海河沉积物中磷释放的模拟研究

在实验室条件下,分别对海河沉积物中磷的释放量与沉积物磷形态分布的关系及好氧/厌氧条件,pH,温度,外源磷含量,微生物活动等环境因素对其的影响进行了模拟研究. 结果表明,微生物作用是影响海河沉积物中磷释放量的主要因素;厌氧条件下,磷从沉积物向水体的释放量远高于好氧条件下沉积物磷的释放量;温度升高有利于沉积物中磷的释放;酸性和碱性条件下沉积物磷的释放量略高于中性条件下沉积物磷的释放量;当上覆水磷含量较高时,沉积物中的磷呈“负释放"状态. 研究还显示,沉积物中不同形态的磷含量与沉积物磷释放量有不同程度的相关性,其中可交换态磷(NH₄Cl-P)和可还原态磷(BD-P)含量与沉积物磷的释放量高度相关(R2分别为0.99和0.84).      

海河沉积物磷释放模拟实验研究

在实验室条件下,分别对海河沉积物中磷的释放量与沉积物磷形态分布的关系及好氧/厌氧条件,pH,温度,外源磷含量,微生物活动等环境因素对其的影响进行了模拟研究. 结果表明,微生物作用是影响海河沉积物中磷释放量的主要因素;厌氧条件下,磷从沉积物向水体的释放量远高于好氧条件下沉积物磷的释放量;温度升高有利于沉积物中磷的释放;酸性和碱性条件下沉积物磷的释放量略高于中性条件下沉积物磷的释放量;当上覆水磷含量较高时,沉积物中的磷呈“负释放”状态. 研究还显示,沉积物中不同形态的磷含量与沉积物磷释放量有不同程度的相关性,其中可交换态磷（NH4Cl-P）和可还原态磷（BD-P）含量与沉积物磷的释放量高度相关（R^2分别为0.99和0.84）.     

三峡水库主要支流沉积物的磷吸附/释放特性

以三峡水库主要支流寸滩、小江、大宁和香溪表层沉积物为对象,通过连续提取法分析4种沉积物磷的赋存形态,模拟研究了pH和温度对不同沉积物磷吸附/释放的影响.结果表明,寸滩、小江、大宁和香溪表层沉积物磷赋存形态均以无机磷为主(占总磷含量的59.29%～78.82%),其中钙结合态磷(Ca-P)含量大于铁/铝结合态磷(Fe/Al-P).上覆水pH值对沉积物磷释放有明显的影响,中性条件下磷释放量最低,酸性条件下由于占优势的Ca-P大量溶解导致磷释放量大于碱性条件,因此,水体酸化易增加三峡主要支流(寸滩、小江、大宁和香溪)的磷释放风险.pH值变化亦明显影响沉积物对于磷的吸附,pH在6～8范围内,4种沉积物对于磷的吸附量保持在较高的水平,吸附量从大到小的顺序为:小江大宁寸滩香溪.偏酸性条件(pH6)下过多的H 与固体表面竞争溶解态活性磷(SRP);偏碱性条件(pH>8)下大量的OH->与SRP竞争沉积物表面的吸附位,故这-pH值范围内(pH<6或pH>8)磷的吸附量明显减少.磷在4种沉积物上的吸附为吸热过程,不同温度下(278K、293K、303K)沉积物对P的吸附均符合修正后的Langmuir模型,标准吸附热为18.92～46.63 kJ·mol-1其中,磷从水体分配到大宁河沉积物中的标准吸附热最大.     

黄河中下游沉积物对磷酸盐的吸附特征

研究了黄河中下游12个沉积物的临界磷平衡浓度(EPCo),以此判断沉积物是磷"源"还是磷"汇".用修改后的Langmuir 等温吸附模型对吸附实验数据进行了拟合.结果得到最大吸附容量(PAC).Langrnuir吸附平衡常数(k).利用所得拟合参数通过公式计算方法得到EPC0、原有交换态磷(NAP)以及固·液分配系数Kp值并考察了环境因子(pH、离子强度)对吸附作用的影响·沉积物的EPCo均大于上覆水体中的磷浓度,沉积物有向上覆水体释放磷的能力.吸附容量与总有机碳(TOC)含量有较好的正相关关系.pH<6.0,沉积物释放磷并且随着pH增大吸附量增加很快;69.7.吸附量略有增高.随着Ca2 离子强度的增加,沉积物对磷的吸附量减小.     

江苏西部湖泊沉积物营养盐赋存形态和释放潜力差异性分析

为了探索湖泊沉积物对上覆水中氮磷营养盐特别是磷(P)浓度的影响,研究了江苏西部10个湖泊沉积物P形态、吸附解吸作用和间隙水、上覆水之间扩散通量.对P形态的分级提取研究表明,各湖泊沉积物中P以无机磷为主,无机磷中生物可利用P占总磷(TP)比例较低.与苏北西部湖泊相比,苏南西部湖泊沉积物中Fe-P含量相对较高.江苏西部湖泊沉积物中氮主要以NH4+-N扩散为主,且大部分湖泊氨由上覆水向沉积物扩散,而洪泽湖、石臼湖和玄武湖NO3--N由沉积物向上覆水扩散.偏酸(pH<4)和偏碱(pH>10)条件下均有利于湖泊沉积物P的释放,除玄武湖外,其他湖泊在偏碱条件下P的释放量大于偏酸条件.沉积物对P吸附量随着温度的升高而增大,通过修正的Langmuir方程对湖泊沉积物磷吸附等温线进行拟合得到最大吸附量(Qm)、Langmuir吸附常数(k)与原有吸附态P(QNAP)参数,结果显示洪泽湖和玄武湖沉积物对P的最大吸附量较小,较易发生内源P释放.     

光照对湖泊沉积物磷释放及磷形态变化的影响研究

将采自太湖的沉积物移至实验室内进行磷释放模拟实验.通过对水-沉积物界面在不同照度下的磷释放趋势研究发现,照度与水-沉积物界面的磷释放量有明显的负相关性.而藻类计数的结果表明,照度与底栖藻类生物量存在正相关性.由此可以推断,光照对沉积物磷释放的影响主要表现为受照度控制生长的底栖藻类吸收沉积物中释放的磷,阻挡其进入上覆水中.不同照度下pH变化的研究结果表明,pH的升高趋势随照度的增强而升高,稳定后的水体偏碱性.通过对在不同照度下沉积物中总磷及磷形态变化规律研究发现沉积物中总磷减少量表现为无光＞中照度＞高照度;沉积物中磷出现无机态减少,有机态增加的现象;照度越高,沉积物中NaOH-P(Fe(Al)-P)减少量与HCl-P(Ca-P)减少量的比例越大.     

硬毛藻生长对水体和沉积物中碱性磷酸酶活性及磷含量的影响

为研究水体与沉积物中APA(碱性磷酸酶活性)与磷含量的相互关系,于山东省荣成天鹅湖藻类暴发区采集丝状硬毛藻和表层沉积物,进行室内模拟试验,分析了藻类生长过程中水体和沉积物中APA、磷含量、藻体生物量及磷富集量的动态变化. 结果表明:①试验初期(0~3 d),水体中ρ(TP)较高,无沉积物组各处理水体总APA变化不大,有沉积物组有所下降. 1周后,除ρ(TP)为2.00 mg/L处理外,其余处理水体ρ(SRP)(SRP为可溶性磷)降至较低水平(0~0.06 mg/L);水体总APA增加,其中无沉积物组低磷(0~0.20 mg/L)处理下APA变幅为6.02~18.32 μmol/(L·h),远高于相同初始ρ(TP)的有沉积物处理. ②与初始值相比,试验结束时低磷处理沉积物中各形态磷含量下降,APA升高. ③不同初始ρ(TP)条件下,藻体生物量相差很大,试验结束时藻体磷富集量与初始ρ(TP)呈显著正相关(P<0.05). 研究显示,硬毛藻生长可大量吸收水体中的磷,从而诱导水体中总APA增加,试验中期(4~12 d)低磷处理中AP(碱性磷酸酶)以颗粒态为主,而高磷(0.50~2.00 mg/L)处理中溶解态APA较高;另一方面,藻类生长使沉积物中APA升高,并加大了水-土界面磷的浓度梯度,从而可促进沉积物中可还原态磷和铁锰结合态磷向上覆水体释放.      

巢湖底泥磷的释放模拟实验研究

在实验室条件下，模拟了DO控制、pH值调节、温度调节、水动力条件等，进行了底泥释磷实验。实验表明：（1）厌氧条件下，底泥中的磷向水体释放，且释放强度随pH值的升高而升高。好氧条件下，底泥非但没有向水体释放磷，反而从水体中吸附磷，呈“负释放”状态；且pH值越低，“负释放强度”越大。（2）温度升高有利于底泥中磷的释放，最大释放强度随温度的升高而提前。（3）搅动条件下的底泥磷释放量大于静置条件下的底泥磷释放量。（4）微生物对磷释放有明显的影响。从本次模拟实验结果看，体系温度升高、减少溶解氧、提高pH以及施以水动力作用，均可使底泥中的磷释放量增加，在常温（25℃）、厌氧、pH=7.5条件下，底泥中磷向水体的释放量将增加17％左右。     

长江河口水库沉积物磷形态、吸附和释放特性

为了对长江河口青草沙水库沉积物磷形态分布、磷吸附特性和磷释放特性进行分析,2011年4月~2012年1月对沉积物进行实地调查分析.磷形态分析结果表明沉积物总磷含量范围为535.07~910.9 mg·kg-1,以无机磷为主,有机磷含量相对较低.无机磷主要以钙结合态的磷存在,钙结合态磷占总磷的75.57%.磷吸附特性结果表明沉积物磷的等温吸附特征符合修正的Langmuir模型,沉积物磷的最大吸附量为9.78~39.84 mg·kg-1,沉积物-水界面平衡浓度EPC0(equilibrium phosphorus concentration)范围为0.024~0.12 mg·L-1,均高于上覆水体中相应的磷含量,因此,沉积物有向上覆水体释放磷的趋势.磷的释放特性结果表明沉积物最大释放量为11.03 mg·kg-1,在6 h左右达到最大值.沉积物磷释放量来自沉积物的铁/锰结合态的磷、钙结合态磷和有机磷,其中,铁/锰结合态磷和沉积物释放量呈相关性(P0.01).总体上,青草沙水库沉积物呈现释放状态,影响水库水体磷含量.     

氧化还原循环过程中沉积物磷的形态及迁移转化规律

为研究沉积物在氧化还原循环过程中磷循环迁移转化机制,通过控制实验模拟分析氧化还原条件下,上覆水理化性质变化特征、沉积物各形态磷变化及机制研究,并量化沉积物中磷的重新分配和沉积物磷酸盐的释放通量影响。结果表明,(1)氧化还原电位Eh和pH体系、硫体系、碳体系以及与磷相关性密切的铁体系变化规律具有周期性,并对解释沉积物-水两相界面磷的迁移转化机制有重要作用;(2)在氧化还原循环过程中,各形态磷含量随着氧化还原条件和时间变化,根据水-沉积物磷素变化量化分析可得,可还原态磷(BD-P)和铁铝结合态磷(NaOH-rP)是可逆地重新分配到弱吸附态磷(NH4Cl-P)、聚磷/有机磷(NaOH-nrP)、残渣态磷(Rest-P)和间隙水溶解性活性磷(SRP)中,且沉积物中变化量93.7%的磷在还原反应时不会释放到水体中;(3)上覆水总磷(TP)浓度变化的92%为上覆水的SRP,表明水-沉积物在该循环过程中以水溶性磷交换为主;(4)根据Fick第一定律得,还原阶段磷扩散通量最大值为0.58mg·(m2·d)-1,而氧化阶段第7d扩散通量约为0.16~0.22mg·(m2·d)-1;氧化反应阶段,扩散通量随时间逐渐降低,还原阶段的变化趋势相反,表明还原状态会加速沉积物磷的扩散程度,而曝氧降低了沉积物磷扩散通量。     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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