HCI改性沸石和方解石复合覆盖层控制底泥氮磷释放的效果及机理研究

提出了HCl改性沸石和方解石复合覆盖控制底泥氮磷释放的新方法,利用摇床振荡试验和底泥氮磷释放控制模拟试验,设计了5种底泥处理方案,重点针对HCl改性沸石和方解石复合覆盖技术研究了其抑制底泥氮磷释放的效果及机理.结果表明,方解石覆盖层可以较好地抑制底泥磷的释放,而对底泥氨氮释放的抑制效果较差.天然沸石和方解石复合覆盖层不仅可以有效地抑制底泥氨氮的释放,而且可以有效地抑制底泥磷的释放.采用HCl对沸石进行改性,可以提高沸石和方解石复合覆盖层抑制底泥磷释放的效率,模拟期间复合覆盖层对底泥磷释放通量的抑制率由天然沸石的84%提高到HCl改性沸石的91%.采用HCl对沸石进行改性,降低了沸石和方解石复合覆盖系统有效控制底泥氨氮释放的持续时间,与天然沸石相比,相同投加量条件下HCl改性沸石有效控制底泥氨氮释放的持续时间缩短了1/3左右.采用HCl对沸石进行改性增强了复合覆盖系统抑制底泥磷释放效率的机理与HCl改性降低了沸石Na 的交换量并提高了沸石H 的交换量相关.     

HCl改性沸石和方解石复合覆盖层控制底泥氮磷释放的效果及机理研究

提出了HCl改性沸石和方解石复合覆盖控制底泥氮磷释放的新方法,利用摇床振荡试验和底泥氮磷释放控制模拟试验,设计了5种底泥处理方案,重点针对HCl改性沸石和方解石复合覆盖技术研究了其抑制底泥氮磷释放的效果及机理.结果表明,方解石覆盖层可以较好地抑制底泥磷的释放,而对底泥氨氮释放的抑制效果较差.天然沸石和方解石复合覆盖层不仅可以有效地抑制底泥氨氮的释放,而且可以有效地抑制底泥磷的释放.采用HCl对沸石进行改性,可以提高沸石和方解石复合覆盖层抑制底泥磷释放的效率,模拟期间复合覆盖层对底泥磷释放通量的抑制率由天然沸石的84%提高到HCl改性沸石的91%.采用HCl对沸石进行改性,降低了沸石和方解石复合覆盖系统有效控制底泥氨氮释放的持续时间,与天然沸石相比,相同投加量条件下HCl改性沸石有效控制底泥氨氮释放的持续时间缩短了1/3左右.采用HCl对沸石进行改性增强了复合覆盖系统抑制底泥磷释放效率的机理与HCl改性降低了沸石Na⁺的交换量并提高了沸石H⁺的交换量相关.     

原位掩蔽对底泥汞释放的抑制效果及中试评估

为解决贵州省百花湖底泥中的汞污染问题,研究了原位掩蔽对底泥中汞释放的抑制效果. 选择沸石、高岭土和赤铁矿为掩蔽材料,通过模拟试验,确定原位掩蔽的最佳覆盖厚度为2.0 cm,此时沸石、高岭土和赤铁矿对底泥汞释放的控制率分别为47.1%、64.9%和62.3%,说明最佳掩蔽材料为高岭土. 以高岭土为掩蔽材料的情况下,试验实施7 d后,水体扰动对控制率的影响不足6.7%. 中试区位于百花湖重度污染区,面积约为22 000 m2,采用驳船少量多次撒布高岭土原位掩蔽汞污染底泥,控制覆盖厚度为2.0~3.0 cm,按月连续监测6次. 结果显示,高岭土对汞污染底泥的控制率达到47.1%. 模拟试验及中试效果显示,高岭土原位掩蔽可有效抑制底泥中汞的释放,并且较薄的覆盖厚度可降低工程成本和对湖底生态系统的影响.      

原位活性覆盖抑制河道底泥营养盐释放的效果研究及工程化应用

针对太湖流域梁塘河开展底泥原位活性覆盖实验室模拟研究及工程化应用,比较多种覆盖材料对底泥氮、磷释放量的削减效果。研究结果表明:原位活性覆盖能够有效抑制底泥向水体中释放氮、磷等营养盐;沸石和细砂2种覆盖材料的抑制效果优于石灰和石膏2种钙盐;方解石+沸石组合覆盖可稳定削减TN、TP的释放量,并且平均削减率达到60%,可作为该河道富营养化控制效果最佳的覆盖材料;细砂覆盖对TP的抑制效果优于TN;膨润土覆盖对TN、TP抑制效果最差。在治理成本相近的情况下,方解石+沸石组合覆盖材料效果明显优于膨润土。建议在未来应用中结合河道污染情况及覆盖材料的相适性和经济性进行综合考虑。     

纳米伊/蒙黏土去除微污染水体中Cd~(2+)、Tl~+的特性分析

针对太湖流域梁塘河开展底泥原位活性覆盖实验室模拟研究及工程化应用,比较多种覆盖材料对底泥氮、磷释放量的削减效果。研究结果表明:原位活性覆盖能够有效抑制底泥向水体中释放氮、磷等营养盐;沸石和细砂2种覆盖材料的抑制效果优于石灰和石膏2种钙盐;方解石+沸石组合覆盖可稳定削减TN、TP的释放量,并且平均削减率达到60%,可作为该河道富营养化控制效果最佳的覆盖材料;细砂覆盖对TP的抑制效果优于TN;膨润土覆盖对TN、TP抑制效果最差。在治理成本相近的情况下,方解石+沸石组合覆盖材料效果明显优于膨润土。建议在未来应用中结合河道污染情况及覆盖材料的相适性和经济性进行综合考虑。     

几种覆盖材料抑制湖泊污染底泥氮释放的试验研究

建立了一套模拟湖泊小试装置,分别采用含黏土的沙子、清洁黄土和土工布3种材料覆盖湖泊污染底泥,抑制底泥中的氮释放。试验控制在恒温25℃厌氧条件下进行,经过75d静置试验,结果表明:含黏土的沙子和清洁黄土均能有效抑制污染底泥的氮释放,而单独使用土工布的效果不佳;覆盖材料的覆盖厚度越厚,抑制污染底泥氮释放的效果越好;覆盖厚度为5cm、15cm和30cm的沙子对污染底泥氮释放的抑制率分别为74.9%、94.0%和96.8%,覆盖厚度为5cm、15cm和30cm的黄土对污染底泥氮释放的抑制率分别为77.2%、95.5%和98.8%,可见黄土的效果更优;从工程成本考虑,采用15cm覆盖厚度即可。     

天然沸石和方解石复合覆盖技术抑制底泥磷释放的影响因素研究

提出了天然沸石和方解石复合覆盖控制底泥氮磷释放的新技术,并对该技术抑制底泥磷释放的能力及影响因素进行了研究.结果表明,天然沸石和方解石复合覆盖层不仅可以有效抑制底泥氨氮释放,也可以有效抑制磷的释放.复合覆盖层抑制底泥磷释放的效率受天然沸石投加量、方解石投加量、天然沸石粒径、沸石与方解石组合方式等因素的影响.随天然沸石和方解石投加量的增加,复合覆盖层抑制底泥磷释放的效率明显提高;随天然沸石粒径的减小,复合覆盖层抑制底泥磷释放的效果略微增强.沸石和方解石的组合方式对复合覆盖层抑制底泥磷释放的规律为：先覆盖沸石后覆盖方解石对底泥磷释放的抑制效果明显强于先覆盖方解石再覆盖沸石条件下的情况,与沸石方解石混合均匀覆盖情况相比,先覆盖沸石后覆盖方解石对底泥磷释放的效果也略有提高.     

厌氧条件下深谷型湖泊底泥覆盖效果研究

为有效控制深谷型湖泊内源污染,构建底泥活性覆盖系统,以脱碱赤泥为主料,粉煤灰、黏土和Ca CO3为辅料,制作了不同配比的底泥覆盖材料,并评价其在厌氧条件下对湖泊内源污染物的控制效果。结果表明:底泥覆盖后上覆水体水质总体趋于稳定,DO水平能够得到改善,TP和COD的释放受到抑制,对NH3-N虽有一定控制作用但短期效果不理想;3种材料覆盖后,上覆水体中均低检出或未检出Cu、Pb、Zn、Cr、Cd,Fe、Mn、Ca、Mg的含量也较对照组低,削弱了金属元素的释放迁移;结合底泥内源污染物的控制效果和上覆水体水质的稳定性两方面因素,3种材料中,材料2(配料为赤泥38.9%,黏土14.4%,粉煤灰38.9%,Ca CO37.8%)最适于深谷型湖泊底泥覆盖。该覆盖方法原料获取方便、材料制作简单、经济成本低廉、操作方法简易、污染控制效果优良,可用于深谷型湖泊底泥原位控制。     

贵州红枫湖底泥磷释放的模拟实验研究

在实验室条件下,模拟了温度、溶解氧(Dissolved Oxygen,DO)、pH、扰动、微生物等环境因子对红枫湖底泥磷释放的影响。实验结果表明:(1)底泥磷的释放量随温度的升高而增大,5℃时底泥磷的释放通量为0.59mg·m-2·d-1;25℃和35℃时底泥磷的释放通量分别为1.25和3.68mg·m-2·d-1。(2)厌氧(DO2.0mg/L)条件下,底泥磷释放显著,释放通量在1.15~4.57mg·m-2·d-1之间;好氧(DO6.0mg/L)条件下,底泥磷的释放通量仅为0.82mg·m-2·d-1。(3)底泥磷的释放与上覆水pH值密切相关,且释放量随上覆水pH值的升高而增大,当pH=5.5和pH=7.5时,底泥磷的释放通量分别为1.15和1.25mg·m-2·d-1;当pH=9.5时,底泥磷的释放通量为4.57mg·m-2·d-1。(4)扰动条件下的底泥磷释放通量(2.62mg·m-2·d-1)明显大于静置条件下的底泥磷释放通量(1.25mg·m-2·d-1)。(5)微生物对底泥磷释放有明显影响,灭菌条件下的底泥磷释放量明显大于有微生物条件下的底泥磷释放量。综上所述,高温、厌氧、高pH值、强烈扰动均可促进红枫湖底泥磷的释放,微生物对底泥磷释放有明显抑制作用。基于红枫湖底泥磷释放模拟实验结果,计算了不同环境条件下红枫湖底泥磷的释放通量,在此基础上估算出红枫湖夏季热分层期间(6~9月)底泥磷释放量约为8.58t,占红枫湖水体总磷负荷(约28t)的30.6%,表明红枫湖底泥内源磷释放对水体磷负荷和富营养化有重要贡献,亟待开展底泥内源污染治理。     

生物炭覆盖对底泥污染物释放的影响

为研究生物炭对底泥污染物释放的影响,将芦竹茎、芦苇茎、花生壳及玉米芯利用限氧升温炭化法烧制成生物炭(Biochar),在模拟反应器中覆盖在受污染底泥上,研究生物炭对上覆水NH4+-N、NO3--N、NO2--N、COD及PO34--P浓度的影响,并计算各指标累积释放量及释放速率;同时测定了生物炭可溶性NH4+-N和PO34--P的释放量.结果表明,未覆盖生物炭的对照组上覆水氨氮浓度在第25 d达到最大值4.27 mg·L-1,之后稳定在4.02 mg·L-1左右,而4种生物炭处理组在第25 d以后,氨氮浓度稳定在0.3 mg·L-1以下,其中芦苇处理组抑制效果最明显,氨氮累积释放量减少了85.61%;4种生物炭组COD累积释放量较未添加生物炭处理组减少了28.83%～30%;玉米芯生物炭处理组磷酸盐浓度高于对照组,芦竹及花生壳处理组对底泥磷的释放抑制效果较好.生物炭NH4+-N和PO34--P的释放量在前3 d最大,花生壳生物炭组氨氮释放量最大,为36.79mg·kg-1,玉米芯生物炭处理组磷酸盐释放量最大,为70.64 mg·kg-1.结果表明生物炭对底泥NH4+-N、COD及PO34--P的释放有削减作用,具有应用到污染水体底泥修复的潜力.     

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.     

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.     

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.     

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.     

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.     

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.