Zn系LDHs覆膜改性人工湿地沸石基质除磷机制

选择Zn系层状双金属氢氧化物(LDHs),采用水热-共沉淀法合成3种不同类型的Zn-LDHs(Fe Zn-LDHs、Co Zn-LDHs和Al Zn-LDHs)并覆膜于常用人工湿地沸石基质表面;利用模拟垂直流人工湿地小试系统,对原始沸石及3种Zn-LDHs覆膜改性沸石基质进行除磷净化实验、等温吸附-解吸实验以及动力学吸附实验,通过上述实验对以Zn-LDHs覆膜改性沸石基质为代表的改性基质除磷机制进行研究.结果表明,Zn-LDHs覆膜改性沸石基质对磷素净化效果具有明显的提升功能,其中以Fe Zn-LDHs覆膜改性基质尤为突出;改性使基质的饱和吸附容量得以提高,增强了基质对磷酸盐的解吸性能,并使沸石基质对磷酸盐的主要吸附类型由物理吸附向化学吸附转换;通过对沸石基质类型及其改性方式的合理选择,可达到利用沸石人工湿地强化除磷以高效净化富营养化水体的目的.     

铵饱和天然钙型沸石基质人工湿地对模拟养猪废水的处理效能

针对养猪废水中有机污染物和氨氮(NH4+-N)浓度高、悬浮物含量高的特点,采用循环流人工湿地工艺对其进行处理,研究以天然钙型沸石为基质的人工湿地对模拟养猪废水的处理效能。结果表明:历时22个月的高NH4+-N负荷运行,已使人工湿地中的钙型沸石对NH4+-N的吸附达到饱和。在天然钙型沸石填料铵饱和条件下,湿地系统对模拟养猪废水中NH4+-N的处理效果仍可达61%~76%,对TN的去除率可达66%~80%,对CODCr的去除率一直维持在78%~92%之间。     

人工湿地生物沸石快速吸附-再生性能与再生机理研究

在填充生物沸石和石灰石的强化硝化模拟人工湿地中,考察了生物沸石快速吸附-再生动态平衡性能和生物沸石再生的机理.研究结果表明,生物沸石模拟人工湿地中硝化作用明显,产生的氧化态氮主要为硝氮,平均浓度为106.31 mg·L~(-1)(大于吸附去除的氨氮浓度).模拟人工湿地出水中的金属阳离子主要为Na+和Ca~(2+),30 d后Ca~(2+)浓度大于Na+浓度.生物沸石的再生是离子交换释放氨氮和微生物协同作用的结果.石灰石缓慢释放的Ca~(2+)可促进生物沸石再生,生物沸石与石灰石投加量的最佳质量比为5∶1.生物沸石再生过程中,微生物起主导作用.     

不同基质垂直流人工湿地对猪场污水季节性处理效果的研究

研究了3套不同基质垂直流人工湿地小试装置在不同季节处理猪场污水的运行效果.结果表明,垂直流人工湿地对有机污染物的去除效果随季节变化差异不明显,对有机物降解情况可用一级降解模型模拟;传统型湿地系统NH4 -N去除率在各季节稳定在52%,而沸石和沸石-煤渣型系统冬季NH4 -N去除效率分别从秋季的89.8%和93.4%下降至冬季的64.2%和73.5%,春、夏季回升至80%左右.冬季湿地系统中生物硝化与反硝化作用的减弱影响了垂直流人工湿地系统TN的去除;3套不同基质系统中,沸石-煤渣型系统各高度层硝化强度均为最高,沸石型和沸石-煤渣型系统的反硝化强度明显高于传统型系统,与实际运行过程TN去除率变化相吻合.采用沸石作为基质有利于系统的反硝化进程和TN的去除.垂直流系统对TP去除率随季节性变化波动不显著,但随着垂直流人工湿地系统的运行,基质层对TP的吸附逐渐饱和,去除效率明显下降.     

不同基质的人工湿地去除猪场沼液中磷的性能

以猪场沼液为研究对象,通过静态吸附试验研究沸石、硅藻土、煤渣、铁粉、石英砂5种基质对磷的等温吸附特征,并采用一级和二级动力学模型分析吸附动力学过程。根据试验结果,构建了4种人工湿地单元研究人工湿地对猪场沼液处理效果及对高浓度沼液的抗冲击能力。结果表明,5种基质对总磷的吸附更符合非线性Langmuir方程。准二级动力学方程更能描述各种基质对总磷的动力学吸附过程。沸石对磷的最大饱和吸附量1.868 mg/g,对磷去除率最高,可达到96.01%。沸石-垂直流人工湿地在构建的4种人工湿地单元中具有最强抗冲击能力。     

垂直流人工湿地LDHs覆膜改性沸石基质强化除磷效果及其机制

采用碱性水热-共沉淀法,将6种金属化合物(CaCl2、ZnCl2、MgCl2、FeCl3、AlCl3、CoCl3)两两组合生成9种不同类型的层状双金属氢氧化物并覆膜于常用垂直流人工湿地沸石基质表面;利用分别填充原始沸石及9种LDHs覆膜改性沸石基质的模拟垂直流人工湿地小试系统进行除磷净化实验,并结合10种沸石基质的等温吸附实验结果,对LDHs覆膜改性沸石基质的强化除磷机制进行研究.结果表明,相对于原始沸石基质,9种不同组合方式生成的LDHs覆膜改性沸石基质除磷效果均有不同程度的提高;Zn2+参与合成的改性基质除磷效果优良,其中ZnFe-LDHs改性沸石基质对总磷、溶解性总磷及磷酸盐的平均去除率超过90%,其最大理论吸附量达到了原始沸石基质的3倍;LDHs覆膜改性沸石基质通过增加化学吸附容量、提高物理吸附能力达到强化除磷效果的目的.     

人工湿地污水处理系统的蛭石缓冲单元及缓冲能力生物再生研究

针对当前人工湿地污水处理中普遍存在的冬季处理效果差等问题,研究了在处理系统中构建天然蛭石缓冲单元及其吸附饱和后进行生物再生的可行性.结果表明,在水力负荷为1.4 m3·m-2·d-1(COD:150～350mg·L-1、NH 4-N:10～30 mg·L-1、TP:1.0～4.5 mg·L-1)和蛭石层填充高度≥60cm的条件下,无植物天然蛭石缓冲单元可至少在45d内保持出水各项水质指标达到一级排放标准(GB 18918-2002),从而可基本满足人工湿地在植物换季时期的处理需要,而且,增加系统含氧量和蛭石用量可提高体系缓冲性能.在夏秋季温度较高的条件下(25～30℃),利用微生物的硝化与反硝化作用和植物根系的吸收与复氧功能,可有效提高蛭石再吸附的能力,其中有植物的湿地单元90d后蛭石吸附容量的再生率可达88.2%～91.3%,生物再生过程的动力学方程符合指数关系,植物种类、干湿交替时间和碳源对蛭石生物再生过程有较为显著的影响.     

几种人工湿地基质净化磷素污染性能的分析

通过基质磷素等温吸附、净化磷素污染效果和基质磷素饱和吸附后磷素释放实验,研究了砂子、沸石、蛭石、黄褐土、下蜀黄土、粉煤灰和矿渣7种人工湿地基质净化磷素污染效果和影响因素,并评价了基质磷素饱和吸附后磷素释放可能造成的二次污染风险结果表明:Freundlich和Langmuir等温吸附曲线方程均能很好地描述上述基质磷素吸附过程,其磷素理论饱和吸附量依次为矿渣＞粉煤灰＞蛭石＞表土＞下蜀黄土＞沸石＞砂子.磷素的净化能力依次为矿渣＞粉煤灰＞蛭石＞表土＞下蜀黄土＞沸石＞砂子,模拟污水磷素净化实验也证实矿渣、粉煤灰、蛭石净化磷素污染效果较好,表土和下蜀黄土次之,沸石和砂子净化磷素污染效果较差.矿渣和粉煤灰等钙素含量较高的碱性基质,影响磷素吸附净化效果的主要因素是基质的全钙含量,碱性条件下,基质全钙含量越高,其吸附的磷素越多,净化磷素污染的效果越好.砂子、沸石、下蜀黄土、黄褐土和蛭石等活性胶体氧化铁铝含量较多的中性基质,影响其磷素吸附净化效果的主导因素是其胶体氧化铁的含量,胶体氧化铁能促进基质吸附磷素效应,提高磷素净化能力.基质磷素饱和吸附后磷素释放实验也表明:除砂子基质磷素释放比例较高以外,其它基质磷素释放的比例很低,加强人工湿地基质的管理,上述人工湿地基质一般不会对水体环境造成二次污染.     

铵饱和天然钙型沸石的化学再生效果

为实现沸石人工湿地的长期高效运行,以铵饱和天然钙型沸石为对象,通过沸石化学再生试验,从6种常用化学再生剂(NaCl+NaOH,NaCl+CaCl₂和NaCl+NaHCO₃组合型,以及NaCl,CaCl₂和NaHCO₃)中筛选出最佳再生剂,并优化了再生剂适用条件. 结果表明,NaCl+CaCl₂组合型再生剂能提升沸石再生率10%～20%,且不影响沸石结构,是一种较优的再生剂. 采用NaCl+CaCl₂组合型再生剂,Na+在沸石再生初期起主导作用,而当c(Na＋)较低时,Ca2+的离子交换作用逐渐起主导作用,因而采用该组合型再生剂能显著提升再生剂效果的持久性. 再生条件优化试验表明,当c(NaCl)∶c(CaCl₂)为7∶3,即当Ca2+和Na+所带正电荷数接近时,组合型再生剂再生率相对较高;当再生温度低于45℃时,升高温度能显著提升沸石再生率;而再生剂投加量为0.6 mol/L(以再生剂中的阳离子浓度计)时,组合型再生剂投加量最经济.      

垂直流人工湿地系统基质优化级配研究

选取生物陶粒、无烟煤、沸石、钢渣和蛭石为基质,按不同的级配方式填充成基质柱,进行垂直流人工湿地模拟柱净化污水实验.研究表明,粒径分层级配基质对COD的去除率均高于单一粒径基质,其中分层生物陶粒对COD的平均去除率高达72.91%.分层沸石对总氮的净化能力较单一粒径基质有所提高,平均去除率高达91.23%.填充了生物陶粒、沸石和无烟煤的模拟柱对有机物和氮的净化效果和单一基质没有显著性差异(p0.05).填充钢渣和无烟煤的模拟柱出水pH值均在正常范围内,但是除从上到下依次填充无烟煤、蛭石和钢渣的基质柱外,其它填充钢渣和无烟煤的模拟柱对磷素的净化能力都低于单一基质.种植植物对净化效果没有明显影响.在垂直流人工湿地中,针对水质特点选择高效的级配基质,如分层生物陶粒、分层沸石、分层无烟煤以及生物陶粒、沸石和无烟煤组合,在高水力负荷条件下可获得更好的处理效果.     

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.     

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.     

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.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.