北黄海表层沉积物中颗粒态磷的形态分布

于2007年10月乘东方红2号科考船在北黄海采集表层沉积物,应用改进的SEDEX法对表层沉积物中的可交换态磷、有机磷、铁结合态磷、自生磷灰石磷、碎屑磷和难分解有机磷等6种颗粒态磷的含量进行了测定,并分析了其分布状况及其影响因素.结果表明,碎屑磷和自生磷灰石磷是总颗粒态磷的主要组分,含量的变化范围分别为25.7～122.5μg.g-1和5.7～176.2μg.g-1,分别占总颗粒态磷的质量分数为17.0%～56.9%和10.2%～49.8%.弱吸附态磷、可提取态有机磷、铁结合态磷、难分解有机磷含量的变化范围分别为5.5～43.9、4.1～41.4、2.3～26.7、6.0～33.6μg.g-1.碎屑磷和自生磷灰石磷含量之和占据了总颗粒态磷的大部分,表明总磷以自然来源磷为主;铁结合态磷含量较低,表明北黄海受人为输入引起的污染程度较轻;可提取态有机磷与难分解有机磷之和占总颗粒态磷的质量分数很低,表明颗粒态磷中有机态含量较低,主要以无机态的形式为主;生物可利用磷即弱吸附态磷、可提取态有机磷、铁结合态磷之和,占总颗粒态磷的质量分数为6.7%～33.2%,表明调查区表层沉积物中磷的生物可利用性较低.     

长江口沙洲表层沉积物磷的赋存形态及生物有效性

利用磷的连续分级提取方法,研究了长江口沙洲沉积物中磷的赋存形态分布特征,并探讨了沉积物中磷的生物有效性.结果表明,沙洲沉积物中总磷的含量为437.6～1103.7μg·g-1,其中79.5%以无机磷的形式存在,而无机磷中以碎屑态磷灰石磷为主;有机磷约占总磷的20.5%.磷的生物有效性分析结果显示,潜在的生物有效性磷主要包括弱吸附态磷、铁结合态磷和有机磷等3种赋存形态,而长江口沙洲沉积物中潜在的生物有效性磷含量较少,约为60.5～510.9μg·g-1,平均仅占沉积物总磷的28.86%.     

2008年调水调沙期间黄河下游悬浮颗粒物中磷的赋存形态

2008年调水调沙期间在黄河利津采集悬浮颗粒物样品,并采用水淘选法对样品进行了粒径分级,应用改进后的SEDEX法对颗粒物中磷的赋存形态进行了分析.结果表明,自生磷灰石磷和有机磷是调水调沙期间黄河悬浮颗粒物中磷的主要赋存形态;调水调沙期间悬浮颗粒物中总磷、弱吸附态磷、有机磷和非活性有机磷的含量低于非调水调沙时期,而碎屑磷...     

岷江干流表层沉积物中磷形态空间分布特征

近些年,岷江水体TP污染情况严重,而水体沉积物这一潜在污染源,对水质安全带来的威胁也不容忽视.为揭示岷江干流表层沉积物中磷形态的空间分布特征,于2016年12月,采集了岷江干流(阿坝~宜宾)表层沉积物样品,应用改进的SEDEX法对表层沉积物中的弱吸附态磷Ex-P、可提取态有机磷Org-P、铁结合态磷Fe-P、自生磷灰石磷Ca-P、碎屑磷De-P和非活性磷Res-P等6种磷形态质量浓度进行了测定.结果表明,岷江干流表层沉积物中总磷TP的质量浓度为522.17~979.22μg·g~(-1),已远超全国土壤磷素背景值700μg·g~(-1),表明岷江沉积物中TP浓度较高.从空间分布来看,岷江中游眉山河段中的表层沉积物是颗粒最细、有机质和TP质量浓度最高的区域.岷江干流表层沉积物磷的主要赋存形态为Ca-P和DeP,两者共占TP的质量分数为75%以上.同时,岷江干流表层沉积物中的生物可利用磷(Ex-P、Org-P和Fe-P总和)占TP的质量分数为10.31%~29.62%,其中以中游河段(尤其是眉山段、乐山段)质量浓度最高,这表明岷江中游河段表层沉积物中磷的生物可利用性较强,潜在环境风险较高.     

山东省南四湖底泥中磷的形态分布特征

利用分级提取法分析了山东省南四湖下级湖区及其主要入湖河流底泥中磷的化学形态,并研究了磷在表层沉积物与沉积柱芯中的形态分布规律.结果表明,表层沉积物中各形态磷的空间分布规律不明显,且含量存在较大的差异.表层沉积物中活性磷(可交换态磷、铝结合态磷、铁结合态磷三者之和)的含量占总提取磷的 41%~65%,提示沉积物中磷的生物可利用性较高.沉积物柱芯中活性磷含量较大,以交换态磷和铁结合态磷为主,铝结合态磷含量较少;闭蓄态磷、自生磷、碎屑磷和有机磷在垂向上的含量分布较为稳定,有机磷含量最低.在表层沉积物和沉积柱芯中无机磷占绝对优势,表明南四湖底泥主要为无机相沉积.     

海州湾秋季沉积物磷的形态分布及生物有效性

采用改进的连续提取法（SEDEX法）对2016年秋季（10月）海州湾的表层和柱状沉积物进行磷形态测定,研究不同形态磷的分布特征并分析其生物有效性.结果表明：表层沉积物样品总磷的含量为0.340~0.445mg/g,无机磷的含量为0.271~0.350mg/g;柱状沉积物中总磷的含量为0.367~0.614mg/g,无机磷的含量为0.302~0.443mg/g.总磷中以无机磷为主要赋存形态,无机磷中又以原生碎屑磷为主,各形态磷的含量大小顺序为;总磷（TP） > 无机磷（IP） > 原生碎屑磷（DAP） > 自生钙结合态磷（ACa-P） > 有机磷（OP） > 不稳态磷及铁结合态磷（Fe-P）.通过对磷的生物有效性研究发现,本次调查海域表层沉积物中的生物有效磷（BAP）含量为0.069~0.143mg/g,在TP中所占的百分比为19.44%~32.66%,平均值为24.17%;柱状沉积物的BAP含量为0.062~0.217mg/g,在TP中所占的百分比为16.11%~43.54%,平均值为30.77%,磷的释放风险较小.沉积物各形态磷与粒径的相关性结果显示,在柱状沉积物中,Fe-P、OP和ACa-P与细粘土、粗粘土和细粉砂为正相关性,而与粗粉砂、细砂和中砂则为负相关性,DAP则主要与粗粉砂、细砂和中砂表现出了极显著正相关性,与细粘土、粗粘土和细粉砂表现出显著负相关性,BAP与颗粒物粒径的相关性则具有一定的差异性,具体表现在不同粒径组成和平面分布上.     

荆州市地表水沉积物中磷的形态分析

通过对荆州地区主要地表水沉积物中磷的形态分析,揭示了地表水沉积物中不同形态磷的分布特征。结果表明：地表水沉积物中磷主要有交换态磷（Ex—P）、铝磷（Al-P）、铁磷（Fe—P）、闭蓄态磷（Oe—P）、自生钙磷（ACa—P）、碎屑钙磷（De—P）、有机磷（Or—P）7种磷,其中以自生钙磷（ACa—P）、碎屑钙磷（De—P）和有机磷（Or—P）为主,约占总提取磷的95％。自然条件下,绝大部分湖泊的沉积物中95％以上的磷是以生物较难利用的形态存在的,活性磷所占比例较小,不足沉积物总磷的3％;沉积物中铝磷、铁磷、闭蓄态磷、自生钙磷的含量与总磷含量均没有明显相关性。各形态磷的含量分布与水体沉积物的释磷特点及其地球化学循环规律,并受沿岸污水排放及近岸养殖排污等人为活动的影响。     

黄东海表层沉积物中磷的分布特征

于2011年3~6月分两个航次在黄东海采集了表层沉积物样品,测定了其中总磷(TP)、无机磷(IP)和有机磷(OP)的含量.结果表明,TP的变化范围为10.50~24.10μmol·g-1,IP的变化范围为7.14~17.10μmol·g-1,IP是TP的主要赋存形态,平均占TP的70%以上;黄东海大部分站位IP与TP的百分比在50%~90%之间,有4个站位的百分比高于90%,都分布在东海.沉积物中磷的含量和平面分布特征受到人类活动、物质来源、沉积物的粒度、沉积环境和水文条件等多种因素的影响.黄东海沉积物中总磷的埋藏通量呈现出区域性的差异,埋藏通量主要受沉积速率、沉积物的孔隙度和底层水含氧量等多种因素的影响,其中沉积物中总磷的含量和沉积速率是决定埋藏通量大小的关键因素.     

鄱阳湖沉积物有机磷形态及对水位变化响应

选取鄱阳湖枯水期不同高程出露表层沉积物,通过研究有机磷含量及形态差异,试图揭示江湖关系变化引起的水位下降对鄱阳湖沉积物有机磷潜在释放风险的影响.结果表明:1鄱阳湖枯水期表层沉积物有机磷含量(115.2~448.3 mg·kg-1)占总磷的19.3%~45.1%,有机磷含量空间分布呈"五河"入湖尾闾区高于湖心区和北部湖区.2鄱阳湖表层沉积物各形态有机磷含量大小顺序为:残渣态有机磷盐酸提取有机磷胡敏酸有机磷碳酸氢钠提取有机磷富里酸有机磷.3水位下降引起的沉积物出露时间延长是引起鄱阳湖不同高程沉积物有机磷形态变化的重要原因.沉积物出露时间越长,碳酸氢钠提取有机磷、盐酸提取有机磷与富里酸有机磷的含量越低,而胡敏酸有机磷和残渣态有机磷含量越高.同时,水位下降引起的沉积物出露时间延长致使活性有机磷和中活性有机磷占总有机磷比例下降,而非活性有机磷占总有机磷比例增加,反映了沉积物出露时间延长可能会促进有机磷形态由活性向非活性转化,在一定程度上能够降低沉积物有机磷的潜在性风险.     

三峡水库蓄水至175 m后干流沉积物理化性质与磷形态分布特征

为研究三峡水库蓄水至175 m后干流沉积物总磷(TP)及各形态磷的分布状况,2010年10月采集了乌江、茅坪等13个断面表层沉积物样品,分析了有机质、矿物成分、粒径等理化参数,测定了沉积物总磷、可交换态磷(Ex-P)、铝结合态磷(Al-P)、铁结合态磷(Fe-P)、闭蓄态磷(Oc-P)和钙结合态磷(Ca-P)的含量,探讨了磷形态赋存与沉积物理化性质间的相关性,评估了蓄水对沉积物磷的蓄积及生物可利用性的影响.结果表明,三峡水库干流沉积物有机质含量为7.79~55.63g·kg~(-1),主要矿物成分为绿泥石、伊利石和石英.沉积物的主要组成为黏土质粉砂,中值粒径(d_(50))范围为3.84~23.65μm.沉积物总磷含量为557.06~837.92 mg·kg~(-1),各采样点总磷富集指数均大于1,存在潜在的磷污染风险.沉积物磷形态以CaP和Oc-P为主,Ex-P、Fe-P和Al-P含量相对较低,生物可利用性磷仅占总磷含量的2%~8%.与历史资料相比,蓄水后三峡水库沉积物的粒径有细化变小的趋势,易风化矿物组分含量略有增加,蓄水水位的增加并未导致沉积物总磷含量出现明显升高趋势.未来,随着三峡水库来沙进一步减少和泥沙颗粒的逐渐细化,磷在三峡水库部分宽谷河段沉积物有可能逐步蓄积;蓄水运行过程引起的大面积消落带干湿交替以及近坝段浮泥再悬浮都将影响沉积物中磷的生物可利用性水平.     

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.