太湖不同营养水平湖区沉积物理化性质和磷的垂向变化

利用SMT标准测试程序对太湖3个不同营养水平湖区表层10 cm柱状沉积物进行磷赋存形态的垂向分析,并在此基础上讨论了沉积物有机质总量(w(OM)),细颗粒组成与磷赋存形态间的相关关系.结果表明,研究区各采样点沉积物的w(TP)平均值为437～1 650 mg/kg,最高为1 809 mg/kg; w(OM)平均值为17.93～38.76 mg/g;沉积物颗粒组成以粉砂和粘粒为主,占总量的49.64%～83.57%.不同湖区沉积物磷形态的垂向分布规律不同,总体上TP,无机磷(IP),铁铝结合态磷(Fe/Al-P)表现出在表层富集的现象, 钙结合态磷(Ca-P)和有机磷(OP)随深度的变化不大; w(OM)自表层向下逐渐降低. 无机磷占沉积物中总磷的比例较大,且其含量与Fe/Al-P的含量密切相关.Fe/Al-P占TP的比例随沉积物污染程度的增加而升高,是与人类活动密切相关的;有机质总量与OP显著相关;粘粒比例随污染程度的增加逐渐增大.      

滇池沉积物内源氮释放风险及控制分区

采用淹水培养法测定了滇池20cm沉积物可释放态氮(EN)、潜在可释放态氮(MN)及稳定态氮(FN)含量,并分析了其空间分布特征,结合沉积物定年数据计算了不同形态氮蓄积量.依据沉积物-水界面氮释放通量、EN蓄积量及MN蓄积量对滇池沉积物内源氮污染状况进行分区,评估了不同区域滇池沉积物内源氮释放风险,并对不同分区提出了污染控制措施.结果表明,滇池沉积物内源氮释放风险:外海南部 >外海北部 >外海中部 >草海,潜在释放风险:外海南部 >外海中部 >草海 >外海北部;滇池沉积物氮污染有由北向南转移趋势;滇池全湖20cm沉积物蓄积TN5757.90t,EN637.72t,MN1320.76t,FN3799.42t.根据沉积物氮污染滇池可划分为高污染区、中度污染区、低污染区及安全区,分别占全湖面积的13.51%、15.02%、46.06%、25.42%,其中高污染区主要分布在草海、外海北部盘龙江附近;中度污染区主要分布在高污染区以下从宝象河到观音山区域及滇池出水口海口等区域;低污染区主要分布在中度污染区以下从广谱大沟到整个外海南部区域.高污染区可采取底泥环保疏浚技术,中度污染区可采取安全生态性高的原位控制技术,低污染区可采取覆盖技术,配合水生植被修复技术.     

滇池表层沉积物对磷的吸附特征

在室内模拟条件下,从滇池表层沉积物对磷的吸附动力学与热力学两个角度出发,研究了滇池沉积物对磷的吸附特征,同时探讨了不同磷形态对磷吸附特性的影响,结果表明:1滇池不同形态磷含量顺序为:有机磷钙(O-P)钙结合态磷(Ca-P)金属氧化物结合态磷(Al-P)残渣态磷(Res-P)可还原态磷(Fe-P)弱吸附态磷(NH4Cl-P);2沉积物对磷的吸附动力学过程分为2个阶段,即快吸附和慢吸附阶段.快吸附阶段主要发生在0~0.5 h内,而慢吸附阶段主要发生在0.5~4 h.滇池沉积物对磷的吸附过程主要在4 h内完成.3外海北部上覆水磷酸盐(SRP)浓度低于沉积物中磷的吸附/解吸平衡浓度(EPC0),可初步判断该区域沉积物有向上覆水体释放磷的风险.4不同区域沉积物磷的最大吸附量(Qmax)和总最大吸附量(TQmax)均以外海南部最大.5沉积物本底吸附态磷含量(NAP)与钙结合态磷(Ca-P)呈显著正相关关系(R2=0.5139,p0.05),而其他吸附特征参数与磷形态之间相关性均不显著.6与洱海、太湖等湖泊相比,滇池沉积物磷的本底吸附态磷(NAP)和最大吸附量(Qmax)均处于较高水平,磷污染较为严重.     

滇池不同湖区沉积物正构烷烃的分布特征及其环境意义

为探明滇池沉积物中有机质的组成特征及其环境意义,2014年7月采集滇池北部和南部各一根柱状沉积物样品,分析了TOC(总有机碳)、TN(总氮)、正构烷烃含量剖面变化规律.结果表明:1滇池沉积物中TOC与TN自20世纪70年代以后增加显著,说明了滇池初级生产力不断提高;2滇池沉积物正构烷烃代用指标n-C27/n-C31比值及Paq和CPI表明,滇池沉积物从下往上草本植物与木本植物交替变化,且沉积物中的高碳数有机质主要来自滇池内源的沉水和漂浮大型植物;3C/N比值及正构烷烃分布特征表明,滇池不同湖区沉积物有机质来源存在差异:滇池北部沉积物中有机质主要来源于內源植物和陆源有机物的人为源;滇池南部沉积物中有机质主要来源于內源大型水生植物和陆源高等植物混源.为此,在今后滇池沉积物有机质的研究中,应加强对滇池不同湖区有机质的深入分析.     

滇池沉积物间隙水中氮、磷形态及相关性的研究

对滇池40个样点沉积物间隙水中的氮、磷形态与浓度分析研究结果表明，滇池沉积物间隙水中磷的区域分布特征与其在水体中的分布特征相似，滇池南部间隙水中无机磷浓度较高，有机磷的浓度极低，而北部有机磷浓度较高；间隙水中氨氮（NH4^＋ -N），浓度高出硝酸盐氮（NO3^- -N）浓度约2个数量级，间隙水中氮向上覆水的扩散主要以氨氮为主．滇池沉积物间隙水中氮、磷浓度远高于水体中氮磷浓度，有较强的释放趋势．进一步研究间隙水中氮、磷的关系则表明，沉积物间隙水中总磷和总氮未见明显相关性，但间隙水中总磷、有机磷均与硝酸盐态氮呈负相关．     

洱海沉积物有机质、铁、锰对磷的赋存特征和释放影响

利用SMT磷连续提取分级方法研究了洱海表层沉积物中磷的赋存特征,探讨有机质(OM),Fe和Mn对磷赋存形态及释放的影响,同时评估了洱海沉积物磷的释放风险. 结果表明:洱海表层沉积物w(TP)为710.3～1 961.2 mg/kg,其中w(Ca-P)最高(占36.9%～59.2%),w(OP)次之(占24.6%～36.9%),w(Fe/Al-P)最低(占9.8%～20.7%);w(OM)为25.0～119.6 mg/g,与w(TP)和w(Ca-P)呈显著负相关;w(总锰)为0.8～3.8 mg/g,w(总铁)为34.3～127.2 mg/g,均与w(TP)及其各形态磷含量呈显著正相关. 沉积物中w(Fe/Al-P)/w(Ca-P)比低于0.5,且w(总铁)/w(TP)远大于20,表明磷释放强度小,但w(TOC)/w(OP)<200,说明有机磷的潜在释放风险较大. w(TP)及其各形态磷含量均与无定形铁氧化物(Feo-Fep)含量呈显著正相关,而与结晶态铁氧化物(Fed-Feo)含量的相关性不显著,且全湖沉积物中的铁氧化物以Feo-Fep为主,表明洱海沉积物磷释放主要受Feo-Fep控制.      

滇池草海沉积物磷形态、空间分布特征及影响因素

研究滇池草海沉积物中磷的分布特征、影响因素对研究草海水体富营养化具有重要的意义.研究表明:草海中各形态磷含量和空间分布特征呈现明显差异, O-P、Ca-P、Al-P、Fe-P平均含量分别为804.08、768.35、167.29、63.01mg/kg.沉积物磷形态平均含量O-P>Ca-P>Al-P>Fe-P.沉积物总磷及各形态磷在空间上存在差异, 滇池草海西南部、北部和东部区域中全P、O-P、Ca-P、Al-P、Fe-P各形态磷都属于高含量区域.沉积物理化性质与上覆水性质是影响沉积物中磷形态的重要因素.其中沉积物全磷与O-P(R2=0.741*)、Ca-P(R2=0.678*)呈现显著性正相关关系;pH值与Al-P(R2=0.714*)、Fe-P(R2=0.664*)呈现显著负相关关系;沉积物有机质与O-P呈显著正相关性(R2=0.758*).沉积物上覆水DO与Fe-P呈显著负相关(R2=0.750*),上覆水中叶绿素a和Al-P存在显著正相关关系(R2=0.601*).表明沉积物磷形态释放与沉积物中有机质、pH值有关;同时上覆水中溶解氧制约沉积物Fe-P释放,叶绿素a含量促进沉积物Al-P的释放.     

滇池表层沉积物氮污染特征及其潜在矿化能力

利用滇池53个表层沉积物样品,研究了其不同形态氮含量及空间分布特征,探讨了滇池沉积物氮潜在矿化能力及其污染特征,以期揭示滇池沉积物氮污染影响因素及沉积物氮释放风险.结果表明:1滇池全湖表层沉积物总氮(TN)平均含量为3 515.60 mg·kg-1,其中草海北部疏挖区、盘龙江入湖口及海口入湖区域含量较高,宝象河河口疏挖区域TN含量相对较低;总有机氮(TON)含量较高,占TN的85.86%;溶解态无机氮(DIN)含量较低,占TN的14.10%,TON与TN空间分布趋势一致,而DIN则不同;与我国其他湖泊相比,滇池沉积物氮含量已经处于较高水平,其污染程度仅低于污染严重的城市湖泊;2滇池全湖表层沉积物潜在可矿化氮(PMN)平均含量1 154.76 mg·kg-1,占TN的32.90%,潜在释放风险较大;其中草海湖区、外海北部盘龙江入湖口湖区、中部洛龙河和梁王河入湖口湖区及白鱼口湖区显著高于其它湖区;目前滇池p H值有利于其沉积物氮矿化,有机质通过释放NH+4-N影响其沉积物氮矿化;污染较重的水域,滇池上覆水氮浓度受其沉积物氮矿化影响较大,而污染较轻水域,则受影响较小.     

滇池水生植物分布对沉积物间隙水磷浓度的影响

为揭示滇池水生植物分布对沉积物间隙水磷的质量浓度的影响,分别采集滇池有植物区域和无植物区域沉积物柱状样,测定间隙水和上覆水溶解性总磷(DTP)、溶解性活性磷(SRP)和溶解性有机磷(DOP)的质量浓度,分析其沉积物间隙水磷的垂向变化特征,探讨水生植物对沉积物间隙水磷形态特征的影响及控制效果,结果表明:1水生植物对滇池不同湖区沉积物间隙水各形态磷的质量浓度影响显著,但因分布站点不同、深度层次变化所呈现的规律也各不相同;2水生植物显著降低了沉积物间隙水DOP的贡献率,有植物区域DOP平均贡献为32.87%,无植物区域则平均贡献为57.68%;3水生植物抑制了沉积物无机磷的释放,促进了DOP的转化.有植物区域SRP沉积物-水界面扩散通量比无植物区域平均降低39.99%;4水生植物生长对沉积物间隙水各形态磷的浓度削减比较明显,尤其是DOP,削减率达到了38.02%~85.49%.因此分析水生植物对沉积物间隙水DOP贡献率及削减率,对深入理解水生植物与间隙水DOP之间的关系及沉积物有机磷的矿化降解具有重要意义.     

海河干流表层沉积物总磷、总铁和有机质的含量及相关性分析

采用深水表层沉积物采样器采集海河干流8个断面的表层沉积物,测定不同粒径表层沉积物的总磷(TP)、总铁(TFe)和有机质(OM)含量,并采用多元线性回归分析方法对TP与TFe和OM含量进行相关性分析.结果表明:海河干流表层沉积物的颗粒组成除光华桥断面分布较均匀外,其余各断面主要以砂粒(>54%)为主;沉积物的TP含量为29.00～78.99 μmol/g,TFe含量为595.67～719.91 μmol/g,w(OM)为3.77%～8.79%;同一断面不同粉砂粒之间的TP,TFe和OM含量没有显著性差异(P>0.05),而不同断面之间的差异十分显著(P<0.01).TP与OM和TFe的相关分析结果显示:除金刚桥、外环河桥与中心桥外,其余断面的TP与TFe和OM均具有良好的相关性(R2>0.85).      

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.