobacillus ferrooxidans)SW-02为浸提菌株,研究氮源对氧化亚铁硫杆菌浸提废旧印刷线路板覆层铜的影响。分析发现,以(NH4)2SO4作为氮源含量为1g/L时,浸提84h后铜浓度达到2.73g/L,铜的浸出效率较好。而采用(NH4)2HPO4作为氮源替代(NH4)2SO4,(NH4)2HPO4加入量在1g/L时效果较好,浸提84h后铜浓度达到3.52g/L。当(NH4)2HPO4在2g/L及以上时,会抑制细菌生长,导致浸出效率降低。实验结果表明,以(NH4)2HPO4作为氧化亚铁硫杆菌生长所需氮源,其浸出废旧印刷线路板覆层铜的效果优于(NH4)2SO4,最佳含量为1g/L。     

氨浸-加压氢还原法回收电镀污泥中的铜和镍

研究采用氨浸-加压氢还原法对电镀污泥中的铜和镍进行了分离回收,分析了氨浸和氢还原过程中各因素的影响。结果表明,采用NH3-(NH4)2SO4氨浸体系,在温度25℃,时间60min,NH3浓度6.5mol/L,液固比3的条件下,Ni、Cu、Zn的浸出率分别达到80.25%、77.42%、91.07%;当浸出液pH5.4～5.6,温度160℃,时间60min,搅拌转速500r/min,氢分压2MPa时,氢还原铜和镍的回收率分别达到71%和64%。     

典型航空装备用金属材料在不同酸性盐雾环境下的腐蚀效应及机理

目的对比分析硫酸盐雾试验和盐雾/SO2复合试验的环境效应及机理差异。方法针对硫酸盐雾试验和ASTM G85附录A4-X4中的盐雾/SO2复合试验两种酸性盐雾试验方法,选取3种金属试片(4130高强度合金钢镀铬、40CrNiSi合金钢镀镍、2A12铝合金导电氧化)和2种合金钢自锁螺母(30CrMnSiA镀镉钝化螺母、30CrMnSiA镀锌钝化螺母)作为试验对象,对其开展两种酸性盐雾试验条件下的腐蚀试验,采用扫描电子显微镜、能谱分析研究各试验件表面生成的腐蚀产物形貌及组分特征,对比分析两种试验条件下的环境效应及机理差异,并结合耦合多电极矩阵(CMAS)测试技术,对比分析两种酸性盐雾试验条件下的环境腐蚀性特点及严酷性差异,初步探讨了两种试验条件与外场舰载平台环境的相关性关系。结果盐雾/SO2复合试验条件下CMAS电极的腐蚀深度达到同周期硫酸盐雾试验下的10倍左右。盐雾/SO2复合试验下,试样表面腐蚀产物中均检测出S元素的存在。相比于硫酸盐雾试验,盐雾/SO2复合试验与外场舰载平台环境具有更好的一致性。结论美军现行的盐雾/SO2复合试验方法与外场舰载平台环境具有更好的相符性。     

硝酸根电化学还原去除过程阴极电位振荡研究

硝酸根在电化学还原去除过程中存在多价态变化行为,该过程是一个典型的远离平衡态的非线性体系.为探明硝酸根在去除过程中发生的电化学行为,研究了H₂SO₄浓度、电流、反应温度及NO₃^-浓度对阴极电位振荡的影响规律.采用循环伏安法、XRD、SEM-EDS及XPS表征方法,分析了反应体系循环伏安特性,以及反应前后阴极Cu表面的物相组成、微观形貌、表面电子价态等变化规律.研究结果表明,在恒流条件下(Pt作为阳极、Cu作为阴极),H₂SO₄-NaNO₃体系发生了明显的电位振荡;当H₂SO₄浓度为0.10mol/L,电流为12mA,温度为20℃,NaNO₃浓度为0.20mol/L最佳电位振荡条件下,振荡平均振幅为1.15V,振荡平均周期为3s.另外,硝酸根在电化学还原去除过程产生的周期性电位振荡主要原因是阴极Cu表面生成的致密CuO薄膜不断溶解和形成,以及阴极表面H₂的周期性产生与消失.     

白铜和黄铜在SO2气氛中的腐蚀对比

通过SO2气体腐蚀试验、腐蚀表面的形貌观察和产物分析,对白铜和黄铜进行了对比研究。结果表明:两种铜的质量损失与SO2体积分数均成线性关系,在SO2污染环境中白铜的抗蚀能力优于黄铜;黄铜腐蚀产物主要为CuSO4.5H2O、Cu4(SO4)(OH)6.2H2O和Cu2O,白铜腐蚀产物主要为Cu4(SO4)(OH)6.2H2O和Cu2O。     

天然海水中铜离子的添加对EH40钢腐蚀的影响

目的 研究天然海水中添加1.5、15 mmol/L铜离子对EH40钢腐蚀速率、腐蚀产物形貌及成分的影响规律,并揭示其作用机制.方法 采用天然海水实验室挂片的方式进行4周的腐蚀实验,定期对试样进行表征,并检测海水环境参数.结果 在海水中添加1.5、15 mmol/L铜离子后,EH40钢的腐蚀速率加快,同时表面腐蚀产物出现特殊分层现象,并包含铜单质层.结论 海水中添加1.5、15 mmol/L铜离子,对EH40钢腐蚀的促进作用主要通过三种机制,铜离子水解形成酸性腐蚀环境、铁和铜离子的置换反应消耗试样基体、Fe-Cu电偶腐蚀池加速阳极铁的溶解.     

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.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.