氧化聚合型包覆技术（OTC）在热带海洋大气环境螺栓中的应用

目的 研究氧化聚合型技术(OTC)在热带海洋大气环境中对高强螺栓的防护效果。方法 在三亚大气腐蚀试验站开展OTC包覆和未保护的高强螺栓6 a的大气曝晒试验,通过扫描电镜(SEM)、X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)和激光共聚焦显微镜(LSCM)开展腐蚀形貌和成分分析,通过质量损失试验考察OTC包覆和未保护的高强螺栓的腐蚀行为。结果 未经保护的螺栓表面生成大量棕红色的腐蚀产物,XRD分析表明,其主要成分为α-Fe OOH、β-Fe OOH、γ-Fe OOH、Fe3O4和Fe₂O₃等,其中β-Fe OOH晶体结构中含有Cl–,会加速基体腐蚀。经LSCM分析,螺栓垫片整体呈全面腐蚀状态,但同时发生局部腐蚀,最深的点蚀坑达120μm以上。经OTC技术保护的高强螺栓,仅在底部出现少量棕色物质,大部分仍呈现原有的黑色基体表面,OTC包覆螺栓6 a的腐蚀速率约为未保护螺栓的腐蚀速率1/15,OTC包覆垫片表面未出现明显腐蚀。结论 氧化聚合型包覆技术显著降低了高强螺栓的腐蚀速率,具有优良的耐腐蚀性能,在热带海洋大气环境对高强螺栓起到良好的长...     

P265GH低合金钢在模拟污染大气环境中的腐蚀行为

目的研究P265GH钢在模拟污染大气环境中的腐蚀行为,探讨Na HSO3和Na Cl的协同作用对P265GH钢大气腐蚀影响。方法利用SEM,XRD和FTIR技术以及腐蚀质量损失分析。结果在Na HSO3存在的环境中,α-Fe OOH易于形成,而在Na Cl存在的环境中,γ-Fe2O3和Fe3O4易于形成,两者同时存在的环境中,P265GH钢腐蚀质量损失比单一腐蚀介质存在时的质量损失大。结论Na HSO3和Na Cl之间存在协同效应,腐蚀介质对P265GH钢腐蚀影响顺序为Na HSO3+Na Cl>Na HSO3>Na Cl。     

不锈钢在西太平洋深海环境中腐蚀规律研究

目的 研究不锈钢在西太平洋海域深海环境中的腐蚀规律。方法 采用深海高效串型试验装置对304不锈钢和316L不锈钢在西太平洋深海环境中进行深海实海腐蚀试验,分析不锈钢的腐蚀形貌、腐蚀速率和点蚀深度规律等,研究2种不锈钢在500、800、1 200、2 000 m海深下的腐蚀规律。结果 304不锈钢与316L不锈钢腐蚀质量损失主要由缝隙腐蚀引起,316L不锈钢的腐蚀程度总体上低于304不锈钢,304不锈钢的腐蚀速率低于0.4 mm/a,316L不锈钢的腐蚀速率低于0.25 μm/a。深海环境中,304不锈钢的腐蚀产物主要是α-Fe2O3、γ-FeOOH、γ-Fe2O3,316L不锈钢的腐蚀产物主要是α-FeOOH、γ-FeOOH、γ-Fe2O3。结论304不锈钢和316L不锈钢在西太深海环境中使用过程中应避免缝隙的形成,降低其发生缝隙腐蚀和点蚀的概率。     

不同腐蚀体系中低合金钢锈层的拉曼光谱研究

利用激光拉曼光谱法研究了舰船用镍铬系低合金钢在天然海水以及分别添加双氧水、高氯酸钾和过硫酸钠的NaCl（3.5％）溶液等4种体系中浸泡后腐蚀锈层的物相组成。结果表明：在含双氧水体系和天然海水体系中,钢样的内外锈层物相主要是α-Fe2O3、γ-FeOOH和Fe3O4。高氯酸钾和过硫酸钠腐蚀体系,其腐蚀锈层的外锈层除了含有α-Fe2O3和γ-FeOOH外还出现了γ-Fe2O3,内锈层只含有α-Fe2O3和γ-FeOOH,未发现Fe3O4。说明镍铬系低合金钢在含双氧水体系和天然海水体系中的腐蚀锈层物相组成差异最小。     

碳钢和耐候钢加速腐蚀实验研究

通过对Q235碳钢和09CuPCrNi耐候钢的周期浸润加速腐蚀实验所得到的锈层结构的XRD和拉曼光谱分析表明:γ-Fe2O3、γ-FeOOH和α-FeOOH是构成锈层的主要腐蚀产物.锈层中最终形成的稳定的α-FeOOH腐蚀产物所占比例和分布都将影响耐候钢的耐蚀性能.耐候钢中的Cr可在表面形成致密的氧化膜,同时Cr在缺陷处沉淀析出,可以加速锈层中缺陷的愈合,从而可抵御大气中水气及其有害离子的侵入,防止基体金属进一步腐蚀.因此,增加耐候钢中的Cr的含量将有助于提高耐候钢的耐蚀性能.     

Q235钢在模拟自然环境下失效行为的电化学研究

采用电化学阻抗谱(EIS)和阴极极化曲线研究了Q235钢在薄液膜条件下的大气腐蚀过程,探讨了液膜厚度、Cl-和腐蚀产物对Q235钢失效过程的影响.结果表明液膜厚度会影响O2的扩散过程,并进一步影响腐蚀速率;C1～环境下,Q235钢腐蚀产物分成2层,外层为多孔疏松层,内层主要为α-FeOOH和γ -FeOOH组成的锈层,...     

三维花状结构α-FeOOH协同H2O2可见光催化降解双氯芬酸钠

采用油浴回流法,在常压回流反应条件下批量制备出三维花状结构的α-Fe OOH纳米材料,并利用XRD、FT-IR和SEM等仪器对其进行分析表征;以双氯芬酸钠为目标污染物,考察三维花状结构α-Fe OOH纳米材料,在模拟太阳光照射下,催化H2O2降解有机污染物的性能.结果表明,三维花状结构α-Fe OOH由纳米棒自组装形成,纳米棒的长度约400~500 nm,直径约40~60 nm.以模拟可见光为光源,三维花状结构α-Fe OOH与H2O2构成光助异相类Fenton体系,对双氯芬酸钠有良好的光催化降解效果,在90 min内对初始浓度为30 mg·L-1的双氯芬酸钠降解去除率达到99%以上,催化降解反应以羟基自由基氧化反应为主.     

安徽省内电网设备常用钢材大气腐蚀试验研究

目的针对在安徽省内H1、R1及T28三个站点自然环境下暴露1年后的Q235、40Cr及镀锌钢,开展腐蚀速率、腐蚀产物及腐蚀层形貌的研究,探讨其大气腐蚀机理。方法采用称量法计算腐蚀质量损失,通过光学及电子显微镜法观察腐蚀层表面及截面形貌,用电子能谱仪测试微区成分,用X-射线衍射法测试腐蚀层的物相构成。结果 Q235、40Cr的大气腐蚀产物为Fe OOH、Fe3O4、Fe(OH)3及FeSO4,镀锌钢则为Zn O及Zn SO4。Q235、40Cr腐蚀层表面分布着绒球状的α-FeOOH及片状的γ-FeOOH,镀锌钢大气腐蚀层致密,但T28站点镀锌钢表面形成点状的腐蚀坑,腐蚀防护能力降低。结论同一站点三种钢腐蚀速率大小次序为40CrQ235镀锌钢,站点R1钢的腐蚀速率最大,站点T28的腐蚀速率最小。     

模拟酸雨大气环境中Cl-浓度对镀锌钢腐蚀行为的影响

目的研究模拟酸雨环境中Cl-浓度对镀锌钢腐蚀行为的影响与作用机理。方法以p H为3.05的模拟酸雨溶液作为空白溶液,在每升空白溶液中分别加入0.01,0.1和0.5 mol的Na Cl,浸泡3天和7天后取出试样,进行形貌、成分分析以及电化学分析。结果浸泡后镀锌钢表面形成的腐蚀产物主要为Na Zn4SO4Cl(OH)6·6H2O。随着溶液中Cl-浓度的增加,镀锌钢的腐蚀电位逐渐减小,腐蚀电流密度逐渐增大,阻抗值逐渐减小。结论通过不同时间的浸泡,随着溶液中Cl-浓度的增加,镀锌钢表面腐蚀产物对基体都有一定的保护作用,但保护作用逐渐减小,尤其在浸泡3天时的变化最明显。     

南海岛礁海洋环境中典型不锈钢浪花飞溅区腐蚀规律

目的 研究南海岛礁环境浪花飞溅区中典型不锈钢的腐蚀规律.方法 在南海岛礁进行现场腐蚀试验,利用表面微观形貌观测、腐蚀产物分析及失重测试等手段,对比分析了304、316L和2205不锈钢在浪花飞溅区中的腐蚀形貌、腐蚀速率和腐蚀深度.结果 在浪花飞溅区,304不锈钢的腐蚀速率最大,316L不锈钢次之,2205不锈钢最小;在浪花飞溅区304不锈钢和316L不锈钢局部腐蚀主要以点蚀和缝隙腐蚀为主,2205不锈钢耐腐蚀性良好,局部腐蚀不明显;三种不锈钢的腐蚀产物主要包括 α-FeOOH、γ-FeOOH、γ-Fe2O3.结论 三种不锈钢的腐蚀产物基本相同,但2205不锈钢腐蚀速率变化趋势与另外两种不锈钢明显不同.     

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.     

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.     

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.     

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.     

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.     

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.