海州湾海洋牧场海域表层沉积物磷的形态与环境意义

采用沉积物无机磷分级方法结合上覆水初级生产力测定研究了海州湾海洋牧场海域表层沉积物磷的赋存形态及其生物有效性.结果表明:夏季总磷的含量高于春、秋两季,赋存形态以无机磷为主,平均占总磷的45.50%,各无机磷赋存形态的含量大小依次为:残渣态磷钙结合态磷铁铝结合态磷可交换态磷.其中可交换态磷、铁铝结合态磷以及钙结合态磷与有机碳含量成显著正相关(P0.01,R0.8).平面分布整体上呈现由近岸向远岸减小的趋势,这主要与陆源物质排放及沉积物自身质地有关.沉积物中的生物有效磷含量占总磷的36.95%,所占比例较大.     

洱海沉积物溶解性有机氮释放及环境影响机制

通过模拟实验,结合紫外与荧光光谱技术,研究了洱海表层沉积物DON释放特征,并探讨其环境影响因素及环境学意义.结果表明:(1)一级动力学模型可很好地拟合洱海表层沉积物DON释放动力学过程,其最大释放量在24.387~46.949mg/kg之间,空间分布呈现北部南部中部;最先释放(10min内达到最大值)组分主要为类蛋白组分P_(Ⅰ+Ⅱ,n),而释放量最大的组分是类腐殖质组分P_(Ⅲ+Ⅳ,n),约占76%;(2)洱海沉积物DON在好氧(DO=8~10mg/L)和适中pH值(pH=8)的环境中释放量相对较小,pH值增加或DO含量降低均会促进其释放.(3)洱海沉积物DON组成特征参数与其释放量显著相关(r=0.813~0.919,P0.01),随沉积物DON取代基增多,分子量增大,芳香性增强,释放量逐渐增大;类蛋白与类腐殖质组分比值P_(Ⅰ+Ⅱ,n)/P_(Ⅲ+Ⅳ,n)也可间接作为衡量沉积物DON释放量的指标,即沉积物DON结构组分特征参数可反映其释放特征,在一定程度上可用于指示洱海沉积物DON释放风险.     

我国红树林主要分布区表层沉积物砷的分布及形态特征

利用ICP-MS分析了我国红树林主要分布区表层沉积物的As含量和形态,阐明As的分布及其形态特征.结果表明,表层沉积物中w(As)为3.14～19.16 mg/g,平均值为8.14 mg/g.表层沉积物中w(As)与w(Fe),w(Mn),pH,w(有机质),粉粒和黏粒所占比例呈显著或极显著正相关.表层沉积物中的As主要以残渣态存在,其次为有机质-硫化物结合态.在整个研究区域,As的5种形态在总量中的所占比例:可交换离子态为14.40%,碳酸盐结合态为1.41%,铁锰氧化物结合态为2.16%,有机质-硫化物结合态为30.40%,残渣态为50.65%.可交换离子态所占比例与w(有机质)和pH呈极显著正相关.有机质-硫化物结合态所占比例与盐度、黏粒和粉粒所占比例呈显著或极显著正相关.残渣态所占比例与盐度、粉粒和黏粒所占比例呈极显著正相关.      

pH和盐度对海河干流表层沉积物吸附解吸磷(P)的影响

采用等温吸附解吸方法,研究大范围pH（2~12）和盐度（2‰~32‰）对海河表层沉积物吸附解吸磷的影响,并与分级提取技术得到的海河沉积物中磷形态分布相结合,进一步探讨磷在沉积物-水界面的迁移转化机理.结果表明,钙磷（Ca-P）和难溶态磷（Re-P）为海河表层沉积物磷的主要形态.沉积物对磷的吸附符合修正的Langmuir吸附等温线(R2>0.90).海河沉积物（8个典型断面）对磷的理论吸附量较大,说明在今后上覆水含磷浓度较高的情况下,沉积物仍能吸附大量的磷污染物.在海河水磷污染较轻的情况下,沉积物中的磷将释放并导致水体发生富营养化.pH对磷的吸附影响呈“U”型,且随着pH增大,磷的解吸量也增大,这是由于OH-交换能力的增强所致;盐度增大,沉积物对磷的吸附总体呈下降趋势,但在10‰~15‰之间有反复,并且随着盐度增大,磷的解吸量也下降.     

黄河(清水河段)沉积物中重金属的存在形式

应用连续化学浸提技术对黄河水体中重金属在不同粒径沉积物上的分布特征以及存在的化学形态进行了分析。结果表明 :(1 )沉积物的粒径越小 ,重金属的含量越高 ;(2 )黄河 (清水河段 ) 1 2 0目沉积物中不同形态的重金属分布为Pb:Ⅵ >Ⅳ >Ⅲ >Ⅴ >Ⅰ、Ⅱ ;Ni:Ⅵ >Ⅴ >Ⅳ >Ⅰ >Ⅲ >Ⅱ ;Cu:Ⅵ >Ⅳ >Ⅴ >Ⅲ >Ⅰ >Ⅱ ;Mn :Ⅵ >Ⅲ >Ⅳ >Ⅴ >Ⅰ、Ⅱ ;Fe:Ⅵ >Ⅳ >Ⅴ >Ⅲ >Ⅰ >Ⅱ ;Zn :Ⅴ >Ⅵ >Ⅳ >Ⅲ >Ⅰ、Ⅱ ;Co:Ⅵ >Ⅳ >Ⅴ >Ⅰ、Ⅱ、Ⅲ ;Cd :Ⅱ >Ⅲ >Ⅳ >Ⅰ、Ⅴ、Ⅵ (Ⅰ—水溶态 ,Ⅱ—可交换态 ,Ⅲ—碳酸盐结合态 ,Ⅳ—Fe Mn氧化物态 ,Ⅴ—有机态 ,Ⅵ—残渣态 ) :     

岱海沉积物氟化物赋存特征及其释放风险

为揭示岱海水-沉积物中氟化物的迁移转化规律,采用连续分级法研究了岱海间隙水,表层沉积物,柱状沉积物系统中氟化物的空间分布,赋存形态及释放风险.结果表明：岱海间隙水体中氟离子浓度平均值为（4.82±0.06）mg/L,显著高于地表水V类阈值（1.5mg/L）,并与上覆水中氟离子浓度（4.77±0.04）mg/L达到相对稳定平衡状态.表层沉积物总氟化物含量均值为（934.13±36.79）mg/kg,其中水溶态,可交换态,Fe/Mn结合态,有机束缚态和残渣态氟化物含量均值分别为（34.39±1.69）,（7.11±0.93）,（3.07±0.50）,（11.97±0.79）和（934.13±36.79）mg/kg;柱状沉积物水溶态,可交换态,有机束缚态氟化物含量随沉积物深度的增加呈下降趋势,并在40cm以下基本稳定;而Fe/Mn结合态氟化物在表层含量较低,在25cm后逐步稳定.多元回归分析可知,岱海沉积物中水溶态,可交换态氟化物含量与间隙水氟离子浓度呈显著正相关,且具有较强的迁移能力;SAC（稳定度）风险评估表明,表层沉积物中SAC范围在55.53%~69.52%,平均值为60.63%,处于极不稳定状态,且SAC从表层向下20cm呈逐步降低的趋势,间接反映出近年来可提取态氟化物富集明显,处于较强的释放风险状态.     

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.     

潮间带海洋沉积物中痕量汞的释放过程及其影响因素研究

海洋沉积物对重金属污染物的吸附是1种物理吸附过程,在一定的条件下（波浪和潮汐等）,吸附于沉积物中的汞可能重新释放出来,对滨海海洋生态环境造成永久性的潜在危害。在对厦门海域汞污染调查的基础上,选择代表性的海洋沉积物进行取样,系统测定潮间带海洋沉积物痕量汞的释放动力学过程,并分析了盐度、pH、温度和振荡频率对释放作用的影响。结果表明,潮间带海洋沉积物中痕量汞的释放动力学符合Ho的二级动力学方程,即随着时间的延续释放速度逐渐降低,沉积物中痕量汞的释放平衡时间约为24h．沉积物痕量汞的释放量随盐度的增加有所减小,随温度和振荡频率的增加而增加;在pH〈7时释放量随pH值的增加而降低．pH〉7时,释放量随pH值的增加而升高。     

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.     

不同模拟条件下太湖沉积物-水界面磷行为的研究

随着大量的磷输入水体,太湖富营养化已经成为一个严重的环境问题。沉积物内源磷的释放是湖泊上覆水体磷浓度升高的重要因素之一。文章针对太湖特征,模拟影响沉积物内源磷释放过程因素中的扰动、溶解氧和pH条件研究表层沉积物的内源磷行为。结果表明,在厌氧环境下有利于磷的释放,且没有扰动条件要比有扰动的释放量大,达到0.297 mg/L;好氧条件不利于磷的释放,经过好氧培养的沉积物中有机磷平均减少了约50%,好氧-厌氧交替使得铁结合态磷提高了0.001 8 mg/g。pH 8.2~8.6有助于沉积物磷的释放,且不同pH值下沉积物磷的最大释放时间不同,pH 9.0沉积物磷在1 d时最大释放量达到0.162 mg/L;沉积物中磷在不同pH下的形态会发生不同程度的转变,其中铁结合态磷(Fe-P)的转变最大。可见扰动、溶解氧、pH对沉积物内源磷的释放有着显著影响。     

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.