10CrNi3MoV船用钢港口环境腐蚀行为对比研究

目的对比研究10CrNi3MoV船用钢在我国黄海、东海和南海海域具有代表性的港口海水环境中的腐蚀行为。方法在青岛、舟山和三亚港口进行10CrNi3MoV船用钢的实海暴露实验,通过腐蚀形貌观察、腐蚀速率和点蚀深度测量,结合各海域环境因素的监测和腐蚀产物成分的XRD分析,研究材料暴露0.5a的腐蚀规律和腐蚀机制。结果 10CrNi3MoV钢在青岛港口主要发生均匀腐蚀,在舟山和三亚港口以点蚀为主要腐蚀形式。10CrNi3MoV钢腐蚀速率受温度、盐度、溶氧量和泥沙冲刷综合作用的影响,随港口纬度的降低,材料腐蚀速率增大。附着海生物是影响10CrNi3MoV钢点蚀的重要因素,材料在附着率高的三亚和舟山港口具有更高的点蚀深度。结论附着区与非附着区形成的电偶效应使阴阳极反应界面分离,具有保护性的α-FeOOH的阴极去极化加快了附着海生物闭塞区的阳极溶解。     

两种不锈钢在港口海水环境中的腐蚀行为和规律研究

目的研究304和316L不锈钢在我国不同港口海水全浸区浸泡不同周期后的腐蚀规律。方法进行港口海域实海全浸试验,利用三维视频拍摄、质量损失分析及图像处理等手段,对比分析不锈钢在青岛、舟山、三亚港口海水全浸区的腐蚀形貌、腐蚀速率、腐蚀深度和海生物附着面积。结果两种不锈钢表面以点蚀和缝隙腐蚀为主,304不锈钢表面还产生严重的隧道腐蚀。不同港口海水中,304和316L不锈钢的腐蚀速率均较低,316L不锈钢的耐蚀性优于304不锈钢。三港口海域不锈钢表面形貌的差异明显,三亚试样表面海生物附着最多,舟山试样表面附着大量泥沙,三亚港口海域不锈钢的腐蚀速率小于舟山港口海域。结论不同港口海水环境对不锈钢表面海生物种类及附着面积的影响显著,而不锈钢表面状态直接影响其腐蚀形貌。     

不同海域40Cr低合金钢腐蚀行为研究

目的 研究40Cr在海水环境中的自然腐蚀行为.方法 采用形貌分析、腐蚀质量损失分析、XRD分析等方法对40Cr在青岛、舟山、三亚海水全浸区的腐蚀行为进行研究.结果 40Cr在不同海域中的腐蚀均较为严重,青岛及三亚海域的试样表面被大量海生物附着,舟山海域的试样表面则以泥沙沉积为主.去掉腐蚀产物后试样的腐蚀形貌以坑蚀为主.在试验周期内,随着时间的延长,试样的腐蚀速率逐渐减小,在不同周期内均以三亚海域的为最高.在相同条件下与普通碳钢(Q235)相比,40Cr的腐蚀速率偏高.随着时间的延长,青岛、舟山试样点蚀深度逐渐增加,而三亚试样点蚀深度则先增加后减小,同周期下青岛海域试样的点蚀深度最小.不同海域及周期下40Cr的腐蚀产物以稳态α-FeOOH及Fe2O3为主.结论 40Cr在三个海域的腐蚀形貌均以坑蚀为主,试验周期内试样在三个海域的腐蚀速率随时间延长逐渐减小,同周期下三亚海域试样的腐蚀最为严重;40Cr中C含量较高,在相同条件下其腐蚀速率要高于普通碳钢;40Cr的腐蚀产物以稳态成分为主,是由于Cr元素含量较普通碳钢增加,加速了钢的腐蚀产物到热力学稳定状态的转化.     

AH36钢在西沙海域不同区带腐蚀行为研究

目的研究AH36钢在西沙海域不同区带的腐蚀行为。方法通过在西沙海域不同区带进行暴露试验,回收后进行腐蚀质量损失、形貌及产物成分分析。结果试样在不同区带的腐蚀质量损失与周期之间遵循幂函数变化规律,飞溅区试样腐蚀速率最快。大气区试样发生较轻的全面腐蚀,飞溅区试样表面可观察到大量明显蚀坑,全浸区试样发生不均匀全面腐蚀。不同区带腐蚀产物均以稳态的α-FeO(OH)以及铁氧化物为主,飞溅区试样腐蚀产物中,稳态物质含量高于大气区,全浸区试样腐蚀产物中含有钙镁沉积物。结论 AH36钢在西沙海域不同区带腐蚀速率快,飞溅区腐蚀最为严重,腐蚀产物生成及转化速度快,腐蚀易趋于稳定。     

飞溅区挂样位置、高度对钢腐蚀的影响

目的研究飞溅区挂样位置、高度对钢腐蚀的影响。方法采用海水飞溅区暴露试验。结果在青岛和三亚获得了5种钢在飞溅区暴露的腐蚀结果。结论在不同海域试验地点的飞溅区暴露,因环境条件不同,钢的飞溅区范围区间有较大差别,腐蚀速率峰值相对平均高潮位的高度也不同。在同一试验地点,暴露位置、条件的不同都会使钢的飞溅区范围区间及腐蚀速率峰值的高度不同。     

不同港口海域铝合金腐蚀行为研究

目的获得1060铝合金和5083铝合金在不同港口海域的腐蚀规律。方法采用实海试验方法获得材料表面的腐蚀形貌及腐蚀速率,并利用腐蚀图像处理技术分析海生物覆盖状态。结果不同海域铝合金试样表面附着海生物种类不同,青岛海域试样表面主要附着牡蛎,舟山海域试样主要附着藤壶和海藻,三亚海域主要附着藤壶和牡蛎。1060铝合金和5083铝合金在不同海域海水中以点蚀和缝隙腐蚀为主,海生物附着对铝合金腐蚀有明显影响,较严重的腐蚀点出现在牡蛎或藤壶下面及边缘。三海域中两种铝合金在舟山海域的腐蚀速率最大,三亚海域次之,青岛海域最小。不同海域铝合金试样表面海生物覆盖面积不同,三亚海域试样表面海生物覆盖面积百分比最大,青岛海域次之,舟山海域最小。结论由于海水环境不同,青岛、舟山及三亚海域铝合金试样表面海生物种类以及海生物覆盖面积明显不同,海生物的附着在一定程度上减缓了铝合金的腐蚀,另外也使得铝合金更易产生缝隙腐蚀和点蚀。     

海工钢在热带海域长尺试验腐蚀行为研究

目的获得A517Q海工钢长尺试样在热带海域的腐蚀行为。方法通过贯穿海洋大气、飞溅、潮差和全浸区的长尺电连接试验进行研究。结果试样在飞溅区的腐蚀速率最高,潮差区高潮位部位的腐蚀速率大于低潮位。全浸区上部的腐蚀速率高于其下部。各区带试样的腐蚀形貌存在显著差异。结论三亚海域的海浪飞溅冲刷作用较大,水温和气温较高,导致A517Q长尺试样的飞溅区腐蚀严重。大量的海生物附着,Cr,Mo,Mn,Ni等合金元素的添加,减缓了全浸区的腐蚀。     

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...     

典型海域船舶用铜材表面生物污损与腐蚀性能研究

目的 对比研究铜合金、紫铜在我国黄海、东海和南海海域具有代表性的港口海水环境中的污损、腐蚀行为.方法 依据GB 12763.6—2007《海洋调查规范》和GB/T 5776—2005《金属和合金的腐蚀试验方法》,通过实海挂片研究ZQMnD12-8-3-2、铜镍合金B10/B30和紫铜T2在我国典型海域青岛港口、舟山港口、三亚港口的生物污损与腐蚀状况.结果 铜镍合金B10、B30和紫铜T2在三海域均具有良好的抑制污损生物附着的性能,其中紫铜抑制污损生物附着的性能最为突出,但其腐蚀严重,腐蚀速率为3.97×10–2～8.48×10–2 mm/a;铸造青铜ZQMnD12-8-3-2虽然含铜量略高于铜镍合金B30,但由于其腐蚀产物易附着于材料表面,其污损抑制性能较差.结论 铜镍合金B10、B30和紫铜T2均有抑制污损生物附着的性能,但受不同海域环境因素和材料表面腐蚀产物致密性的影响有所差异.受泥沙水质影响,舟山港口内铜合金的腐蚀速率较高,腐蚀显著,三亚港口内紫铜的腐蚀速率最高.     

2297-T87铝锂合金用于大气腐蚀性的比较

目的利用铝锂合金的大气腐蚀试验结果评价大气腐蚀性。方法对第三代铝锂合金2297-T87在6个自然环境试验站户外暴露后的腐蚀质量损失、腐蚀速率、腐蚀深度、拉伸性能进行分析,综合评价各地区大气腐蚀性。结果2297-T87铝锂合金在团岛、万宁、永兴岛暴露1年后出现显著腐蚀,腐蚀质量损失和腐蚀速率约为江津的2倍、西双版纳的4倍,北京的腐蚀质量损失和腐蚀速率最低。合金最大腐蚀深度的变化趋势与腐蚀质量损失和腐蚀速率的变化趋势一致。观察横截面发现,在万宁、永兴岛、江津暴露后,合金发生严重的点蚀,在腐蚀产物覆盖区域下方形成不规则蚀坑,而在团岛暴露后,合金内部发生晶间腐蚀。合金在江津、永兴岛、万宁、团岛暴露后的拉伸性能仍比较接近,且拉伸强度保持率在90%以上。结论将2297-T87铝锂合金暴露1年后的腐蚀质量损失、腐蚀速率、腐蚀深度作为表征指标,获得各试验站的大气腐蚀性顺序为:北京<西双版纳<江津<永兴岛<万宁<团岛。     

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.     

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.     

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.     

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.     

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.     

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.