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。     

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。     

不同水文条件下巢湖典型河流磷形态研究

河流输送是受纳水体中磷的主要来源,不同水文条件对其输送有很大影响。选择巢湖典型入湖河流丰乐和柘皋,在不同水文条件下,即非洪水期（丰乐和柘皋）、洪水涨水段（丰乐）与退水段（柘皋）对河水和沉积物进行分布式采样,测定磷的不同形态。其中,河水测定总磷（TP）和可溶性磷（DP）,沉积物测定总磷（TP）、无机磷（IP）、有机磷（OP）、铁铝磷（Fe/AL-P）和钙磷（Ca-P）。结果表明：非洪水期丰乐和柘皋河河水和沉积物中TP含量均为柘皋河高于丰乐河,两河都存在着富营养化风险,两河沉积物IP含量都显著高于OP。IP中,柘皋河Fe/Al-P含量略高于Ca-P,丰乐河相反。洪水涨水期,丰乐河河水TP和DP含量显著高于其非洪水期含量,沉积物不同形态磷均值含量较非洪水期略有降低,表明洪水涨水段降雨径流对不同来源磷冲刷、输送和泛起作用;洪水退水期,柘皋河河水TP和DP含量低于其非洪水期含量,河道沉积物不同形态磷均值含量较非洪水期有所升高,表明在退水段以稀释和沉淀作用为主。     

太湖及其主要入湖河流沉积磷形态分布研究

选择了我国第三大浅水湖泊--太湖及其主要入湖河流进行沉积磷形态的连续提取研究.太湖湖区沉积磷中不稳态磷(LP)及铝结合态磷(Al-P)含量很低,其余形态磷为铁结合态磷(Fe-P)＜钙结合态磷(Ca-P)＜有机磷(Org-P).河流沉积物中有机磷的相对含量高于湖泊沉积物,绝对含量平均值约为湖泊沉积物的3.9倍,铁结合态磷的绝对含量约为湖泊沉积物的3/4,湖区沉积物Fe-P含量与水体中PO3-4-、Chla呈显著正相关关系,同时与间隙水的氧化性呈显著负相关关系.太湖各湖区沉积物的磷形态表现为空间差异较大,活性组分的差异性要大于活性较差的组分.总的来说北部湖区沉积物中Fe-P和Org-P含量高于其他湖区,这与太湖北部湖区水体高营养级和藻类爆发关系密切.湖区沉积磷的垂直分布规律较复杂,既有随深度增加的,也有随深度降低的,河流沉积物同样如此.这与太湖及河流生态条件、污染物排放以及沉积动力学条件不同有关.     

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。     

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...     

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。     

滇池内源磷释放潜力的区域差异:来自沉积物磷形态的证据

采集了7组滇池近代沉积物柱芯,测定了其中总P(TP)、Fe、Al、Ca的含量,并首次获得了埋深大于25 cm的沉积物的不同形态磷的数据,分析了TP与不同形态磷的时空分布特征及TP与总Fe、Al、Ca含量的关系,探讨了滇池内源磷释放潜力的区域差异和制约因素。结果表明,自北向南,TP含量出现随深度先升高后降低的变化特征,各形态P之间的关系为:碎屑磷(DP)>有机磷(OP)≈铁结合态磷(Fe-P)>闭蓄态磷(Oc P)>钙结合态磷(Ca-P)>铝结合态磷(Al-P)>可交换态磷(SRP)。纵向上Fe-P随深度逐渐升高,Oc P逐渐降低,其它形态P的变化规律不明显;区域上TP、DP、OP、Fe-P、Ca-P和Al-P南部高于北部。在滇池南部DP通量较高的区域,TP与Fe、Al呈正相关关系,与Ca呈负相关关系,其它区域无相关性。分析表明,滇池南部内源磷的释放潜力大于中部和北部,而南部内源磷受DP输入的影响,风浪扰动对北部内源磷的释放有更强的抑制作用。     

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。      

湖泊沉积物中磷形态标准物质研制

水体富营养化与沉积物中磷元素的形态有密切关系。为了准确测定沉积物中不同形态的磷的含量,欧盟在2000年研制了第一个湖泊沉积物中磷形态标准物质(BCR 684),但基本用尽已不能满足需求,而且该标准物质采集于欧洲某湖泊,沉积物类型及污染情况与我国湖泊不相匹配。本文结合我国沉积物的类型和湖泊污染状况,研制了我国首批2个湖泊沉积物中磷形态标准物质(编号为 GBW 07462和GBW 07463)。候选物样品采集地点为江苏太湖和湖南洞庭湖,样品经过自然干燥、研磨、灭菌、陈化等加工处理,随机抽取15个子样采用单因素方差分析(F检验法)进行均匀性检验,检验的F实测值均小于临界值,表明样品均匀性良好。根据ISO导则35推荐方法对候选物样品在一年内进行四次稳定性检查,分析结果无方向性变化,再通过2次验证实验,样品稳定性良好。此批磷形态标准物质采用8家实验室联合定值,定值参数包括五种磷形态:总磷、无机磷、有机磷、磷灰石态磷、非磷灰石态磷;磷形态提取方法采用欧盟SMT法,测定方法采用钼锑钪光度法和电感耦合等离子体发射光谱法(实验过程中用欧盟BCR 684作为质量监控);按照《一级标准物质研制规范》(JJG 1006—1994)和ISO导则35的要求给出了五种磷形态的标准值和不确定度。此批磷形态标准物质样品代表了我国典型富营养化湖泊的沉积物类型,采样点的区域代表性强,定值项目选择合理、量值准确,可应用于环境、地质、农业、地球化学等研究领域沉积物的磷形态样品质量监控。     

南四湖及主要入湖河流沉积物中磷的赋存形态研究

应用沉积物磷形态SMT提取方法,分析了南四湖及主要入湖河流丰水季节表层沉积物、独山湖及微山湖区沉积岩芯中磷的含量及形态组成变化,研究了磷的埋藏演化过程与人为污染特征.结果表明,老运河表层沉积物中磷的含量最高,为13068.3 mg/kg,以OP及NaOH-P为主,其富集系数分别为6.5和9.0,主要是与来自济宁市的废水污染有关.其余表层沉积物以HCl-P为主;受人为污染的影响,NaOH-P、OP产生一定程度的富集,其富集系数分别为1.0.3.7、1.3～6.0;部分沉积物中高含量的有机质加重了OP的富集.独山湖及微山湖沉积岩芯中以HCl-P和OP为主;20世纪60年代末期以来,随着湖泊生产力的提高及早期成岩过程中有机质的矿化分解,独山湖及微山湖沉积岩芯中TOC含量自下而上呈指数增加,这也导致了沉积物中OP的增加;独山湖及微山湖沉积岩芯6～0 cm和5～0 cm较高的OP及NaOH-P含量,指示了20世纪80年代中期以来磷的人为污染过程.     

Sediment phosphorus fractions and profile distribution at different vegetation growth zones in a macrophyte dominated shallow Wuliangsuhai Lake,China

Sediment phosphorus (P) fractions and profile distribution at submerged macrophyte growth zone, emergent macrophyte growth zone and open-water zone were studied in Wuliangsuhai Lake, China, as well as the correlations among water content, grain size, and organic matter and P fractions. Among the three surveyed zones, the highest concentrations of most P forms occurred in the surface sediment and the lowest between a depth of 12 and 22 cm, except HCl-P and NaOH-P. Sediment phosphorus was mainly associated to inorganic forms (>50%) in three surveyed areas, and the highest value of inorganic phosphorus (IP) in the surface sediment was obtained from submerged macrophyte growth zone. Submerged and emergent macrophytes increased the IP content by 107 and 44 μg/g, respectively, in the surface sediment compared with open-water zone. Vertical profiles of IP in the three surveyed zones showed that the concentrations decreased from surface to 12 cm depth and then increased. There was a similar trend in the sediment profiles of organic phosphorus (OP) and total phosphorus (TP), but the highest concentration of OP and TP in surface sediment was obtained from the emergent macrophyte growth zone. Compared with open-water zone, the emergent macrophyte increased TP content in surface sediment by 1.73 times to 1,320 μg/g, while submerged macrophyte enhanced TP content in the surface sediment by 1.13 times to 865 μg/g. It was observed that in macrophyte growth zones, a strong linear correlation existed between organic matter and OP (r > 0.98), and the maximum concentrations of OP were present in the areas with maximum concentrations of organic matter. Results show that, although rooted macrophyte could uptake directly P from sediments, it is responsible for increasing the internal P loading especially OP by reducing current velocities, attenuating wave energy and generating organic residue in Wuliangsuhai Lake.     

崇明东滩沉积物磷的分布特征及环境意义

对崇明东滩采集的表层样和柱状样品，进行样品的总磷(TP)、无机磷(IP)和有机磷(OP)以及有机质含量等的测定，分析了磷的分布变化特征并对其影响因素和环境意义进行了探讨。     

Distributions of total,inorganic and organic phosphorus in surface and recent sediments of the sub-tropical and semi-pristine Guaratuba Bay estuary,SE Brazil

This study addresses the distribution of total phosphorus (TP) and its inorganic (IP) and organic (OP) fractions, grain-size and organic matter of surface and recent sediments, coupled to the behavior of total and dissolved inorganic phosphorus (TP and DIP) of the water column, of the semi-pristine Guaratuba Bay estuary, SE Brazil. Surface sediment samples were taken at 43 sites spread along the estuarine gradient and recent sediments from 3 short (35 cm long) cores from the upper, central and lower portions of the estuary, respectively. Highest TP and IP concentrations of surface sediments were detected within the upper sector and the transition zone between the upper and central sectors, all characterized by fine sediments, low salinities and water depths. In contrast, the lower sector and its narrow and deep tidal channel, subject to more intense tidal forcing, exhibited a higher fraction of sandy sediments with lower TP, IP and OP contents. In spite of the spatial variability in sediment grain size, IP corresponded to the major fraction of TP in all estuarine sectors and both TP and IP correlated significantly with the fine sedimentary (silt + clay) grain-size fraction. The fine surface sediments acted as a trap for IP at the fresh water–low salinity interface, which also corresponded to the region of a DIP sink in surface waters. In general, the short sediment cores showed that TP and IP contents increased from 15 cm depths to the top layer. Published sedimentation rates from additional cores taken at the sites of the short cores of this study, implied that depositional alterations of TP and IP increased during the early 1970s, which corresponded to the onset of anthropogenic disturbances from crop plantations in the lowland plains of the river end-member and urbanization at the estuary’s mouth and along the adjacent coast.     

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.     

Modeling bioavailable phosphorus via other phosphorus fractions in sediment cores from Jiulongkou Lake, China

Bioavailable phosphorus (BAP) plays an important role in phosphorus (P) release from lake and river sediments, as well as serves as an indicator for the potential P-release risk in sediment. Developing a feasible model which could predict BAP via other P fractions is needed for the lakes and reservoirs without regular BAP monitoring. The algal available P (AAP), NaHCO₃ extractable P (Olsen-P), water soluble P (WSP) and readily desorption P (RDP) are four fractions of BAP. The vertical and spatial distributions of BAP fractions of three sediment cores from Jiulongkou Lake were analyzed. In addition, the P fractions, including total P (TP), organic P (OP), inorganic P (IP), non-apatite inorganic P (NAIP), and apatite P (AP) were measured to develop a model for predicting BAP. The model for each BAP fraction was developed based on datasets from Jiulongkou Lake and validated by the datasets collected from Wujin and Wugong Lake. The results showed that all of the four BAP fractions decreased with depth, along the direction of contaminant transport. Their rank order was AAP > Olsen-P > WSP > RDP in all samples. The concentration of BAP was affected by the anthropogenic input and aquatic macrophyte growth. Each of the four BAP fractions could be simulated by different P fractions: both AAP and Olsen-P were expressed by NAIP and OP, WSP had a significant relationship with OP, and RDP had significant relationship with IP. NAIP and OP were the major sources of the BAP fraction. The simulated results in two other lakes further illustrated that this model could be used to successfully predict the BAP concentrations in lakes in the study area, and holds promise for predicting the BAP levels in other lakes and reservoirs as well.     

Distribution and speciation of phosphorus in sediments of Dongping Lake,North China

Dongping Lake is an important regulator for the Eastern Route of South-to-North Water Diversion Project in China, and the water quality assurance of it is of great importance. To investigate the distribution characteristics and burial process of phosphorus (P) in Dongping Lake as well as their relationship with regional economic development and human activities, 33 spatially distributed surface sediment samples and one lake sediment core were extracted from Dongping Lake. A harmonized procedure for the P forms in freshwater sediments developed by the European Programme, Standards, Measurements, and Testing was used in this paper. The results show that NaOH–P (P bound to Al, Fe, Mn oxides or hydroxides), HCl–P (Ca-bound P), inorganic phosphorus (IP), organic phosphorus (OP), and total phosphorus (TP) in the surface sediments show a strong spatial variability. The highest NaOH–P and OP concentrations were observed in the eastern and south-eastern region of the lake and decreased gradually away from the mouth area of Dawen River. We deduced that anthropogenic input via the Dawen River is the main contributor. The higher concentration of HCl–P occurred in the north-west region of the lake and increased in a gradient away from the mouth area of Dawen River, and this pattern of distribution could be related to grain-size effects and higher transport energies close to riverine inlets. Pollution reflected by phosphorus in the core sediments of Dongping Lake is well consistent with the economic development history of Dongping County. From the beginning of the 20th century to the middle 1970s, the concentrations of each P speciation did not vary largely and runoff of the Yellow River mainly contributed to the P accumulation in the sediment, which might reflect the background values of them in the lake in pre-industrial period. The stable Mz (mean grain size), low loss-on-ignition (LOI), and high sedimentary flux also support this. The rapid increase of NaOH–P and OP at 10–0 cm (especially 5–0 cm) indicates the enhancing anthropogenic eutrophication since the middle 1970s. The LOI peak period and a coarsening of particle size also support this interpretation. However, the decreasing of TP and HCl–P was attributed to the change in sediment supply. As due to construction of dams around the lake, runoff of the Dawen River mainly contributed to the P accumulation in the sediment during this period.     

Vertical variation of phosphorus forms in surface sediments from Wuli Bay, Taihu Lake, China

1IntroductionPhosphorus,an essential nutrient for the primaryproductivity in freshwater systems,is an important fac-tor controlling lacustrine eutrophication.Although ex-ternal input of phosphorus has been assumed as the vi-tal responsibility for the eutrophication of lakes(ZhuJun et al.,2005),the remobilization of phosphorus insediments has a distinct influence on it as well(Bostr m et al.,1982).The concentrations of totalphosphorus(Ptotal)in the sediments are often related tothe trophic st…