OH自由基引发光氧化氟氯碳化合物的研究

研究了ＣＦＣ－１１＋Ｈ２Ｏ２，ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２，ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋Ｈ２Ｏ２＋Ｏ２４个体系的光化学反应，这些体系在低压尔照射下，Ｈ２Ｏ２产生了ＯＨ自由基，ＯＨ自由基能引发ＣＦＣ的光氧化反应，其产物在２０ｍ长的漪避用富叶红外光谱仪测量，发现在ＣＦＣ－１１＋Ｈ２Ｏ２和ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２体系中有ＣＯＦＣｌ，ＣＯ２和ＨＣｌ，而在ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋     

改性ACF－PAN吸附SO_2前后表面结构变化及机机理究

以自制ＰＡＮ－基聚丙烯腈活性碳纤维ＡＣＦ－ＰＡＮ（ＡＣＦ－活性碳纤维、ＰＡＮ－聚丙烯腈）和改性处理的ＡＣＦ－ＰＡＮ吸附ＳＯ_２，借助ＩＲ、ｘ－光电子能谱分析等研究ＡＣＦ－ＰＡＮ改性处理及吸附ＳＯ_２前后表面结构变化。结果表明：各型ＡＣＦ－ＰＡＮ吸附ＳＯ_２的活性中心为表面结构中的含氮官能团以及引入的金属氧化物，其吸附机理是活性氮催化或电子传递。     

还原法处理转炉渣研究

测定了１６００℃下用不同还原剂处理上钢三厂转炉渣时渣中ＦｅＯ的还原动力学曲线。研究了用Ｃ及煤矸石作还原剂时，渣中ＦｅＯ和Ｐ２Ｏ５的变化关系，确定了还原后转炉渣直接作水泥熟料的最佳条件。     

PrO/γAl2O3等稀土氧化物催化还原SO2的研究

进行了负载于氧化铝上的镨，钕，锌，镧，钐等稀土氧化物上，ＣＯ，ＣＨ３及Ｈ２催化还原ＳＯ２反应的研究。实验着重考察了Ｐｒ－Ｏ／γ－Ａｌ２Ｏ３上ＣＯ２催化还在ＳＯ２的反应，测定了不同反应温度，不同反应物配比及不同空速下的活性，同时对Ｐｒ－ｏ／γ－Ａｌ２Ｏ３催化剂进行了ＴＰＤ，ＴＧ，ＸＲＤ，ＸＰＳ表征。结果表明，稀土氧化物具有非常高的ＣＯ催化还原ＳＯ２反应的活性，在５００℃，ＣＯ：ＳＯ２＝２：１，空速比     

Fe~（2＋）－H_2O_2法处理DSD酸生产氧化母液的研究

为改善ＤＳＤ酸氧化母液的可生化降解性，将废液先用有机絮凝剂ＴＳ－１（一种季胺盐）处理，ＴＳ－１的投加量为３ｇ／Ｌ，其后用Ｆｅ２＋－Ｈ２Ｏ２法氧化，Ｆｅ２＋和Ｈ２Ｏ２的量分别为１５０ｍｇ／Ｌ，７ｇ／Ｌ，废液ＣＯＤ和色度的去除率分别可达６４％和６２％。经处理后的废水，其ＢＯＤ５／ＣＯＤ≈０．３，可以认为已达到生化处理的要求。当Ｈ２Ｏ２的投量为２ｇ／Ｌ，经Ｆｅ２＋－Ｈ２Ｏ氧化处理后的废液，再用ＦｅＣｌ３进行两级混凝处理（ＦｅＣｌ３的投加量分别为ｓｇ／Ｌ和２ｇ／Ｌ），则ＣＯＤ和色度的去除率可达９０％和９５％。     

新型复合金属氧化物催化剂用于汽车尾气NOx净化的实验研究

采用固定床反应装置,模拟汽车尾气,研究新型复合金属氧化催化剂ＷＣＸ－Ｉ（Ｒｅ－Ｎｉ－Ｃｏ－Ｃｕ－Ｏｘ／Ｆｅ２Ｏ３）对ＣＯ还原ＮＯ反应和ＣＨ４还原ＮＯ反应的催化活性,催化剂的抗ＳＯ２中毒性能,抗积炭性能．结果表明ＷＣＸ－Ｉ催化剂对ＮＯ／ＣＯ和ＮＯ／ＣＨ４反应均具有较好的高温活性．在本研究实验条件下,４００℃以上时ＣＯ对ＮＯ的稳定还原率在９３％以上,６００℃以上时ＣＨ４对ＮＯ的稳定还原率在９２％以上．在１０００ｍｌ／ｍ３ＳＯ２－Ｎ２的高硫气氛中强制中毒及在１．０％ＣＯ－１０％ＣＯ２－Ｎ２的缺氧气氛中强制积炭若干小时后的催化剂试样对ＮＯ／ＣＯ反应的催化活性几乎未见降低     

以干吸着剂喷射法同时脱除SO2和NO的实验研究

炉膛吸着制度射（ＦＳＩ）与选择性非催化还原（ＳＮＣＲ）相结合同时脱除ＳＯ＿２和ＮＯ，在夹带流反应器中进行实验研究。在８００－１２００℃下喷射石灰石／尿素吸着剂或石灰石／铵盐吸着剂能同时脱除ＳＯ＿２和ＮＯ。石灰石／尿素吸着剂表现出最高的脱硫脱硝能力，当Ｃａ／Ｓ＝２和Ｎ／ＮＯ＝２时，其ＳＯ＿２和ＮＯ脱除率分别能达到９０％和８０％。主要的ＮＯ脱除是ＮＨ＿３与ＮＯ反应生成Ｎ＿２所致，少量的ＮＯ脱除率（１０％）是在ＣａＳＯ＿４的催化下，ＣａＯ与ＮＯ反应生成Ｃａ（ＮＯ＿２）＿２的结果。本文还考察了反应温度和时间对脱硫脱硝反应速度的影响。     

离子色谱法同时测定有机和无机阴离子

用离子色谱法同时测定有机阴离子和无机阴离子，实验中采用一种新型高容量分离柱，灵敏度高，选择性好。讨论了最佳实验条件的选择测定了Ｆ＾－，Ｃｌ＾－，ＳＯ４＾２－，ＮＯ２＾－，ＳｅＯ３＾２－、Ｃ２Ｏ４＾２－、甲酸奶和乙酸根等阴离子，并且分析了沈阳地区雪样中的几种阴离子。     

光催经氧化法处理染料中间体H酸水溶液

为了去除水中难氧化的有害染料中间体Ｈ酸，研究以ＴｉＯ２，ＺｎＯ，ＣｄＳ和Ｆｅ２Ｏ３为催化剂，采用低压汞灯为光源，对Ｈ酸水溶液进行光催化氧化实验。结果表明：ＴｉＯ２和ＣｄＳ的催化效果最好。采用ＴｉＯ２作催化剂，光催化氧化５ｈ后，Ｈ酸分解率可达９０％，反应速率遵大Ｌａｎｇｍｕｉｒ－Ｈｉｎｓｈｅｌｗｏｄｄ方程，Ｋ＝１２．３Ｌｍｍｏｌ，ｋ＝２５．２×１－０＾－６ｍｏｌ／ｈ。     

催化加氢转化CO2的研究

研究催化加氢法转化ＣＯ２,在Ｆｅ／ＡＣ催化剂上采用不同的反应条件,可将ＣＯ２分别转化成低碳烯烃,液化石油气和液态烃,其转化率均在４０％－５０％之间。在Ｃｕ－Ｚｎ－分子筛催化剂上,３５％ＣＯ２可被转化成二甲醚;在Ｒｈ－Ｖ／ＳｉＯ２催化剂上,ＣＯ２可被转化成乙醇,其单程转化率在５％以上。     

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.