NH_4~+对镁改性生物炭除磷效果的影响

为提高人工湿地收割植物利用率并探讨水体中氨氮对镁改性生物炭(magnesium modified biochar,MBC)除磷效果的影响,本文以人工湿地植物芦苇为原料,引入金属镁离子对其改性,制备MBC,并以未改性生物炭(biochar,BC)为对照,通过批量摇床实验,研究了不同氮磷摩尔比(0、5、10)和初始磷浓度(100~500mg·L-1)条件下,MBC、BC、BC与金属镁离子(BC+Mg2+)、Mg2+这4种处理方式对磷酸盐的去除效果。结果表明4种处理方式对磷的去除量排序为MBCBC+Mg2+≈Mg2+BC,溶液中NH4+的存在促进MBC吸附除磷,氮磷摩尔比越大,初始磷浓度越高,MBC的磷吸附能力越强。XRD图谱分析结果表明,在MBC、BC+Mg2+、Mg2+这3种处理方式中,当氮磷摩尔比为5、10时,NH4+与溶液中的Mg2+和PO43-发生沉淀反应,生成鸟粪石(MgNH4PO4·6H2O),促进磷的去除。本研究利用人工湿地废弃生物质对富含氨氮和磷酸盐的溶液进行处理,确定了氨氮对水体中磷酸盐去除的促进作用,达到了回收利用、以废治废的目的,为水体富营养化治理提供了新的理论依据和数据支持。     

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.     

聚丙烯小球对人工垂直潜流湿地氮磷去除性能的优化研究

采用页岩和香蒲(Typha latifolia L.)构建人工垂直潜流湿地处理津河富营养化水体,并用聚丙烯小球替代部分页岩研究其对垂直潜流湿地氮磷去除性能的影响.设计水力负荷800 mm/d,理论水力停留时间12h.试验期间(2006-06～2006-11),氮磷月平均去除率在8月份达到最大值.与全页岩湿地相比,聚丙烯小球使氨氮(NH 4-N)、总氮(TN)、溶解性活性磷(SRP)和总磷(TP)月平均去除率分别提高13.38%、8.9%、9.29%和8.25%,使用聚丙烯小球能够有效提高人工垂直潜流湿地氮磷去除效率.试验结束后收割香蒲地上组织(茎和叶),测定地上组织生物量及茎、叶中的氮磷含量.结果表明,聚丙烯小球虽然抑制香蒲地上组织生物量的增加,但却能够有效提高茎、叶中氮磷含量.通过收割香蒲地上组织可使TN和TP去除分别增加29.382 g·m-2和13.469 g·m-2.     

载氧化镁水生植物生物炭的特性表征及对水中磷的吸附

为去除富营养化水体中的磷并实现水生植物的资源化利用,以水生植物芦苇和互花米草为原材料,通过MgCl_2改性制备了不同Mg~(2+)和植物配比的共12种生物炭,考察对水体中磷的吸附能力及镁改性前后生物炭特性的差异.结果表明,当Mg~(2+)与芦苇、Mg~(2+)与互花米草的质量比为0.48、0.36时,制得的两种生物炭对20 mg·L~(-1)磷的吸附能力最强,分别为8.52 mg·g~(-1)和9.21 mg·g~(-1),是未改性时的79倍和66倍;对溶液中20mg·L~(-1)磷的去除率分别达到85.2%和92.1%.改性后芦苇和互花米草生物炭C、H、N含量减少,Mg含量分别增加到22.77%和23.46%.芦苇生物炭改性后比表面积减小了118.71 m~2·g~(-1),互花米草生物炭增加了22.59 m2·g~(-1);二者孔容和平均孔径均有所增加.改性前后生物炭的表面官能团种类相同.XRD测试指出MgO为改性生物炭的复合纳米颗粒中最主要的晶相;SEM展现了布满MgO的改性生物炭表面及孔道.机理分析表明,MgO是生物炭吸附磷的关键.     

磷酸铵镁沉淀法预处理7-ACA综合废水试验研究

采用磷酸铵镁(MAP)沉淀法对高氨氮7-ACA综合废水进行了预处理试验研究,以Na2HPO4和MgCl2.6H2O作为沉淀剂,探讨了初始反应pH值、n(Mg2+):n(PO43-)/:n(NH4+)投配比及反应时间等因素对氨氮去除效果的影响。结合结晶物SEM分析,确定预处理的最佳工艺条件为:初始反应pH 9.0、n(Mg2+):n(PO43-):n(NH4+)投配比1.0:1.1:1和反应时间20 min。平行试验结果表明,在最佳工艺条件下,当进水氨氮浓度为1 020~1 190 mg/L时,处理后出水氨氮浓度为小于150.0 mg/L,氨氮去除率在85.0%以上,残磷量小于40.0 mg/L,为7-ACA综合废水的后续生化处理创造了有利条件。     

间歇曝气对人工垂直潜流湿地氮磷去除性能的影响

采用页岩和香蒲(Typha latifolia)构建人工垂直潜流湿地处理津河富营养化水体,研究间歇曝气对潜流湿地氮磷去除效果的影响.设计水力负荷800 mm/d,气水比5∶1.试验期间(2006-06～2006-11),氮磷月平均去除率在8月份达到最大值.与无曝气系统相比,中部曝气使氨氮(NH 4-N)、总氮(TN)、可溶性活性磷(SRP)和总磷(TP)月平均去除率分别提高10.1%、4.7%、10.2%和8.8%,底部曝气则为25.1%、10.0%、7.7%和7.4%,间歇曝气能够有效提高人工潜流湿地氮磷去除效率.曝气产生的有氧环境不利于硝酸盐氮(NO-3-N)去除,试验期间底部曝气和中部曝气NO-3-N月平均去除率一直低于无曝气系统.试验结束后收割香蒲地上组织(茎和叶),测定地上组织生物量及茎、叶中的氮磷含量,结果表明,间歇曝气虽然抑制香蒲地上组织生物量的增加,但却能够有效提高茎、叶中氮磷含量.与无曝气系统相比,通过收割香蒲地上组织可使TN去除分别增加11.6g·m-2(中部曝气)和12.6 g·m-2(底部曝气).     

生物质粒径对负载MgO生物炭吸附水体中磷的影响

为研究生物质粒径对负载MgO芦苇生物炭（MBC）去除水体中磷的速率和能力的影响,以0~0.5、1~2和6~8 mm这3种不同粒径的芦苇颗粒为原料、MgCl₂为改性剂制备MBC,用傅里叶变换红外光谱仪（FTIR）、X射线衍射仪（XRD）和扫描电子显微镜（SEM）等对MBC表征,开展MBC吸附溶液中磷酸盐（PO₄^3--P）动力学和等温线实验以及实验数据模型拟合.结果表明,MBC对溶液中PO₄^3--P的吸附速率随生物质粒径增大而增大,0~0.5、1~2和6~8 mm芦苇颗粒制备的MBC对PO₄^3--P的吸附量在2 h内分别达到平衡吸附量的15.4%、25.8%和80.8%,而生物质粒径对MBC的PO₄^3--P最大吸附量（249.0~254.7 mg·g^-1）无明显影响.6~8 mm芦苇颗粒制备的MBC保留了较完整的芦苇细胞壁结构,且含有丰富的微孔和中孔,形成多层次、规则的、连通性好的孔隙结构.0~0.5 mm和1~2 mm芦苇颗粒制备的MBC孔隙结构较差,孔隙连通性受损,影响了磷酸根离子在MBC内部的扩散速率,限制了对磷的吸附速率.因此,以人工湿地收割的废弃植物芦苇为原料制备MBC用于去除水体中磷时,将芦苇破碎至6~8 mm即可,过度破碎会破坏MBC的孔隙结构,减小MBC对磷的去除速率.     

潮汐流人工湿地对高污染河水氮磷的去除特性

通过一年半的实验,对比研究了不同运行方式下垂直潜流人工湿地对高污染河水氮磷的去除特性,并分析了各种因素对潮汐流人工湿地(TF CW)脱氮除磷的影响作用。结果表明:潮汐流的运行方式能够提高系统对氮磷的去除效果,其对总氮(TN)、氨氮(NH_4~+-N)、总磷(TP)和磷酸盐(PO_4~(3-)-P)的平均去除率分别为37.6%、51.6%、54.1%和41.4%;系统对氮磷的去除效果表现出显著的四季性差异(P0.05),系统在夏季的效果最好,冬季最差;且系统对TN、NH_4~+-N、TP、PO_4~(3-)-P的去除与进水负荷有较强的相关性;运用冗余分析(RDA),得出水环境因子对氮磷去除负荷的影响作用,其中TN去除负荷与悬浮性颗粒物浓度(ρ(SS))、碳源浓度、温度(T)呈正相关,且相关性依次增大,而与溶解氧浓度(ρ(DO))则呈负相关性;NH_4~+-N去除负荷与氧化还原电位(ORP)、ρ(DO)均呈正相关,且相关性依次增大;TP去除负荷与pH、ρ(SS)均呈正相关,且相关性相近;PO_4~(3-)-P去除负荷与pH呈正相关,且相关性极为显著。     

太湖蓝藻水华衰亡对沉积物氮、磷释放的影响

在太湖草型区、藻型区及河口区采集原状泥柱进行加藻培养实验,监测培养过程中溶解氧(DO)、总氮(TN)、总磷(TP)、氨氮(NH4+-N)、磷酸根(PO43--P)等相关指标的变化.结果表明,蔽光培养导致加藻体系中蓝藻大量死亡,形成水体极度缺氧环境(DO接近0),沉积物氮、磷释放量改变,上覆水NH4+-N、PO43--P...     

海水MAP法去除N、P废水实验研究

海水中富含大量的镁盐,利用镁盐和废水中的氮、磷生成白色的磷酸铵镁沉淀,可以实现废水中氮磷的脱除。本研究首先测出海水中镁的含量,然后根据镁含量设计正交试验开展研究。实验结果表明,对于废水中氮元素的去除,时间因素的影响程度较大,对于废水中磷元素的去除,pH值的影响程度较大;当pH=9.5,n(Mg2+):n(NH4+):n(PO34-)=1.3∶1∶1.08,反应时间为60 min时,氮磷的去除率可以达到63.01%和95.39%。因此,利用海水中的镁盐,去除废水中的氮磷元素,可以实现海水资源的有效利用,同时,可以提高去除氮磷的效率,降低废水处理的费用。本研究可实现氮磷废水处理的同时,实现海水资源化利用。     

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.