核磁共振技术在沉积物磷素组分及迁移转化规律研究中的应用

沉积物磷素释放是造成湖泊水体发生富营养化的主要原因之一,而磷的活性又取决于其在沉积物中的化学赋存形态.磷-31核磁共振(31PNMR)技术因可以增强研究者对环境中磷素组分信息的认识而广受关注.本文主要综述了该技术在沉积物磷素形态表征以及迁移转化规律方面的研究成果,对技术原理和分类、分析流程以及具体应用领域进行了全面阐述.目前,应用核磁共振技术分析沉积物磷素的研究主要集中于不同形态磷化合物表征、微生物对磷素迁移转化的影响和定量研究三方面,而关于提取剂和提取方法的研究也是热点之一.最后,对未来31PNMR技术在环境样品中应用研究的重点和发展趋势进行了展望.     

富营养化湖泊沉积物磷原位控制技术

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水体的富营养化及其治理

简要介绍了富营养化的概念和我国目前天然表面水体富营养化的严重情况。重点介绍了利用活性污泥系统去除水中氮特别是磷的一种方法。     

富营养化湖泊沉积物磷原位控制技术简

正湖泊沉积物是指湖泊中沉积的物质,湖泊中大量营养盐富集在沉积物中。水体中各形态的磷通过污水排入、地表径流及水生生物残骸等多种途径输入至湖泊,在温度、上覆水pH、溶解氧及氧化还原电位等环境因素的影响下,经过一系列变化,其中水体中的部分磷在沉积物吸附、化学絮凝、共沉淀等作用下蓄存于湖泊沉积物中,     

苦草生长对沉积物中磷迁移转化的影响

构建了不同营养盐负荷的沉积物环境"水-苦草-沉积物"生态系统,监测分析了沉积物中总磷(TP)、生物可获得磷及其环境因子的垂直分布及变化,以苦草为例,研究了沉水植物生长对沉积物中磷迁移转化的影响,结果表明:生长期的苦草通过改变沉积物环境因子或自身的生理活动,直接或间接地对沉积物中不同形态磷的迁移转化产生了影响,并随着深度的增加而出现不同的变化。具体表现在,低(L)、中(M)、高(H)营养负荷的沉积物总磷(TP),相对于初始值均有不同程度的下降,但苦草组下降的幅度大,分别比对照组多下降了11.63、18.50和46.25 mg/kg;在垂直方向上均表现出随深度的增加TP呈减少趋势,苦草对沉积物影响的深度随根系的活动范围变化而变化,根系增长最长(比试验初始增加了9.2 cm)的低营养负荷苦草组(LV),可影响到6 cm以下的沉积物;中营养负荷苦草组(MV)、高营养负荷苦草组(HV)根系增加不明显(分别为2.60和2.10 cm),影响深度主要在6 cm以内;检验发现,苦草组与对照组差异显著(P0.05)。交换态磷(Ex-P)、铝磷(Al-P)随深度增加而升高,苦草组小于对照组;铁磷(Fe-P),随深度的增加而降低,苦草组大于对照组,其中,在L、M、H中,苦草组的Ex-P分别比对照组下降了0.065、0.215和1.483 mg/kg,Al-P分别为1.198、2.040和2.390 mg/kg;LV中苦草的影响深度可达到10 cm的深,而MV、HV中主要集中在6 cm以内;苦草组中的Fe-P分别比对照组高8.135、16.689和8.598 mg/kg,在垂直方向上的变化幅度亦大于对照组。检验发现,L中苦草组Ex-P与对照组有极显著差异(P0.01),M、H苦草组与对照组无显著差异(P0.05);L、M、H中Al-P、FeP苦草组与对照组均无显著差异(P0.05)。     

湘西河流表层沉积物重金属污染特征及其潜在生态毒性风险

花垣河和峒河是湘西地区受到锰矿和铅锌矿生产影响严重的两条河流。通过表层沉积物采样分析了Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量,根据BCR连续提取程序分析沉积物样品中重金属的地球化学赋存形态,采用内梅罗指数法和地积累指数法评价了沉积物重金属污染特征,根据重金属的富集程度探讨了重金属污染来源,采用淡水生态系统沉积物质量基准(SQGs,TEL/PEL)和毒性单位评价了花垣河和峒河沉积物中重金属元素的生态毒性风险。结果表明,花垣河和峒河绝大多数位点的表层沉积物中Cd、Pb、Cu、Ni、Cr、Zn和Mn的总量高于参照点,形成严重的复合污染,花垣河沉积物中重金属的污染水平明显高于峒河,但沿程变化规律不明显,而峒河沉积物中重金属的沿程变化较有规律,即上游含量低,中下游含量较高。两条河流表层沉积物中富集程度居前列的均为Cd、Pb、Zn和Mn。花垣河和峒河沉积物重金属污染主要来源于矿业生产所产生废渣和废水的点排放。在花垣河和峒河的大多数位点,Cd、Pb和Mn的形态具有共同特征,其生物可利用态均较大程度地超过生物不可利用态,而且Mn和Cd的生物可直接利用态所占比例远高于其它重金属,而Cu和Cr的生物可直接利用态所占比例很低。花垣河沉积物中Cd、Pb和Zn在所有位点极大地超过PEL,在峒河中下游,Cd、Pb、Ni和Zn超过PEL,具有较大的潜在生物毒性。除上游S1位点外,花垣河的其余各位点都具有明显的急性毒性,峒河中下游各位点具有明显的急性毒性,这些河段需要重点治理。     

南太湖浮游植物特征及其富营养化评价

2008年8-9月对南太湖的浮游植物进行了调查,并对9个采样点水样进行了分析.结果表明:共有浮游植物47种,隶属于7门28属,其中蓝藻门 6属9种,绿藻门10属13种,硅藻门7属18种,裸藻门2属3种,隐藻门 1属2种,金藻门1种,甲藻门1种;南太湖浮游植物的密度为3.56×10~6～7.99×10~6 cells·L~(-1);浮游植物的Shannon-Weaver多样性指数为0.29～2.27,均匀度指数在多数位点<0.5,卡尔森营养状态指数(TSIM)均大于64;根据浮游植物的优势种组成、密度、多样性指数及富营养状态指数的评价结果说明南太湖处于富营养化阶段.

Abstract：

In August-September 2008, an investigation was made on the phytoplankton in south-ern Taihu Lake, and the water quality at nine sampling sites was analyzed. A total of 47 phyto-plankton species belonging to 28 genera and 7 phylums were collected, with 9 species of Cyano-phyta, 13 species of Chlorophyta, 18 species of Diatoms, 3 species of Euglenophyta, 2 species of Cryptophyta, 1 specie of Chrysophyta, and 1 specie of Dinophyta. The phytoplankton density was 3.56×10~6-7.99×10~6 cells·L~(-1), Shannon-Weaver index was 0. 29-2. 77, evenness was low-er than 0. 5, and trophic state index (TSIM) was higher than 64. Based on the evaluation of the dominant species composition, density, and Shannon-Weaver index of phytoplankton, and of the TSIM, the southern Taihu Lake was considered at the stage of eutrophication.     

人工湿地脱除富营养化水体氮磷的研究进展

水体中氮磷营养物质不断积累,部分藻类及水生生物的过度繁殖,导致了水体的富营养化。水体富营养化防治的关键是减小水中氮、磷的含量。人工湿地是一项新型的废水处理技术,近年来在脱除富营养化水体氮磷中获得广泛研究和应用。本文在简述脱氮除磷机理的基础上,较系统地阐述了影响人工湿地脱除氮磷的因素及工艺的在改善水体富营养化的研究进展,以便在构建人工湿地中对各项因素综合考虑及兼顾利用,提高人工湿地修复富营养化水体的综合效能。     

滇池、红枫湖沉积物中总磷、分态磷及生物硅形态与分布特征

通过对不同富营养化程度的湖泊（滇池及红枫湖）沉积柱剖面进行不同形态磷以及生物硅含量分析,对比了磷及生物硅的沉积分布特征,并探讨了其与湖泊富营养化演化的关系。结果表明：滇池沉积物中碎屑磷和有机磷在总磷中占50.5%～80.8%,是影响总磷趋势的主要原因;红枫湖中有机磷对总磷的贡献较大,占总磷的53%～60.9%;且两湖各形态磷均随深度的增加而减少;两湖总磷、有机磷、铝磷以及滇池沉积柱中的碎屑磷等的快速增长,表明其主要来源于人为污染;生物硅含量呈现从下层沉积物向上逐渐增加,在上层沉积物中逐渐减少的趋势;总磷、有机磷、铁结合态磷、铝结合态磷、弱结合态磷以及生物硅都能较好地反映富营养化污染的演变和现状。     

富营养化水体沉积物中磷的释放及其影响因素

综述了富营养化水体沉积物中磷的化学形态、释放规律及其影响因素。化学形态分为水溶性磷、铝磷、铁磷、钙磷、还原态可溶性磷、闭蓄磷、有机磷等 7种 ,其分布取决于各形态磷的性质。磷释放受 7种因素影响 ,厌氧、高 pH或低 pH值、高温、扰动、生物活动、底泥与水体含磷量的浓度差值以及钙质沉积物组分等因素均能促进沉积物中磷的释放。     

Phosphorus eutrophication in the SW Frisian lake district 2. Phosphorus balances and simulation of reduction scenarios

The lakes and interconnecting canals in the S.W. Frisian lake district are highly eutrophic. In the mid-1980's a project on eutrophication and lake restoration research was started. This project was aimed at modelling water transport and phosphorus (P) dynamics and at simulating management scenarios. A simple dynamic P-balance model was used to calculate total phosphorus (TP) balances and to simulate three TP reduction scenarios in each of three lakes: Tjeukemeer, Groote Brekken and Slotermeer. The model covered three periods in 1985, 1986 and 1987. The external loads to Tjeukemeer were highest, moderate to Groote Brekken, and lowest to Slotermeer. The major P sources in the area were discharges from the surrounding polders, used mainly for agriculture, and from IJsselmeer.Despite a 75% TP-reduction in water from the surrounding polders the 0.07 mg l^–1 target level could be reached only occasionally in Tjeukemeer, while in the other two lakes this level was not even approached. The effect of a 75% reduction in water from IJsselmeer was greatest in Groote Brekken (but again approached the target only occasionally), moderate in Tjeukemeer and least in Slotermeer. The simulations showed that only a 75% reduction in both external loads (from polders and from IJsselmeer) will lead to achieving the target level in Tjeukemeer and Groote Brekken during the summer periods. In Slotermeer, a relatively isolated lake, other measures are necessary to reach the target level. The results are confirmed by an approximate theoretical analysis of the effects of load reduction.     

Assessment of ecological status in U.K. rivers using diatoms

1. The European Union's Water Framework Directive requires all water bodies to achieve ‘good ecological status’ by 2015 and this paper describes a rationale for defining ‘good ecological status’ based on diatoms, a significant component of the biological quality element ‘macrophyte and phytobenthos’. 2. A database of benthic diatom samples collected over the past 20 years was assembled. New sampling, specifically for this project, was undertaken during 2004 to supplement these data. In total 1051 samples were included in the database with matching environmental data. 3. ‘Reference sites’, relatively unimpacted by human activity, were selected from this database by a series of screening steps and these sites were used to develop a site‐specific reference typology. 4. Environmental variables not related to the pressure gradient were used to predict the ‘expected’ Trophic Diatom Index (TDI) values at each site. Site‐specific TDI predictions were used to generate ecological quality ratios (EQRs) ranging from ≥1, where the diatom assemblage showed no impact, to (theoretically) 0, when the diatom assemblage was indicative of major anthropogenic activities. 5. The boundary between ‘high’ and ‘good’ status was defined as the 25th percentile of EQRs of all reference sites. The boundary between ‘good’ and ‘moderate’ status was set at the point at which nutrient‐sensitive and nutrient‐tolerant taxa were present in equal relative abundance. An ecological rationale for this threshold is outlined in the paper.     

The Trophic Diatom Index: a new index for monitoring eutrophication in rivers

A index for monitoring the trophic status of rivers based on diatom composition (‚trophic diatom index’, TDI) has been developed, in response to the National Rivers Authority (England & Wales)'s needs under the terms of the Urban Wastewater Treatment Directive of the European Community. The index is based on a suite of 86 taxa selected both for their indicator value and ease of identification. When tested on a dataset from 70 sites free of significant organic pollution, this index was more highly correlated with aqueous P concentrations than previous diatom indices. However, where there was heavy organic pollution, it was difficult to separate the effects of eutrophication from other effects. For this reason, the value of TDI is supplemented by an indication of the proportion of the sample that is composed of taxa tolerant to organic pollution. The index was tested on the R. Browney, N-E. England, above and below a major sewage discharge. TDI values indicated that the effect of inorganic nutrients on the river downstream of the discharge was slight as the river was already nutrient-rich, but there was a large increase in the proportion of organic pollution-tolerant taxa. This indicates that the river was already so eutrophic upstream of the discharge that tertiary treatment to remove P would not be effective unless other aspects of the discharge were also improved.     

Biological monitoring of eutrophication in rivers

There is an increasing awareness of the need to assess the impact of nutrient enrichment on river ecosystems separately from the impacts of organic effluents. A range of methods have been proposed and some have moved from the development stage to practical use by water management organizations. The methods can be applied to broad surveys or provide baseline information to assess possible future change. In the latter case it is recommended that several different methods are used, especially where it is important to get reliable information on the long-term impact of improvements in effluent quality. Estimates of biomass measured as chlorophyll a have often been used for phytoplankton and sometimes also for benthic communities. However, a lot of care is needed in applying this method, because of the range of factors besides nutrient concentration which can influence values. Approaches based on the whole community have been developed by a number of research groups, usually involving semiquantitative estimates of abundance. There has also been a rapid increase in the use of indices based on the relative proportions of epilithic diatom species. The methodologies used by a number of research groups in Europe are broadly similar, making it possible to compare results between different regions. The development of indices based on macrophyte floristic composition in relation to river nutrient status is also under development, especially in France and UK. However, interpretation of the results is complicated where long-term changes are taking place in nutrient concentrations in the water, because of the varying contributions of sediment and water to different species of rooted plant. Bioassays can be especially helpful where it is desired to establish whether either N or P is limiting for a population of community.     

The phosphorus status of sediments in a hypertrophic impoundment (Hartbeespoort Dam): implications for eutrophication management

The phosphorus status and distribution of sediments in a hypertrophic water supply reservoir (Hartbeespoort Dam) were investigated, with a view to assessing the role of sediments in counteracting the effects of reduced external phosphorus loading as a restoration measure. In comparison with similar water bodies in South Africa, the sediments in Hartbeespoort Dam contained high levels of both total and potentially mobile phosphorus. The potentially mobile fraction constituted about 60% of the total phosphorus content of the sediments, compared with about 11% in other reservoirs. The excessive eutrophication of Hartbeespoort Dam is clearly reflected in the phosphorus status of the sediments. Sediment distribution in the impoundment was found to be extremely heterogeneous, due to the combined influences of morphometry, hydrology and an imbalance in the nutrient loads entering via rivers at remote points in the water body. It is concluded that sufficient mobile phosphorus has accumulated in the sediments to prolong the response time of the impoundment to phosphorus load reductions. Since phosphorus release from sediments is dependent on dynamic processes not addressed in this study, the extent of the delays in trophic response to load reduction cannot be estimated.     

Long-term (30 years) dynamics of Chironomidae (Diptera) fauna in the Kuibyshev water reservoir associated with eutrophication processes

Benthos investigations were carried out in the channel and flood-plain of the Kuibyshev water reservoir during 1958–1985. Hydrobiological monitoring data obtained at 12–16 stations in all Deeps excluding littoral areas are discussed. In 1987–1900 benthofauna distribution was also studied at the Priplotinny Deep. An increase of the reservoir trophic state is reported. The observed trend was an increase of the total benthos biomass. Changes in both species and trophic structure of the chironomid community due to the eutrophication problem are discussed.     

Phosphorus eutrophication research in the lake district of south western Friesland,The Netherlands. Preliminary results of abiotic studies

The water quality of the lakes in south western Friesland is influenced by a rather complex hydrology. The purpose of the abiotic part of the eutrophication project, started in 1984 and focused on phosphorus, is to model hydrology and phosphorus dynamics, in order to compare scenarios for policy and management.A brief survey is given of the preliminary results of the abiotic studies: hydrology, water quality, external loading from surrounding polders, sedimentary phosphorus and internal loading. The two largest lakes, Tjeukemeer and Slotermeer, are compared regarding these processes.     

Phosphorus eutrophication in the SW Frisian lake district 1. Monitoring and assessment of a dynamic mass balance model

In 1984 a frequent monitoring programme was started in the hypertrophic S.W. Frisian lake district, with emphasis on total phosphorus (TP) and chloride (Cl^–). The main objectives of the project were: to quantify the phosphorus flows, to gain insight in the process of eutrophication, and to simulate management scenarios. The seasonal variability in the lakes is due mainly to the man-made hydrology: reception of humic-rich polder water in wet periods (winter) and inlet of chloride-rich Usselmeer water in dry periods (summer). The yearly means of TP concentrations in the lakes (Tjeukemeer, Groote Brekken and Slotermeer) ranged from 0.23 to 0.29 mg l^–1. However, much higher concentrations (0.9 mg l^–1) were found in periods with high inflow of polder water.The simulations with a mass balance showed an acceptable similarity between measured and simulated concentrations of TP as well as of Cl^–. Chloride was modelled to verify the accuracy of a hydrodynamic model. A sensitivity analysis of the apparent settling rate in the P model showed that sensitivity was lowest in simulations of Groote Brekken and highest in simulations of Slotermeer, the difference being attributable to the influence of the water residence time. The model was found to be appropriate for simulating management scenarios.     

Erosion,phosphorus and phytoplankton response in rivers of South-Eastern Norway

The development of P fractions and phytoplankton was studied in three rivers with varying concentrations of seston.Less than 1% of the yearly TP transport may take place during periods with high algal biomass.The observation of a high growth rate of phytoplankton in the rivers coinciding with high concentrations of RP, low content of seston and high TP:Chl a ratio, indicate that the growth was often not P-limiting. During short periods with high phytoplankton biomass the ratio TP:Chl a may be low, indicating that a high fraction of TP was available.The content of P in soil samples and in samples with high seston content was about 0.1% of dry weight, and the algal availability of P often varied between 25 and 75% of TP for both types of samples.Decreasing biomass or low growth rates were observed at secchi depths less than 0.5 m and seston concentrations less than about 25 mg dry weight 1^–1. High flow rate also depressed the development of the total phytoplankton biomass. The assimilation of available P is incomplete under such conditions, i.e. under conditions of light limitation and high dilution rate.The availability of P for phytoplankton in rivers with different length, light conditions and stream velocity is discussed.     

Phosphorus,nitrogen, and carbon cycling by fish populations in two small lowland rivers in Poland

Amounts of C, P, and N consumed by all fish populations were estimated at 9 sites in two small lowland rivers. They mainly depended on fish density and were: 151.8 (27.9–453.3) kgC ha^–1a^–1, 3.1(0.5–8.8) kgP ha^–1 a^–1, and 30.3 (5.3–89.9) kg N ha^–1 a^–1. To build one kg of each of these elements into their body the fish consumed 7.9 ± 1.7 (% MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGak0Jf9crFfpeea0xh9v8qiW7rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGabeiEayaara% aaaa!3912!\[{\text{\bar x}}\] ± S.D.) kg of C, 3.1 ± 0.8 kg of P, and 6.6 ± 1.3 kg of N. Thus, phosphorus was assimilated twice more efficiently than carbon and nitrogen. Pools of the three elements, calculated as mean biomass, are: 12.7 (1.2–42.1) kg C ha^–1, 0.7(0.1–2.2) kgP ha^–1, and 3.0 (0.3–9.7) kgN ha^–1 The elements were assimilated especially effectively by young stages of fish.