Al-Zn-Sn-Ce牺牲阳极干湿交替环境电化学性能研究

目的 为满足高强钢装备的阴极保护要求,开展新型干湿交替环境牺牲阳极电化学性能测试,评价材料的阴极保护效果。方法 采用高温熔炼方法,制备Al-Zn-Sn-Ce低电位牺牲阳极试样,进行不同浸水率下(干湿态环境时间比为1:1、3:1和7:1)的干湿交替环境牺牲阳极电化学性能试验、电化学表征测试及腐蚀微观形貌表征,通过对比试验数据和材料形貌表征结果,综合分析铝合金牺牲阳极在干湿交替环境下的电化学性能,探究干湿交替环境因素对阳极溶解行为的影响。结果 Al-Zn-Sn-Ce牺牲阳极在多种试验环境下的工作电位为‒0.70~‒0.81 V(vs. SCE),符合高强钢阴极保护电位需求,阳极表面溶解形貌相对均匀,表面阴阳极电化学微区分布均匀。随着干湿态试验环境时间比的增加,阳极工作电位出现正移,干态环境下表面腐蚀产物的沉积和结壳导致阳极活化溶解能力下降,而干湿态环境时间比最大时,阳极自腐蚀反应得到一定的抑制,阳极电流效率均保持在75%以上。结论 随着干湿态试验环境时间比的增加,牺牲阳极在干湿交替试验环境中的工作电位出现正移。由于干态环境下表面腐蚀产物的沉积和结壳,导致阳极活化溶解能力下降,但自腐蚀反应得到抑制。Al-0.7Zn-0.1Sn-0.1Ce低电位牺牲阳极在复杂干湿交替环境中表现出良好的阴极保护性能。     

FPSO工艺水舱阳极快速消耗原因分析

目的 研究FPSO工艺水舱中铝牺牲阳极消耗过快的原因。方法 参照GB 17848—1999牺牲阳极电化学性能试验方法,对比水舱环境与普通环境下,在役阳极的电化学性能数据,并模拟水舱环境,监测阳极工作时实际的发生电流与工作电位等情况,据此分析牺牲阳极在工艺水舱中消耗过快的原因。结果 在常温（25 ℃）、常温充空气、高温（65 ℃）充空气等条件下,阳极的电化学容量分别是2522.07、2464.29、1943.74 Ah/kg,且高温（65 ℃）充空气环境下阳极的晶间腐蚀较其他两组试验严重许多,说明温度是影响阳极电化学容量的关键因素。在模拟工艺水舱环境下,实测的阳极发生电流最高可达100 mA。将工艺水与海水1:5稀释后,实测的保护电流密度最高达45 mA,说明工艺水中存在大量的去极化剂,是造成阳极快速消耗的又一重要因素。结论 工艺水舱环境下,阳极发生严重的晶间腐蚀,严重影响了阳极的电化学容量,使阳极寿命缩短。工艺水成分中含大量去极化剂,使船舱所需的保护电流密度大大增加,促使阳极发生电流加大,亦缩短了阳极的实际服役寿命。     

高强不锈钢在海水环境中的阴极保护行为研究

目的 研究不同阴极极化电位下高强不锈钢的极化行为,确定某高强不锈钢合理的阴极保护电位区间。方法 通过动电位极化测试以及电化学阻抗测试等电化学测试手段,研究此种高强不锈钢在海水中的阴极反应过程,通过不同极化电位下的恒电位极化测试,结合扫描电子显微镜和能谱仪,观察分析试样表面的腐蚀产物,研究阴极极化电位对高强不锈钢表面阴极产物膜的影响规律,以及对高强不锈钢在海水中的阴极保护效果。结果 动电位极化测试表明,在‒0.50~‒0.90 V,只需要施加很小的阴极电流,就可使极化电位发生显著变化。电化学阻抗谱测试及拟合结果表明,极化电位在‒0.70 V时,电极反应的电荷转移电阻最大,此时腐蚀被完全抑制。恒电位极化测试发现,随着电位负移,极化电流密度整体上呈现先减小、后增大的趋势。用能谱仪分析其表面产物发现,钙镁沉积层的致密度呈现先增加、后降低的趋势。结论 此种高强不锈钢在海水环境中施加阴极电位为‒0.50~‒1.00 V时,可以得到有效保护。     

压载舱锌阳极失效原因分析及实验室研究

目的 找到压载舱锌阳极失效原因,并提出整改方案。方法 对服役环境进行调研、阳极化学成分检测、电化学性能检测以及阳极表面形貌检测。结果 干湿交替以及高温的环境是造成锌阳极发生钝化的主要原因。在干湿交替环境下,阳极腐蚀表面晶粒松散,晶界宽度大,发生晶间腐蚀和晶粒脱落,造成了阳极失效。结论 通过该项目的实验研究,得出了锌阳极的适用条件,在干湿交替的环境以及高温环境(50 ℃)下,不推荐使用锌阳极,建议使用铝阳极。     

深水导管架平台外加电流阴极保护优化设计Ⅰ:单座辅助阳极

目的 以南海某200 m深水导管架平台为原型,研究外加电流单座辅助阳极在静态和动态海水条件下的导管架阴极保护电位分布及其变化规律。方法 采用一定比例缩小的导管架模型,对其施加外加电流阴极保护,研究不同条件下的阴极保护电位分布,以及电位分布的变化规律。结果 辅助阳极距离导管架模型越远,模型整体的阴极保护越均匀,反之,则越不均匀。导管架距离辅助阳极最近的区域,阴极保护电流密度最大,易出现过保护风险,而平台内部屏蔽严重区域和距离辅助阳极较远的水面附近导管架结构,阴极保护电位负移程度最小,易出现欠保护风险,这2个典型区域应当是阴极保护监测的重点位置。在相同保护电流密度和保护距离下,从静态到动态转换时,整座导管架表面的电位均呈现上升趋势,电位差值更大,分布更不均匀。随着阴极保护时间的延长,代表沉积层形成质量和覆盖程度的表观电阻率Rsr呈现初期快速增加、后期缓慢升高的趋势。海水流动会导致沉积层变薄,甚至脱落,使得动态海水环境中Rsr较同时期静态环境下的小。结论 在导管架模型的一侧放置一套辅助阳极,可实现整个模型的有效阴极保护。     

Al-Zn-In系牺牲阳极在间浸环境中的性能研究

目的探究4种常用Al-Zn-In系牺牲阳极(Al-Zn-In、Al-Zn-In-Cd、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn)在海水间浸环境中的电化学性能。方法采用恒电流法对4种阳极的开路电位、工作电位、实际电容量、电流效率及溶解形貌等进行研究,并结合电化学阻抗谱、动电位极化曲线等方法进行分析。结果在间浸环境中,Al-Zn-In、Al-Zn-In-Mg-Ti、Al-Zn-In-Mg-Ga-Mn的电流效率均在88.92%以上,3种阳极的工作电位在-0.96~-1.10 V波动,能满足碳钢在间浸环境中的保护需要。Al-Zn-In-Mg-Ga-Mn阳极溶解形貌均匀,Al-Zn-In和Al-Zn-In-Mg-Ti阳极溶解形貌略差。Al-Zn-In-Cd阳极电流效率仅为80.95%,工作电位在-0.93~-1.10 V波动,溶解形貌不均匀,电化学性能最差。研究发现,Al-Zn-In-Cd阳极表面附着的腐蚀产物多次在空气环境中脱水,并形成壳层,导致电位正移,阻碍阳极的进一步活化。结论在间浸环境中,4种阳极的电化学性能由好到差依次为Al-Zn-In-Mg-Ga-Mn阳极、Al-Zn-In阳极、Al-Zn-In-Mg-Ti阳极、Al-Zn-In-Cd阳极,前3种阳极适用于间浸环境中海洋结构物的阴极保护。     

阳极金属喷涂层在海水中的电化学性能

采用电化学方法,研究了喷涂用锌丝、锌铝合金丝和铝丝及其喷涂层在海水环境中的电化学性能和阴极保护性能;测试了3种喷涂层经实海曝露4年后的极化曲线。结果表明,3种喷涂层材料对碳钢在海水环境中均具有阴极保护效果,但喷锌涂层腐蚀较快,喷铝和喷锌铝合金涂层表面生成氧化膜,腐蚀较小。     

抛石环境中铝合金阳极性能评价及其对海底隧道钢壳保护效果评估

目的 解决埋覆介质中牺牲阳极电化学性能评价的不确定性,实现非匀质介质中牺牲阳极电容量测试结果的评价和对比.方法 模拟沉管隧道埋覆的环境介质,对铝合金牺牲阳极的电容量和溶解形貌进行评测.为区别于现有的海水等匀质介质中阳极的检测方法,建立非匀质介质中铝阳极电化学性能评价方法.另外,在上述埋覆介质中,测定阳极和阴极的极化曲线,修正仿真计算的边界条件,有利于模拟这种高电阻率介质环境下阴极保护电位分布.结果 测试箱所测电阻率与商用便携式电导率仪测定精度相当.A1阳极在低电阻率的海水中(25～40?·cm)性能稳定,电容量稳定在2500 A·h/kg,溶解性能良好;在40?·cm海淡水+回填石的混合介质中,电容量测试值数据波动大,重现性差.B1阳极在海水(25～40?·cm)中的电容量和A1阳极相当,未见到差异,在40?·cm海淡水+回填石混合介质中,电容量数值分散性小,电化学活性高.结论 混合介质中的评价试验体现了海淡水、混合介质电阻率和回填石对阳极溶解产物阻滞的综合效应,提高了抛石环境中铝阳极寿命评估的准确性,尤其适用于沉管隧道钢壳用铝合金阳极电化学性能评价和牺牲阳极保护效果评估.     

微生物作用下碳钢阴极保护氢渗透研究方法

为研究微生物、氢渗透和阴极保护三者关系,介绍了微生物生长代谢的测定方法和氢渗透测试的研究方法。分别介绍了微生物生长曲线、菌量及代谢的测试方法。氢渗透测试主要采用Devanathan-Stachurski双电解池技术,试样常采用单面镀镍或镀钯处理,对阴极池施加阴极保护,试样表面产生的氢渗透到阳极池一侧后,利用恒电位仪记录试样表面氢的氧化电流即氢渗透电流。     

船用E500钢在海水中阴极极化氢脆敏感性研究

目的研究阴极保护电位对E500钢在海水中氢脆敏感性的影响。方法采用慢应变速率拉伸试验(SSRT),同时利用三电极体系进行不同电位极化,并结合扫描电镜进行试样断口观察。结果随着阴极保护电位负移,E500钢在海水中的氢脆敏感性增加,阴极保护电位为-0.95 V(vs.SCE)时,拉伸试样出现脆性解理断裂特征,电位为-1.00 V时,E500钢断口呈脆性断裂特征。结论根据氢脆系数拟合曲线得出,当氢脆系数达到25%时,E500钢最负阴极保护电位应为-0.913 V。     

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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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.     

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.     

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.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.