水环境中氮磷形态分析方法研究进展

归纳总结了近年来国内外水环境中氮、磷形态分析方法的研究新进展,并着重介绍了氮、磷在水环境中赋存形态的分类、分析测定方法,这对于深入揭示水环境中氮、磷的赋存形态及研究环境与生物地球化学循环有着重要的指导意义。     

长江悬浮颗粒物中磷的赋存形态

2006年9~10月在长江采集悬浮颗粒物样品,应用改进后的SEDEX法对磷的赋存形态进行了分析.结果表明,自生磷灰石磷是长江悬浮颗粒物中磷的主要赋存形态.涪陵至万州江段,碎屑磷灰石磷的含量较高,弱吸附态磷和有机磷含量较低,磷的赋存形态主要受悬浮颗粒物含量的影响;香溪至葛洲坝下江段,弱吸附态磷和有机磷含量较高,碎屑磷灰石磷含量较低,磷的赋存形态主要受浮游植物生长及泥沙粒径的影响;城陵矶至大通江段,有机磷、碎屑磷灰石磷和铁结合态磷含量较高,弱吸附态磷含量较低,磷的赋存形态主要受泥沙粒径和洞庭湖输入的影响.长江悬浮颗粒物中生物可利用磷占颗粒态磷的45.6%,长江上游水体中生物可利用磷含量较低,下游含量较高.     

化学物相分析法测定瓮福磷尾矿中钙镁磷元素形态含量

用化学物相分析法测定瓮福磷尾矿中钙、镁、磷元素形态含量。结果表明,磷尾矿中钙主要以白云石的形式赋存,并有少量以方解石、磷酸盐形式存在;镁主要以白云石的形式赋存,并有少量以磷酸盐、硅酸盐形式存在;磷主要以磷灰石的形式赋存,并有少量以铁氧化物、独居石、磷钇矿形式存在。各元素形态加标回收率为97.6%~107.2%,相对标准偏差(RSD,n=12)为0.77%~4.85%。各元素形态分析结果表现出较好的稳定性,表明采用化学物相分析法测定瓮福磷尾矿中钙、镁、磷元素形态含量结果准确可靠。     

沱江沉积物-水界面磷形态垂向分布及时空变化特征

水体中富营养化水平与磷元素的赋存形态密切相关。目前围绕引起富营养化关键因子之一的磷形态的垂向分布特征、各磷形态间的迁移转化行为及其影响因素取得了比较明确的研究进展。为进一步揭示不同磷形态在沉积物-水体系中迁移转化行为随时空的变化特征,本文采用磷钼蓝分光光度法对沱江流域简阳段间隙水中可溶性活性磷(SRP)、可溶性非活性磷(SUP)及总溶解性磷(TDP)进行测定;采用SMT法和改进的沉积物无机磷形态连续提取法对沉积物中总无机磷(TIP)、总磷(TP)、难提取磷(Res-P)、可交换态磷(Exc-P)、铁结合态磷(Fe-P)、铝结合态磷(Al-P)、钙结合态磷(Ca-P)进行提取,磷钼蓝分光光度法进行测定,以揭示沉积物-水体系中磷的赋存形态垂向分布行为特征,并将实验数据与十年前该地区磷的赋存形态结果进行对比,探讨磷赋存形态的变化趋势及影响因素。结果表明:间隙水中SRP、SUP和TDP的含量分别为0.004～0.36mg/L、0.080～3.19mg/L和0.056～3.28mg/L;沉积物中TP、TIP、Res-P、Exc-P、Al-P、Ca-P含量分别为1235.40～1646.94mg/kg、860.00～1318.59mg/kg、130.31～537.13mg/kg、1.35～14.10mg/kg、0.007～0.12mg/kg、743.13～1109.91mg/kg,Fe-P未检出。对比十年前后沉积物-水体系中磷赋存形态的变化可知,由于受到外源磷输入的影响,间隙水中SRP、SUP以及TDP含量虽然在-10cm以上变化不明显,但在-10cm以下明显增大,且导致沉积物中TP、TIP含量增加;偏碱性的沉积环境导致Al-P的释放,其含量明显减小;Exc-P含量的减小与其转化为稳定的Ca-P或Res-P形态有关。研究认为:随着时空的变化,沱江简阳段沉积物呈现外源磷输入和内源磷释放的综合污染。总体而言,由于输入的磷形态大部分以稳定的Ca-P和Res-P形态存在于沉积物中,使得表层间隙水中生物可直接利用的磷含量总体变化不大,该地区富营养化程度不会加重。维持沉积环境的弱碱性,有利于Al-P、Exc-P等向Ca-P的有效转换,抑制河流富营养化。     

云南安宁磷矿区水系沉积物磷赋存形态及分布特征

磷污染是水污染的重要组成部分,因其可造成水体富营养化、水质下降,从而引起人们的广泛关注。研究沉积物中不同磷赋存形态及其分布特征有助于了解沉积物中磷的行为特征及迁移能力,从而为水体富营养化防治提供支撑。磷矿的开采、冶炼对矿区内水资源环境可能产生严重影响,本文以安宁磷矿区内河流、水库为研究区域,分析了不同水系沉积物磷元素赋存形态及分布特征,并对其生态风险进行评估。采用X射线荧光光谱法测定研究区水系沉积物总磷(TP)含量,并基于顺序提取及Hupfer改进的磷形态分析方法,将研究区各水系沉积物中磷分为弱吸附态磷(NH₄Cl-P)、可还原态磷(BD-P)、金属氧化物结合态磷(NaOH-P)、钙结合态磷(Ca-P)、残渣态磷(Res-P)等5种形态,采用单因子污染指数法对其进行生态风险评估。结果表明：研究区水系沉积物样品中TP含量范围为567.6～48115.5mg/kg,NH4Cl-P含量范围为0.07～115.2mg/kg,BD-P含量范围为8.84～802.5mg/kg,NaOH-P含量范围为21.3～3129.5mg/kg, Ca-P含量范围为12～45098mg/k...     

钙、铁、铝形态对岩溶石灰土磷有效性的影响

为揭示钙、铁、铝形态与岩溶地区土壤磷有效性关系,通过改进的BCR元素形态连续提取法获取石灰土不同发育阶段土壤矿质元素赋存形态,并分析与总磷及速效磷含量之间的相关关系。初步研究表明:石灰土壤中全磷和速效磷在石灰土发育过程呈降低趋势,从黑色石灰土到黄色石灰土,总磷降低了76.7%,速效磷减少了84.7%。石灰土总磷与速效磷同酸溶态、可还原态及残渣态钙,可氧化态铁、铝和可还原态铝显著正相关,而同总铁、总铝以及残渣态铝显著负相关,相关系数绝对值均达到0.9以上。随着石灰土发育进行,钙总量及其形态均降低,而铝、铁总量和形态呈增加趋势,可能导致岩溶地区石灰土磷及其有效性缺乏越发突出。      

化学连续提取法对太湖沉积物中磷的各种形态测定

为确定太湖沉积物中磷的各种形态含量,本文应用SMT 连续提取法对太湖梅梁湾表层沉积物样品和淡水沉积物标准物质BCＲ --684 中磷的各种形态进行测定。结果表明SMT 法具有一定的适用性和准确性。太湖沉积物中磷形态测定结果表明无机磷是太湖沉积物中磷的主要赋存形态,占总有效磷的 59. 22%,无机磷含量中非磷灰石态磷含量为139 μg /g,大于磷灰石态磷含量113 μg /g。     

华北平原与大同盆地原生高碘地下水赋存主控因素的异同

原生高碘地下水在我国有广泛分布,为查明不同区域地下水碘赋存机理的异同,通过选取我国大同盆地以及华北平原为代表性区域,完成区域地下水样品系统性采集及水化学、碘形态测试工作,对区域地下水水环境及其演化特征完成详细刻画.结果表明:大同盆地地下水总碘含量为2.86~1 286 μg/L,华北平原地下水总碘含量为2.40~1 106 μg/L,分别约有50.0%及49.5%地下水碘含量超过（GB19380- 2016）《水源性高碘地区和高碘病区的划定》中界定的100 μg/L国家标准.地下水水环境特征表明,在大同盆地,第四纪河湖相沉积所形成的,富含有机质、偏碱性、还原性、Na-HCO₃型水环境,利于赋存于固相介质上的碘以碘离子的形式进入地下水中,沿地下水流向,富集于盆地中心排泄区;在华北平原,由第四纪6次海侵形成的冲湖积、海积松散沉积物中富含Na、Cl、I等元素,其偏碱性、还原性、Na-Cl型水环境及低水力坡度的平缓地形利于赋存在固相介质上的碘以碘离子的形式进入地下水,沿地下水流向富集于沿海排泄区.控制两个地区高碘地下水形成的相同因素是偏碱性及偏还原的地下水环境,且该环境下碘的主要赋存形态均为碘离子,但大同盆地高碘地下水形成主要受富有机质环境影响,而华北平原高碘地下水形成的主要受富碘的海相沉积控制.      

沉积物中磷的赋存形态及磷形态顺序提取分析方法

阐述了当前我国水体富营养化的现状,水体的富营养化与水体中磷、氮的浓度以及二者的浓度比值有着密切的关系。水体富营养化时氮和磷的浓度均很高,但没有一个固定的值,是在一个较宽泛的富营养范围内,氮和磷的浓度比值大多在10∶1～20∶1。湖泊沉积物作为湖泊水体中磷的重要蓄积库,是湖泊流域磷循环的重要归属,也是湖泊水体内源性磷的主要来源,沉积物中极少量的稳定磷转化为活性磷就会造成湖泊水体富营养化。文中介绍了沉积物中无机磷形态的分类,评述了欧盟标准局在研制湖泊沉积物磷形态标准物质时比对采用的4种提取方法(Willimas法、Hieltjes-Lijklema法、Ruttenberg法、Golterman法),总结了国内外学者所应用的沉积物中磷的各种形态提取方法和磷各形态的分析测定方法,国内学者应用的方法是在国外学者方法的基础上提出的,阐述了顺序提取方法及其地球化学意义。简要评述了湖泊沉积物中磷的生物释放、物理释放和化学释放三种释放机制,这三种释放机制相辅相成,在一特定的环境条件下某一过程可能占主导地位来控制沉积物磷的释放。最后提出应该加强对沉积物中磷的各种形态的专属提取剂及其提取有效性的分子表征和检测,更加细化对于沉积物中磷形态的分类和创新各种磷形态的分析方法,建立沉积物-水体磷的迁移、循环和转化模型,这对于从根本上解决富营养化问题具有重要意义。     

土地利用方式下岩溶湿地土壤无机磷形态特征及分析方法适用性探讨

本研究利用SMT法和七步连续提取法对桂林市会仙岩溶湿地中典型土地利用方式（水稻田、果园、荒地）的土壤以及河流底泥中磷的赋存形态进行研究。结果表明:岩溶土壤总磷含量大小为底泥＞果园＞水稻田＞荒地;底泥中Ex-P和Fe-P所占比例较大;荒地土壤中Or-P和Res-P为主要磷形态;水稻田和果园土壤中Fe-P所占比例较高。人为干扰明显的果园表层土壤有较大的磷淋溶风险;荒地土壤中磷的生物可利用性低,体现了其缓冲固持湿地水体中磷的生态功能。大量可溶性磷经淋溶迁移富集于底泥中,是河流富营养化的风险源。七步法表现出在提取多种复杂结合态磷上的优势,对岩溶土壤中Ca-P的提取更充分有效,更适用于研究岩溶土壤不同形态的磷分布特征。      

Pb、Zn、Cd和Cr等元素的生物有效性研究——以胶州湾水生系统为例

本文首先利用同站位多介质同采的资料分析研究了各环境介质中的不同痕量金属对生物富集的贡献,提出孔隙水中Pb、Zn、Cd、Cr对生物体中同名组分富集的贡献较大;进而采用PHREEQC软件模拟了孔隙水中Pb、Zn、Cd、Cr四种元素的组分存在形态,结果表明:PbCO3、Zn2 、CdCl2、Cr(OH)3分别为孔隙水中Pb、Zn、Cd、Cr的优势态,但其生物有效形态依次为PbSO4、ZnOHCl、CdCl 、Cr(OH)2 。最后作者提出生物对其所处环境介质中痕量金属的富集并不取决于痕量金属的总量或其相应的优势态浓度的多寡,而是取决于痕量金属的生物有效态的浓度大小。     

Speciation Analysis for Iodine in Groundwater Using High Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS)

Methods based on high performance liquid chromatography coupled with inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) for iodine speciation analysis are described. Experiments were performed relating to iodine species, preservative medium and time. The concentration and pH of the buffer are also discussed in relation to separation efficiency. The developed methods allowed the fast and sensitive determination of iodine species with detection limits of 0.025 μg l⁻¹ (as 1) for both iodide and iodate with < 5% relative standard deviation (RSD) for 50 nmol l⁻¹. Attempts were made to quantify total organo-iodine by size-exclusion chromatography (SEC). By way of example, a number of groundwater samples were analysed by these methods, revealing that iodide is the main iodine species in the sampled waters, but that high concentrations of organo-iodine compounds were observed in some samples as well. In summary, the total concentration and the dominant species of iodine in aquatic freshwater environments is easily and accurately measured using this new method.     

Nutrient contents in bottom sediment samples from a southern Brazilian microbasin

The nutrients, carbon, nitrogen and phosphorus, significantly affect the quality of aquatic environments, especially when present at concentrations above natural levels. In this context, the sedimentary column can act as an environment for storage or accumulation of these nutrients and for the reprocessing of such substances in the water column and aquatic biota. In this context, this study aimed to estimate the concentration of total organic carbon (TOC), total nitrogen (TN), total phosphorus (TP), inorganic phosphorus (IP) and organic phosphorus (OP) in seven sediment samples that were collected from the Marrecas Stream microbasin (Caxias do Sul, Rio Grande do Sul State, Brazil). The relationships among the sediment nutrient concentrations and the levels of organic matter (OM), fine material (silt–clay) and the concentration of the metal species, Al, Fe and Mn, as well as the possible nutrient sources to the stream studied were also evaluated. The data set suggest that the TOC and IP appear to have a direct correlation with the vast riparian vegetation present in areas adjacent to the sampling points and to the physico-chemical properties of the water and sedimentary column. Moreover, the results obtained for TN suggest that its concentration possibly suffers interference from the temperature of the water and its oxygenation, in addition to other biological activities. On the other hand, one cannot rule out human interference, mainly in the levels of OP, possibly due to the inflow of domestic sewage to the stream.     

Analytical Electron-Microscopy Fractionation of Fine and Colloidal Particulate-Phosphorus in Riverbed and Suspended Sediments

The impact particulate-phosphorus (particulate-P) has on eutrophication of aquatic systems that greatly depends on its composition. As a result, analysis methods for evaluating particulate-P speciation must be capable of identifying and/or quantifying the wide range of forms particulate-P can take. In the present study, we compare the particulate P speciation of the fine and colloidal fractions of riverbed sediment and suspended matter from two rivers in the Lake Geneva basin (French Alps) as determined with chemical extractions to results of a combined Transmission Electron Microscopy and Energy Dispersive Detection (TEM–EDS) analysis of the same samples. TEM–EDS provides semi-quantitative information about the distribution of P throughout the solid fraction of a sample and on the diversity of carrier phases, which are identified by their morphology and stochiometry. EDS-detectable quantities of phosphorus were found in 15–35% of the particles in the samples analyzed. As expected, particulate-P existed in a wide variety of forms, mostly associated with Al, Fe, Ca and Si. Some types of particles, often well-crystallized phosphate minerals, had high P contents (10–30%), but the dominant carrier phases of P were diffuse matrices of particles with low P contents (<5%). These matrices had a wide range of chemical compositions and included clay minerals, crystallized and amorphous phases of Fe, as well as intermediary components. Classical chemical extractions showed major differences in P content and speciation between the upstream and downstream sediment samples. The downstream samples showed higher frequencies of particles containing P, a larger diversity of carrier phases, a higher contribution of clays as carrier phases of P, and the presence of a new fraction with Al and Fe amorphous minerals. The processes that create and select carrier phases of particulate-P are part of the general dynamics of P within a watershed.     

Identification of the uranium speciation in an underground acid mine drainage environment

The subsurface acid mine drainage (AMD) environment of an abandoned underground uranium mine in Königstein/Saxony/Germany, currently in the process of remediation, is characterized by low pH, high sulfate concentrations and elevated concentrations of heavy metals, in particular uranium. Acid streamers thrive in the mine drainage channels and are heavily coated with iron precipitates. These precipitates are biologically mediated iron precipitates and related to the presence of Fe-oxidizing microorganisms forming copious biofilms in and on the Fe-precipitates. Similar biomineralisations were also observed in stalactite-like dripstones, called snottites, growing on the gallery ceilings.The uranium speciation in these solutions of underground AMD waters flowing in mine galleries as well as dripping from the ceiling and forming stalactite-like dripstones were studied by time resolved laser-induced fluorescence spectroscopy (TRLFS). The fluorescence lifetime of uranium species in both AMD water environments were best described with a mono-exponential decay, indicating the presence of one major species. The detected positions of the emission bands and by comparing it in a fingerprinting procedure with spectra obtained for acid sulfate reference solutions, in particular Fe(III) - SO₄²⁻ - UO₂²⁺ reference solutions, indicated that the uranium speciation in the AMD environment of Königstein is dominated in the pH range of 2.5-3.0 by the highly mobile aquatic uranium sulfate species UO₂SO_4(aq) and formation of uranium precipitates is rather unlikely as is retardation by sorption processes. The presence of iron in the AMD reduces the fluorescence lifetime of the UO₂SO_4(aq) species from 4.3 μs, found in iron-free uranium sulfate reference solutions, to 0.7 μs observed in both AMD waters of Königstein and also in the iron containing uranium sulfate reference solutions.Colloids were not observed in both drainage water and dripping snottite water as photon correlation spectroscopy analyses and centrifugation experiments at different centrifugal accelerations between 500g and 46000g revealed. Thus transport and uranium speciation at the investigated AMD sites is neither influenced by U(IV) or U(VI) eigencolloids nor by uranium adsorbed on colloidal particles.This study shows that TRLFS is a suitable spectroscopic technique to identify the uranium speciation in bulk solutions of AMD environments.     

环境中硒形态分析方法的研究进展

硒的形态研究是了解环境中硒的毒性、生物可利用性、迁移和生物地球化学循环等方面的基础,其研究方法一般分为直接和间接法。本文总结了环境中硒形态的研究方法,特别是对环境样品中常用的硒形态分析技术——连续化学浸提技术作了全面详细的讨论,并综述了其它硒形态分析方法的最新动态。     

Coastal eutrophication and the Danish national aquatic monitoring and assessment program

Nutrient over-enrichment and cultural eutrophication are significant problems in the Danish marine environment. Symptoms of eutrophication include periods of hypoxia and anoxia in bottom waters, death of benthic-dwelling organisms during anoxia, long-term reductions in the depth distribution of macrophyte communities, changes in the species composition of macrophyte communities, and increases in reports of harmful algal blooms. In 1987 the Action Plan on the Aquatic Environment was adopted to combat nutrient pollution of the aquatic environment with the overall goal of reducing nitrogen loads by 50% and point source phosphorus loads by 80%. The Danish Aquatic Nation-wide Monitoring Program was begun in 1988 in order to describe the status of point sources (industry, sewage treatment plants, stormwater outfalls, scattered dwellings, and fish farms), ground water, springs, agricultural watersheds, streams, lakes, atmospheric deposition, and the marine environment. Another important aspect of the program was to document the effects on the aquatic environment of the measures and investments taken for nutrient reduction as outlined in the Action Plan. The monitoring program should determine if reductions in nutrients are achieved by the measures taken and should help decision makers choose appropriate additional measures to fulfill the objectives. Coordination with international programs and commissions is an important component of the monitoring program to meet internationally agreed upon reductions in nutrient inputs. The future and direction of the Danish National Aquatic Monitoring and Assessment Program will be to a large extent shaped by both the Water Framework Directive and Habitat Directive adopted by the European Union.     

长江河口及其上海岸带水体沉积物中磷的存在形态

讨论了磷的 5种存在形态及其分布规律。河口及岸带水体沉积物中磷主要是以有机磷 (OP)和无机磷 (IP)形式存在的 ,有机磷是有机质的组成部分 ,无机磷又可分为可溶性磷(DP)、铁结合磷 (Fe P)、铝结合磷 (Al P)、钙结合磷 (Ca P)。研究发现 ,沉积物中总磷含量水平在 6 92 79～ 1570 99μg/g之间 ,无机磷含量在 2 2 0 0 2～ 92 8 33μg/g之间 ,占总磷含量的31 8%～ 6 0 5% ,而有机磷含量在 394 89～ 6 4 2 6 6 μg/g之间 ,为总磷含量的 39 5%～ 6 8 2 %。在分析水体沉积物中各形态磷的含量和变化的基础上 ,对磷在时空上的变化、与有机碳、总氮的关系以及污水输入影响等进行了初步的论述 ,并提出沉积物中铁结合磷 (Fe P)和铝结合磷 (Al P)可作为判断污染的指标之一。     

太湖东部湖湾水生植物生长区底泥氮磷污染特征

为了解太湖东部湖湾(贡湖湾、光福湾、渔洋湾)表层底泥中氮、磷的污染特征及其与水生植物生长的关系,采集了各湖湾滨岸带水生植物生长区的表层底泥,探讨了水生植物的生长与分布对表层底泥中总氮(TN)、总磷(TP)及总有机碳(TOC)等含量的影响,并对表层底泥进行营养评价.结果表明,水生植物生长密集区底泥中TN、TP、TOC的含量均显著低于水生植物零星生长区,说明水生植物的生长对太湖东部湖湾表层底泥中营养盐与有机碳含量具有较为明显的影响;相关性分析显示,表层底泥中TOC与TN含量呈显著相关性(R2=0.832 8),而与TP的相关性则较弱(R2=0.166 5),反映了TOC在湖泊底泥中的沉积可能成为湖泊氮的重要来源,而对磷的影响较小.利用有机指数与有机氮指数两种方法分别对东部各湖湾底泥进行污染评价,贡湖湾、光福湾、渔洋湾底泥有机指数平均值分别为0.142 7、0.228 6与0.208 6,均属较清洁与尚清洁水平,而各湖湾有机氮指数平均值均为Ⅲ与Ⅳ级,说明底泥已遭受了一定程度的氮污染.因此,对水生植物零星生长区表层底泥中氮含量的控制与削减有利于湖泊富营养化的预防与治理.