典型金属材料深海腐蚀行为规律与研究热点探讨

综述了碳钢与低合金钢、不锈钢、铜合金、铝合金以及钛合金等典型金属材料深海腐蚀行为规律的研究进展。结合深海环境的苛刻与独特性,探讨了深海腐蚀环境试验及实海原位电化学测试技术等领域研究方向,尤其是中国临近海域深尺度、涵盖当前实际需求材料的大规模深海环境试验以及耐受高静水压、集电化学数据采集与远程数据传输于一体的实海电化学测试技术。此外,从阴极保护、仿真预测、应力腐蚀、涂层防护等方面介绍了实验室深海模拟试验方面的研究热点,进一步展望了典型材料深海腐蚀数据积累及适用性研究发展前景。     

车辆装备涂层局部微小破损对防护性能的影响研究

目的探究车辆装备有机涂层在微小破损之后性能的变化情况,并通过完好涂层防护能力的对比分析,间接预测微小破损涂层的服役寿命。方法利用某型现役装备涂层作为试验样本,进行综合环境下的循环加速腐蚀试验,最后利用EIS分析实验数据,分析两者防护性能的差别。结果完好涂层与破损涂层的防护性能均出现了大幅度的下降,两者在经过10个周期的腐蚀试验之后,都失去了防护能力,出现了大面积锈迹。完好涂层的低频阻抗模值|Z|0.1 Hz在试验初期处于1010Ω·cm2数量级,最后下降到106Ω·cm2以下;初始状态破损涂层的低频阻抗模值|Z|0.1 Hz为1.2×105Ω·cm2,9个腐蚀周期之后下降至5.7×103Ω·cm2,下降了2个数量级。结论破损涂层在腐蚀初期更多地表现出电容性质,其试验初期的防护能力大约相当于完好涂层经历6~7次循环试验之后的防护能力,破损部分随着腐蚀周期的变化呈现“钝化—溶解—再钝化—再溶解”的周期性变化规律。     

广东省夏秋季光化学反应活性空间分布表征

于夏末秋初在深圳市城市和郊区开展了大气OH自由基观测,结果显示OH自由基日间峰值平均浓度分别为6.0×10⁶cm^-3和5.9×10⁶cm^-3,与国内外其他地区相比处于中等水平.基于实测数据构建了拟合效果较好的本地化OH自由基参数化公式,应用于广东省OH自由基空间分布的表征,并进一步利用日间OH和NO₂浓度之积反映光化学反应活性(AP).结果发现,2018年夏秋季广东省大气光化学反应活性总体上呈现珠江三角洲较高,AP达10.1×10⁷μg/(m³·cm³),粤东、粤西、粤北地区较低的分布态势,AP分别为5.4×10⁷, 5.9×10⁷和7.7×10⁷μg/(m³·cm³);同期的PM_2.5和O₃高值区域也集中在珠江三角洲,说明了调控光化学反应活性对珠江三角洲协同控...     

沿海地区输电铁塔防护涂层耐腐蚀性能研究

目的研究沿海地区输电铁塔防护涂层体系的腐蚀失效行为,评估涂层的防护性能,为铁塔防护涂层寿命体系评定和修复提供试验依据。方法分别采用热镀锌、热镀锌/冷涂锌复合涂层、热镀锌/带锈环氧涂层三种技术方案,对铁塔角钢材料进行防腐保护,采用中性盐雾方法模拟沿海环境对试样进行耐蚀性测试,通过试样表面形貌观察、极化曲线、以及阻抗谱等电化学手段对保护效果进行评价。结果热镀锌、热镀锌/冷涂锌复合涂层在盐雾150 h出现大面积腐蚀,热镀锌/带锈环氧涂层在盐雾2000 h未发生明显腐蚀。结论热镀锌/带锈环氧涂层的耐蚀性能优于热镀锌/冷涂锌漆和热镀锌涂层。     

南京北郊夏季云凝结核活化特性研究

采用SMPS-CCNC联用的方法,于2018年7月～8月在南京北郊地区,对大气环境中气溶胶的云凝结核(CCN)活化特性进行了观测研究.观测结果表明南京北郊地区夏季的气溶胶吸湿性参数(κ)平均值为0.31;不同过饱和度(S)下的CCN数浓度(N_CCN)为(1.43±0.60)×10³个/cm³ (S=0.13%),(2.64±1.06)×10³个/cm³ (S=0.23%),(3.88±1.35)×10³个/cm³ (S=0.41%),(4.81±1.64)×10³个/cm³ (S=0.59%),(5.58±1.88)×10³个/cm³ (S=0.77%),并且有明显日变化特征,峰值出现在傍晚18:00～23:00时之间;夏季新粒子生成使总气溶胶数浓度(N_CN)和N_CCN显著提升;同时对比分析典型天气日发现...     

基于TROPOMI的石家庄市NO2柱浓度时空分布及来源分析

为探讨石家庄市NO₂柱浓度时空分布及潜在污染源区，该文利用2019-2021年L2级别的TROPOMI二氧化氮数据、石家庄市8个国控点环境自动监测站的NO₂、O₃、PM_2.5浓度数据和气象要素数据以及全球数据同化系统中的气象数据，对石家庄市NO₂时间变化、空间分布、污染传输通道城市以及潜在源贡献区进行分析。结果表明：石家庄市NO₂浓度年内变化趋势呈“U”型，季节性明显，NO₂浓度冬季(13.33×10¹⁵molec/cm²)>秋季(12.76×10¹⁵molec/cm²)>春季(4.96×10¹⁵molec/cm²)>夏季(4.09×10¹⁵molec/cm²);NO₂浓度空间表现为“主城区高、四周低”的椭圆带状分布，并形...     

陕西省天然源挥发性有机物排放清单及时空分布特征研究

基于Guenther提出的天然源性有机化合物(BVOCs)公式计算模型,利用高精度土地利用遥感资料,模拟估算了2000—2020年陕西省107个区县BVOCs的排放量、排放组成及时空分布规律.测算结果显示,陕西省近20年来BVOCs排放量呈上升趋势,总排放量从101.17×10⁴ t·a^-1上升至111.43×10⁴ t·a^-1.近20年陕西省年平均BVOCs排放量为106.01×10⁴ t·a^-1,其中,异戊二烯排放量为31.65×10⁴ t·a^-1,占比为29.86%;单萜烯排放量为35.61×10⁴ t·a^-1,占比为33.60%;其他VOCs排放量为38.75×10⁴ t·a^-1,占比为36.54%.BVOCs排放总量存在季节性变化,呈夏季高、冬季低的规律,夏、冬两季排放量分别为69.0×10⁴、...     

铝合金牺牲阳极深海应用性能研究

目的评价铝合金牺牲阳极在深海环境的电化学性能。方法通过利用中国船舶重工集团公司第七二五研究所深海试验技术和装置,原位测量三种铝合金牺牲阳极在南海1200 m深海环境的电化学性能。结果三种阳极在1200 m深海环境下的开路电位均在?1.17 V左右,工作电位在?1.11～?0.91 V范围内。1#和2#阳极的实际电容量小于2400A?h/kg,电流效率约为80%,表面存在明显的优先溶解和晶粒脱落现象,表面腐蚀产物有结壳现象发生。3#阳极的实际电容量约为2500A?h/kg,电流效率大于85%,表面微观溶解形貌相对均匀,但表面存在大面积未溶解区域,且腐蚀产物不易脱落。结论该研究结果为深海工程装备阴极保护设计提供了支撑。     

环氧涂层在不同温度海水中的失效行为研究

目的研究环氧涂层在不同温度海水环境中的腐蚀失效行为。方法采用电化学阻抗谱(EIS)技术研究两种海水环境中涂层的EIS特征,同时分析涂层电阻和涂层电容的变化,以研究环氧涂层防护性能随浸泡时间的变化。结果涂层在15℃海水中浸泡1440 h时,阻抗值下降至106?·cm2以下,而在30℃海水中仅浸泡72h时,阻抗值就已下降至106?·cm2。随着浸泡时间的增加,涂层在15℃海水中的EIS响应由高阻抗的单容抗弧变为双容抗弧,而在30℃的海水中,EIS响应首先由单容抗弧演变为双容抗弧,随后又出现了明显的Warburg扩散阻抗特征。涂层电容在两种温度的海水中均呈上升趋势,电阻呈下降趋势。结论涂层在30℃海水中的劣化速度加快,是因为升高温度能够降低涂层与金属间的结合力,加快了海水向涂层内部渗透的速率。由于温度的升高加快了溶解氧的扩散速率,使得氧扩散过程成为腐蚀反应的控制步骤,从而导致了涂层在30℃海水中的EIS响应出现了明显的Warburg扩散阻抗特征。当环氧涂层在15℃与30℃的海水中浸泡1800 h时,其防护性能的变化可以分为快速下降、缓慢下降、趋于稳定三个阶段。     

汾渭平原NO2柱浓度时空分布特征及其与O3、HCHO相互关系研究

2018年，汾渭平原首次被确定为大气污染防治重点区域，成为“蓝天保卫战”继京津冀地区的第二个主战场.本文利用卫星OMI传感器反演产品，对汾渭平原2016—2020年二氧化氮、臭氧和甲醛数据进行分析，结果表明：在空间上，汾渭平原NO₂柱浓度有自东向西逐渐减弱的趋势.高浓度地区受煤炭、物流、钢铁、航空等产业，以及特殊地形等因素影响，沿山脉走势呈“人”字形分布.在时间上，年均NO₂浓度呈总体减少趋势，2018年最大，2020年最小；月均变化呈U字型，1—8月，NO₂柱浓度逐月降低，9—12月逐月增加.NO_x敏感控制区、VOCS-NO_x协同控制区，以及VOCS敏感控制区时的年均NO₂柱浓度分别为1.48×10¹⁵～6.3×10¹⁵、6.3×10¹⁵～13.2×10¹⁵、13.2×10¹⁵～20.1×10¹⁵ molec·cm^...     

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.     

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.