船用钢板材料在淡水环境中初期腐蚀行为

目的研究船用钢板材料在长江淡水环境中的初期腐蚀行为。方法运用形貌分析、腐蚀质量损失、XRD、开路电位、极化曲线等方法研究Q235B和CCSA两种船用钢板材料在室外长江淡水环境中不同暴露方式(水面大气、半浸、全浸)及不同浸泡时间(0.5,1 a)腐蚀行为;室内长江淡水环境不同暴露方式(半浸、全浸)浸泡768 h内的腐蚀行为;室内长江淡水环境全浸泡下在不同时间(0~14 d)的电化学腐蚀行为。结果两种船用钢板材料在武汉长江淡水中腐蚀严重,半浸泡环境下腐蚀速率最大,达到100μm/a,水面区大气腐蚀速率最小,腐蚀速率为30μm/a左右,全浸区腐蚀速率为80μm/a左右,1 a和0.5 a的腐蚀速率相近,CCSA耐蚀性优于Q235B。室内长江淡水浸泡环境下两种船用钢板材料腐蚀电位随时间而降低,2d后趋于稳定;半浸泡环境下腐蚀速率大于全浸区;极化曲线说明浸泡2 d后,腐蚀速率降低且趋于稳定。结论 CCSA耐蚀性优于Q235B,半浸泡环境下腐蚀最严重,其次为全浸区,水面大气环境腐蚀最小。     

基于数据分析的大气腐蚀等级细化研究

目的提出一种基于数据分析的方法对大气腐蚀等级进行细化。方法以碳钢为例,采用有序样本聚类方法,对国内大气腐蚀试验站多年积累的腐蚀速率进行分析,将大气腐蚀等级细化为10级。在此基础上,根据腐蚀速率以及相应大气环境中的二氧化硫浓度、氯离子浓度、润湿时间的数据,采用反距离加权插值法,并结合ISO 9223—2012标准获取等级细化后的碳钢大气腐蚀性等级估计表。结果经过细化之后的大气腐蚀等级10级分级结果为0~8μm/a(C1),8~25μm/a(C2),25~40μm/a(C3),40~50μm/a(C4),50~60μm/a(C5),60~75μm/a(C6),75~90μm/a(C7),90~100μm/a(C8),100~200μm/a(C9),200~700μm/a(C10)。结论该10级分级法将大气腐蚀等级划分得更为细化。     

大气腐蚀数据降维最优维度研究

目的确定金属大气腐蚀数据降维的最优维度。方法分别采用PCA、MDS、Isomap和LLE四种方法对大气腐蚀数据进行降维处理,并采用集成学习算法建立预测模型。针对不同的降维方法和近邻点个数计算,使用MAPE(Mean Absolute Percentage Error,相对百分误差绝对值的平均值)对预测结果进行评价,将最佳预测速率所对应的维度作为最优维度。结果不同的降维方法和近邻参数作用下,最优维度从2维到7维不等。流形学习方法对大气腐蚀数据进行降维的MAPE均小于线性降维方法。结论适合每种降维方法的最优维度可能是不同的,通过对MAPE进行对比,得到大气腐蚀数据在各种降维方法的最优维度。     

基于PCA-PSO-SVM模型的海底多相流管道内腐蚀速率预测

针对海底多相流管道内腐蚀速率的预测问题,首先对影响该种类型管道内腐蚀速率的相关因素进行了分析,对PCA算法、PSO算法和SVM算法分别进行了介绍,提出了可用于海底多相流管道内腐蚀速率预测的PCA-PSO-SVM组合模型,在此基础上使用PCA-PSO-SVM组合模型对44组海底多相流管道内腐蚀速率的影响因素和管道内腐蚀速率数据进行了学习训练,对10组数据进行了预测,并将该组合模型与PCA-GA-SVM模型、PCA-LS-SVM模型和PCA-CV-SVM模型3种预测模型的预测结果进行了对比,以验证所提方法的可靠性和可行性。结果表明:温度对海底多相流管道内腐蚀速率的影响相对较大,压力对其的影响相对较小;使用PCA-PSO-SVM组合模型对海底多相流管道内腐蚀速率预测的平均绝对误差仅为1.848%,模型训练时间仅为3.17 s,这两项数据均小于其他预测模型,表明针对海底多相流管道内腐蚀速率的预测问题,PCA-PSO-SVM组合模型具有可靠性和可行性。     

不同海域Custom450高强度不锈钢的腐蚀规律研究

目的 研究Custom450钢在青岛、舟山、厦门及三亚等4个海域大气和飞溅环境中的自然腐蚀规律。方法 采用形貌分析、腐蚀速率、点腐蚀深度分析等方法对Custom450钢在上述4个海域大气和飞溅区的腐蚀规律进行研究。结果 Custom450钢在4个海域大气环境的年平均腐蚀速率相当,且未观察到有点蚀现象发生,舟山海域的年平均腐蚀速率最小,为0.001 41 mm/a,三亚海域的年平均腐蚀速率最大,为0.001 54 mm/a。4个海域飞溅区的年平均腐蚀速率范围为0.0021～0.0028mm/a,舟山海域的年平均腐蚀速率为0.002 1 mm/a,平均及最大点腐蚀深度分别为5.7μm和25.99μm,均低于其他3个海域。结论 Custom450钢在4个海域的大气环境暴露1 a后,未发现明显的腐蚀现象,表明该钢短期内在上述4个海域海洋大气环境中具有良好的耐蚀性。在飞溅环境中的腐蚀速率高于大气环境,且有明显的点腐蚀现象发生,钢中未溶的NbC相会促进点腐蚀现象的发生。     

钢在自然环境中的大气腐蚀研究进展

回顾了近年来钢在自然环境中的大气暴露腐蚀试验和腐蚀行为预测的研究。重点介绍了钢的腐蚀失重规律、环境因素和钢的化学成分对钢的大气腐蚀影响以及锈层分析的研究;此外,还介绍了幂函数预测模型、灰色模型和神经网络预测模型的研究进展。     

耦合多电极矩阵传感技术在埋地金属腐蚀监测中的应用

目的采用耦合多电极矩阵传感器(CMAS)测量不同状态下的埋地金属腐蚀速率。方法将腐蚀探头插入到含蒸馏水和3.5%模拟海水的饱和土壤中,通过将探头向上提升,测量金属在饱和土壤、水-空气界面、疏松土壤中的腐蚀速率。对两只腐蚀探头分别进行杂散电流干扰、阴极保护处理,一只探头处于自由电位状态,测量三只探头在土壤中的腐蚀速率。结果在含蒸馏水和3.5%模拟海水的饱和土壤中,测量的金属稳态腐蚀速率约为2~15μm/a,金属在含海水饱和土壤中的腐蚀速率并未高于含蒸馏水饱和土壤。在土壤中形成充满水的空间里,水-空气界面附近金属材料的腐蚀速率比饱和土壤中高2个数量级。杂散电流对埋地金属的腐蚀速率影响巨大,与自由状态下的埋地金属相比,受杂散电流干扰的埋地金属腐蚀速率提高2个数量级。在阴极保护电位为-0.9 V的情况下,腐蚀速率约为0.01μm/a,接近CMAS系统检测最低限。结论耦合多电极矩阵传感器(CMAS)能够有效测试埋地金属不同状态下的腐蚀速率。     

神经网络在海水腐蚀预测中的应用

根据我国材料自然环境腐蚀网站长期以来积累的海水腐蚀数据,采用BP人工神经网络算法,建立了碳钢及低合金钢的海水腐蚀预测模型.该模型以合金成分、环境因素为输入参数,以平均腐蚀速率为输出参数.以碳钢、低合金钢的17种钢种在青岛、厦门、榆林海水腐蚀试验站16年腐蚀数据建模.选定A3钢与10CrCuSiV在以上三地16年的腐蚀数据为验证样本.结果表明该网络具有良好的预测精度,能够正确反映海水环境腐蚀性因素及金属材料腐蚀暴露时间与其腐蚀速率的关系,用于碳钢及低合金钢在海洋全浸环境中的腐蚀预测.     

基于神经网络的城市夜间环境监控与预测

因夜间天空亮度分布具有非线性变化特点,故引入神经网络算法,建立基于时间序列的夜天空亮度预测模型,夜天空亮度预测模型可为城市光污染防治提供评价依据.文章对神经网络的原理进行了论述,建立了基于时间序列预测模型.以测试数据为训练样本集,基于MATLAB(矩阵实验室,Matrix Laboratory的简称),采用改进的BP算法(误差反向传播算法)对网络进行学习训练,并对存在的误差进行了分析.基于时间序列BP神经网络的夜天空预测模型,当隐含层神经元数目为5,训练函数为L-M优化算法(trainlm)时,最大绝对误差可达到0.003 6 cd/m2,最大相对误差达到2.361 4%.结果表明,模型的运行结果与试验数据比较吻合,输出与目标矢量之间相关性也较好.     

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。     

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.     

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.     

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.     

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.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.