近10 a廉州湾富营养化因子变化特征及其与赤潮演变的关系

利用2005~2015年广西廉州湾每年枯水期、丰水期和平水期共32个航次的监测数据,分析了营养盐等富营养化因子的变化特征,用富营养化指数评价该海域富营养化程度的演变,并探讨富营养化因子变化与浮游植物响应的关系。结果表明,近10 a廉州湾的营养盐及COD最高浓度主要出现在丰水期,DIN和PO₄-P枯水期明显高于平水期,SiO₃-Si和COD在枯水期和平水期浓度相近。PO₄-P年际间变化幅度较大并呈较明显上升趋势,SiO₃-Si呈下降趋势,DIN和COD年均变化总体不大。在枯水期PO₄-P、DIN和COD均呈现出上升趋势。径流输入对海湾的DIN和COD变化起主导作用,生活排污、水产养殖对PO₄-P的分布和变化有重要的作用。年均富营养化指数范围为0.10~1.85,富营养化程度主要由DIN、PO₄-P决定。海湾营养盐结构总体处于P限制状态,近10 a N/P和Si/P比例呈显著下降趋势,P限制在一定程度减轻。廉州湾在高DIN和高SiO₃-Si值的条件下,PO₄-P输入量的徒增及其导致营养盐比例的改变是诱发赤潮的最重要环境因素。近年来营养盐输入增加,富营养化程度有所加重,P限制得到一定的缓解,海湾赤潮的生态风险加大。     

近年来渤海湾赤潮监控区营养盐变化及其结构特征分析

根据2004~2006年进行的连续监测结果,分析、探讨了渤海湾赤潮监控区表层海水营养盐的污染现状、变化规律及其结构特征。结果表明:近年来,渤海湾赤潮监控区海域受到了DIP、DIN污染,水体处于严重的富营养化状态,且DIN的污染程度明显高于DIP;除个别项目外,渤海湾赤潮监控区以S4站营养盐含量最高,原因是S4站靠近河口,大量生活污水排放所致;在赤潮多发期,表层海水N、P、Si含量存在明显的月变化特征。6月份营养盐含量最低,8月份最高。年际变化表明:NH4-N的年际变化最为明显,表现为逐年递减的趋势,而SiO3-Si的年际变化最小。赤潮监控区DIN一直处于热力学平衡状态,NO3-N占DIN含量的57%~78%。近年来DIN/PO4-P和SiO3-Si/PO4-P逐年增加,而SiO3-Si/DIN则逐年降低。     

广西钦州湾近岸海域“十一·五”期间营养盐变化趋势分析及污染控制重点

通过2006年-2010年N、P、Si数据分析广西钦州湾海域N、P、Si的变化趋势、富营养化状况以及限制因子。分析表明:钦州外湾DIN、DIP、SiO3-Si含量呈波浪形变化并有所下降,钦州外湾2006年-2010年均为贫营养,外湾海水水质良好。茅尾海DIN值含量较高,海域受到N的影响。茅尾海2006年-2010年为轻度～中度富营养。茅尾海属于磷中等限制富营养,磷酸盐仅表现为相对不足,仍然有爆发赤潮的危险。控制茅尾海富营养化的关键在于控制磷的入海量。     

广西廉州湾水质状况评价

根据1996-2000年5a对廉州湾枯、丰两期水质监测资料，以DIN、DIP、COD和DO作为化学参数，分析了该海湾有机污染和营养类型。结果表明，海域水质呈高N低P状态，水质基本上属于中度污染，处于富营养化状态。其枯、丰水期水质主要与陆源排污和河流输入有关。     

福宁湾活性磷酸盐和无机氮的时空变化特征

根据2002至2003年福宁湾海域的监测资料,研究该海域PO4-P、DIN的时空变化特征、营养程度现状以及本海域的营养盐限制因子.研究表明：PO4-P、DIN含量均呈冬季最高、夏季最低;福宁湾海域季度平均E值为1.48,水体已呈现富营养化状态;N/P〉16并不是福宁湾海域爆发赤潮的必要条件;福宁湾海域N/P值长期保持较高,秋、冬季N/P值较为稳定;PO4-P为福宁湾海域浮游植物生长营养盐限制因子.     

球形棕囊藻(Phaeocystis globosa Scherffel)赤潮成因分析

对1997年冬季和1999年夏季发生于广东省饶平枯林湾海域的棕囊藻赤进行了现场调查和监测，结果表明，棕囊藻赤潮的爆发是海洋环境变化和棕囊藻自身特性共同决定的，长期集约化养殖引起枯林湾海域的N、P、Fe、Mn浓度较高，特别是Fe浓度明显高于广东沿海的其它海区，为赤潮的爆发提供了物质基础，棕囊藻增殖过程中对DIN（可溶性无机氮）的需求量较高，特别对NO3^－-N有明显的主动吸收，与DIP（可溶性无机氮）相比，海水DIN浓度恢复速率较慢。可能成为限制棕囊藻赤潮的规模和持续时间的关键因子，海水温度的异常增高及降雨量偏少，与棕囊藻赤潮的发生紧密相关。     

2000—2012年深圳湾及邻近沿岸水域溶解无机磷的来源和时空分布

依据2000—2012年每月1次的调查资料,简要描述和讨论了深圳湾及邻近沿岸水域中溶解无机磷(DIP)质量浓度的时空分布,并结合盐度(S)和溶解无机氮实测数据探讨DIP的来源和氮:磷(N∶P)原子比.结果表明,深圳湾和珠江口东南沿岸中DIP质量浓度分别为(0.184±0.167)mg·L-1和(0.025±0.013)mg·L-1.在深圳湾,由于受到周边陆源排放的影响,DIP质量浓度在丰水期较低,枯水期较高.在珠江口东南沿岸,由于受到多个环境因子的制约,DIP质量浓度在夏秋季较高,冬春季较低.2000—2012年珠江口东南沿岸DIP质量浓度的年际变化趋势基本上保持平稳;深圳湾DIP质量浓度在2000—2004年呈上升趋势,从0.173 mg·L-1上升至0.236 mg·L-1,2005—2012年则呈下降趋势,从0.221mg·L-1下降至0.120 mg·L-1;2000—2012年深圳湾和珠江口东南沿岸N∶P原子比的年际变化均呈上升趋势,分别从31.8和41.5上升至44.9和60.1.研究海区中的DIP具有"保守性",主要来自陆源排放.依二元混合质量平衡模式估算的珠江口东南沿岸DIP的陆源质量分数约为63.0%,而深圳湾的都87%.研究海区中N∶P原子比高达48.3±36.9,暗示磷是初级生产的潜在限制因子.     

近5a来深圳大鹏湾南澳赤潮监控区营养盐变化及其结构特征

根据2004～2008年每年3～11月份深圳大鹏湾南澳赤潮监控区表层海水营养盐的监测基础资料,对监控区水域营养盐变化及其结构特征进行了分析评价。结果表明:近5 a监控区Si、N、P营养盐的空间波动程度存在明显年际差异,营养盐含量受监控区藻类等浮游植物的生命活动和陆源径流以及鱼、贝类新陈代谢强弱的共同影响。5 a来NO2-N、NH4-N和SiO3-Si的含量呈波动性升高,PO4-P含量保持稳定,NO3-N含量有所降低,Si∶P值上升比较明显,而N∶P和Si∶N值波动较大。2004～2005年监控区无机氮主要存在形式是NO3-N,2006～2008年主要存在形式为NH4-N。P一直是该海域初级生产力的主要潜在限制性因子。5 a来监控区海水符合养殖功能区的水质标准要求,未受到PO4-P和DIN营养盐的污染,处于贫营养状态。     

钦州湾近20 a来水环境指标的变化趋势Ⅴ. 浮游植物生物量的分布及其影响因素

利用钦州湾20 a(1983～2003年)来10个航次的调查分析资料,分析了该湾浮游植物的分布变化及其与环境因子之间的关系.结果表明:该湾在开发初、中期,浮游植物生物量呈明显上升趋势,相应的营养盐除N明显上升外,均下降显著;在开发盛期,以Chl.a表征的浮游植物生物量则呈明显下降趋势,相应的营养盐仍以N明显上升的趋势出现,而P和Si则保持了相对稳定状态.相关分析显示,开发初期,浮游植物突出了与直接消费者-浮游动物的显著正相关关系;开发中期,浮游植物与环境因子的相关几率明显增加,尤以秋季最好;在开发盛期前期,Chl.a只与COD呈显著的负相关关系,而在中期,无论秋季还是冬季,Chl.a与环境因子的关系均较密切,多在95%置信水平上.这种相关特性的出现,代表了不同时期海湾的水环境特征.     

钦州湾近20a来水环境指标的变化趋势 Ⅵ溶解氧的含量变化及其在生态环境可持续发展中的作用

通过对钦州湾1983～2003年10个航次调查资料的分析,探讨了该湾溶解氧的含量变化及其在生态环境可持续发展中的作用.结果表明:20a来该湾水体中的DO含量变化并不大,所有航次均在一类海水标准范围内,以冬季最高、春季次之、夏秋季较低的特征出现;O2%的变化与DO相一致.但由于浮游植物在海湾生态环境的演变过程中扮演了正、反两方面的角色,从而使DO与环境因子之间的关系趋于复杂,作为温盐函数的DO,与水温之间却多以显著正相关出现,与盐度则多以显著负相关出现,与pH、COD、浮游植物(或chl.a)和N、P、Si的相关性,却体现了时代变迁的特征;O2%的相关变化与DO不尽一致.但总的说来,浮游植物的增氧作用在海湾生态环境可持续发展的进程中起到了主导影响作用.     

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.     

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.