水库现代沉积过程沉积磷的早期成岩作用模型研究

在沉积磷形态分析、孔隙水化学、核素计年以及吸附解吸实验等的基础上,运用一维“反应-平流-扩散”模型,研究了红枫湖现代沉积过程中磷的沉积改造。结果表明:红枫湖现代沉积过程中,有机态磷的矿化分解和铁结合态磷的络合/溶解,是控制沉积物磷迁移转化动力学的主要机制。沉积物-水界面附近有机磷的快速降解,可能克服沉积界面上铁氧化物对溶解磷的吸附缓冲,而形成向水体的磷酸盐迁移通量;自生磷灰石的沉积改造相对不明显,沉积磷向稳定形态含磷矿物(钙氟磷灰石)的转化过程同样不能影响红枫湖现代沉积过程中磷转化的质量平衡。     

密云水库沉积物-水界面磷的地球化学作用

以密云水库为例，研究了水库沉积物中有机质的含量与有机磷的关系，表明表层沉积物中的总有机碳和有机磷的含量都明显高于底层，是由于一些以磷为营养素的富营养化指示藻类在水体中逐年增加，它们死亡后的残骸经分解-矿化后在底积物中累积的结果。沉积物和孔隙水中磷的剖面特征研究表明，表层沉积物和孔隙水中的磷都有明显上升的趋势，是由于沉积物的表层微生物和活性有机碎屑层比较丰富，有机质降解和含磷的有机化合物分解，使溶解性磷酸盐进入孔隙水。对沉积物磷形态、总有机碳及孔隙水中总磷对磷释放的影响进行了线性相关分析，结果表明上覆水中的磷主要来自沉积物的铁结合态磷、铝结合态磷、溶解态磷三种形态，孔隙水中总磷以及总有机碳含量对上覆水中总溶解磷浓度存在较大的影响，这些为研究水库沉积物作为水库内污染源对水质的影响提供了基础资料。     

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。     

淡水水体沉积物磷的环境生态效应研究进展及建议

对淡水水体沉积物磷的环境生态效应的国内外研究热点和领域进行了综述、评价;提出了尽快开展真正内源磷——地质成因磷自然释放的水环境生态效应研究,特别是天然条件下（如人为干扰少的源头河流）,富磷河流水体主要初级生产者——藻类生态响应研究的建议。     

北京官厅水库沉积物-水界面磷的分布和迁移特征

研究官厅水库一个沉积物柱及上覆水体磷的含量和形态特征,指出水体中的磷以颗粒态为主,界面上覆水中磷以无机磷酸盐为主,孔隙水中以有机磷占优势;界面附近湖水中总溶解磷、总无机磷、正磷酸盐和有机磷酸盐从远离界面到界面逐渐升高,孔隙水中总溶解磷、总无机磷、正磷酸盐在界面下10 cm左右达到最大值,有机磷含量由界面向下有增加趋势;计算了沉积物-水界面磷的沉降和扩散通量,分别为1967.5μg/a@cm2和0.5μg/a@cm2,结合沉积物中矿物组成、磷与Fe、Mn、SO2-4的关系,探讨影响磷分布和迁移的影响因素.     

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。     

陆架边缘海沉积物有机碳矿化及其对海洋碳循环的影响

边缘海沉积物是海洋重要的碳储库,其内部的碳循环主要是由有机质矿化分解过程来驱动的。有机碳进入边缘海沉积物后,矿化分解为溶解无机碳(DIC)进入沉积物孔隙水并扩散到上层水柱,参与海洋系统碳循环;同时还有部分DIC与钙镁等离子结合形成自生碳酸盐,保存于沉积物碳库。从生物地球化学角度探讨有机质埋藏机制和效率,在此基础上重点综述沉积物硫酸盐还原、产甲烷和甲烷厌氧氧化过程的耦合机制,以及有机质矿化对自生碳酸盐形成的影响等方面的研究进展,以期加深对陆架边缘海沉积物在全球碳循环收支平衡中的作用及其气候环境效应的认识。     

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。     

滇池现代沉积物中磷的地球化学及其对环境影响

湖泊沉积物中,磷是产生富营养化的重要元素.湖泊中磷元素含量、地球化学行为以及它的复杂矿物学特征,使人们对磷的研究极为重视.滇池湖中总磷超标10.3倍,底泥沉积物中P2O5平均含量0.52%,最高可达1.92%.滇池地处磷矿区,是磷质来源最丰富的湖泊,统计表明,磷含量每年在不断增长.滇池沉积物中磷主要以吸附态、有机态、铁结合态、钙结合态、铝结合态等几种形式存在.这些形态磷在底泥中是不稳定的,它们在环境改变条件下,又将磷释放到水体中.微生物在磷的循环过程中起了重要作用,乳酸菌对不溶性磷酸盐的分解,使湖泊中可溶磷含量增高.聚磷菌对磷元素的富集以及聚磷菌死亡后发生有机磷的矿化作用,是湖泊中水合磷酸盐矿物沉积的重要途径.当湖泊中这种不稳定的水合磷酸盐矿物在条件具备的情况下,经沉积物覆盖成岩作用后,最终形成磷灰石。     

密云水库中总磷迁移转化机制的分析

通过对2001、2002年进行的四次大规模取样测试结果进行分析,认为密云水库目前为中营养型水库,富营养化趋势明显,水中磷的主要来源为以工业、生活污水及水土流失携带进入水体的外源磷和以水库底泥释放为主的内源磷。磷在表层水中浓度小于底层水中的浓度,东西库区的浓度小于内湖的浓度;垂向上由上至下逐渐增高。磷的迁移转化途径为:一部分在水体悬浮物表层吸附或沉积,另一部分被水中的藻类吸收,进入生物作用。对水中磷的迁移转化影响较大的因素为:水中的pH值、溶解氧含量、温度、水动力条件及生物作用。     

沉水植物黑藻对上覆水中各形态磷浓度的影响

室内模拟研究了沉水植物黑藻对上覆水中不同形态磷浓度的影响及其季节性变化,并从沉水植物生长、间隙水和碱性磷酸酶活性(APA)三方面进行了讨论,进一步揭示磷在浅水湖泊水-沉积物界面的交换机理。结果表明,在本研究条件下,上覆水中各形态磷以溶解性总磷(DTP)为主,其他形态磷浓度变异较大,黑藻降低了上覆水中总磷(TP)、溶解性活性磷(SRP)和DTP浓度,也降低了DTP和SRP占总磷的比例,从而使颗粒态总磷(PP)和溶解性有机磷(DOP)占总磷比例升高。黑藻主要通过吸收上覆水中的磷和抑止沉积物、上覆水中APA使上覆水中各形态磷浓度保持较低水平,其中对SRP和DTP浓度的影响更明显。上覆水中各形态磷浓度呈现明显的季节性变化。在7～8月,TP、SRP和DTP浓度呈下降趋势,并在8月达到最低值;9～10月间有所升高,但仍然维持在较低水平,不同采样时间存在波动。     

强弱风浪扰动下太湖的营养盐垂向分布特征

在一次风速12m/s的强风浪过程中及在连续多天弱风浪之后,对太湖梅梁湾一浅水区营养盐、悬浮物等的垂向分布进行了观测和分析。结果表明,在水底沉积物约20cm的情况下,强风浪期间与弱风浪期间相比,湖水中悬浮物浓度提高了10倍,总磷浓度提高了3 6倍。而强风浪期间与弱风浪期间的水体溶解性总磷(DTP)、溶解性活性磷(SRP)的浓度无显著差异。说明尽管强风浪过程引起沉积物大量悬浮,水体悬浮颗粒态营养盐显著增高,但是由于悬浮过程营养盐释放与沉降机制作用十分复杂,活性营养盐的浓度未必能提高。无论强风浪还是弱风浪期间,水体的表层至水土界面上50cm层的悬浮物浓度、营养盐浓度没有明显的分层现象,但明显低于水土界面上50cm内的悬浮物浓度和总磷浓度。无论是强风浪期间还是弱风浪期间,表层到底层水体SRP浓度无显著差异。     

Benthic Phosphorus Dynamics in the Gulf of Finland, Baltic Sea

Benthic fluxes of soluble reactive phosphorus (SRP) and dissolved inorganic carbon (DIC) were measured in situ using autonomous landers in the Gulf of Finland in the Baltic Sea, on four expeditions between 2002 and 2005. These measurements together with model estimates of bottom water oxygen conditions were used to compute the magnitude of the yearly integrated benthic SRP flux (also called internal phosphorus load). The yearly integrated benthic SRP flux was found to be almost 10 times larger than the external (river and land sources) phosphorus load. The average SRP flux was 1.25?±?0.56?mmol?m^?2?d^?1 on anoxic bottoms, and ?0.01?±?0.08?mmol?m^?2?d^?1 on oxic bottoms. The bottom water oxygen conditions determined whether the SRP flux was in a high or low regime, and degradation of organic matter (as estimated from benthic DIC fluxes) correlated positively with SRP fluxes on anoxic bottoms. From this correlation, we estimated a potential increase in phosphorus flux of 0.69?±?0.26?mmol?m^?2?d^?1 from presently oxic bottoms, if they would turn anoxic. An almost full annual data set of in situ bottom water oxygen measurements showed high variability of oxygen concentration. Because of this, an estimate of the time which the sediments were exposed to oxygenated overlying bottom water was computed using a coupled thermohydrodynamic ocean?Csea and ecosystem model. Total phosphorus burial rates were calculated from vertical profiles of total phosphorus in sediment and sediment accumulation rates. Recycling and burial efficiencies for phosphorus of 97 and 3%, respectively, were estimated for anoxic accumulation bottoms from a benthic mass balance, which was based on the measured effluxes and burial rates.     

Intense pyrite formation under low-sulfate conditions in the Achterwasser lagoon, SW Baltic Sea

In comparison to similar low-sulfate coastal environments with anoxic-sulfidic sediments, the Achterwasser lagoon, which is part of the Oder estuary in the SW Baltic Sea, reveals unexpectedly high pyrite concentrations of up to 7.5 wt%. Pyrite occurs mainly as framboidal grains variable in size with diameters between 1 and 20 μm. Pyritization is not uniform down to the investigated sediment depth of 50 cm. The consumption of reactive-Fe is most efficient in the upper 20 cm of the sediment column, leading to degrees of pyritization (DOP) as high as 80 to 95%.Sediment accumulation in the Achterwasser takes place in high productivity waters. The content of organic carbon reaches values of up to 10 wt%, indicating that pyrite formation is not limited by the availability of organic matter. Although dissolved sulfate concentration is relatively low (<2 mmol/L) in the Achterwasser, the presence of H₂S in the pore water suggests that sulfate is unlikely to limit pyrite authigenesis. The lack of free Fe(II) in the pore waters combined with the possibility of a very efficient transformation of Fe-monosulfides to pyrite near the sediment/water interface suggests that pyrite formation is rather controlled by (i) the availability of reactive-Fe, which limits the FeS formation, and by (ii) the availability of an oxidant, which limits the transformation of FeS into pyrite. The ultimate source for reactive-Fe is the river Oder, which provides a high portion of reactive-Fe (∼65% of the total-Fe) in the form of suspended particulate matter. The surficial sediments of the Achterwasser are reduced, but are subject to oxidation from the overlying water by resuspension. Oxidation of the sediments produces sulfur species with oxidation states intermediate between sulfide and sulfate (e.g., thiosulfate and polysulfides), which transform FeS to FeS₂ at a significant rate. This process of FeS-recycling is suggested to be responsible for the formation of pyrite in high concentrations near the sediment surface, with DOP values between 80 and 95% even under low sulfate conditions.A postdepositional sulfidization takes place in the deeper part of the sediment column, at ∼22 cm depth, where the downward diffusion of H₂S is balanced by the upward migration of Fe(II). The vertical fluctuation of the diffusion front intensifies the pyritization of sediments. We suggest that the processes described may occur preferentially in shallow water lagoons with average net-sedimentation rates close to zero. Such environments are prone to surficial sediment resuspension, initiating oxidation of Fe-sulfides near the sediment/water interface. Subsequent FeS₂ formation as well as postdepositional sulfidization leads to a major pyrite spike at depth within the sediment profile.     

Phosphorus Mobilization at the Sediment–Water Interface in Softwater Shield Lakes: the Role of Organic Carbon and Metal Oxyhydroxides

The adsorption of phosphorus on natural diagenetic iron (Feox) and manganese (Mnox) oxyhydroxides was studied in deep and littoral zone sediments of mesotrophic Lac Saint-Charles (46°56 N, 71°23 W), using a Teflon sheet technique for collecting diagenetically produced metal oxyhydroxides. Collected metal oxide amounts were greater at the deep-water station, relative to littoral zone stations reflecting sediment and local diagenetic differences. Two-layer surface complexation modeling on iron oxyhydroxide was consistent with the measured total P/Fe molar ratios except for the upper mixed Mn–Fe oxide layer from the littoral stations, where measured phosphorus exceeded the modeled phosphorus by more than fivefold. Soluble reactive phosphorus (SRP) exchange between oxyhydroxide samples and natural lake water in the laboratory revealed a labile phosphorus pool. Phosphorus determined on the Teflon sheets from the littoral zone stations appears to be related to a distinct non-humic organic carbon pool that readily exchanges SRP, while little exchange was observed from material collected from the deep-water station. We suggest that the enhanced SRP release from littoral zone sediments is due to an organic carbon and/or metal oxide-impoverished sediment matrix, limiting microbial oxide reduction and allowing phosphorus to be rapidly recycled at the sediment–water interface, instead of being slowly incorporated into humic material. The SRP fluxes revealed in our study, which originate from the solid phase at the sediment–water interface, would be difficult to resolve using interstitial pore-water samplers and might be a quantitatively important source of inorganic phosphorus in Shield lakes.     

Settling and resuspended particles: A source or a sink of phosphate in two contrasting oligotrophic high mountain lakes?

This study focuses on two Mediterranean oligotrophic high mountain lakes located in the Sierra Nevada National Park (southern Spain): Río Seco (RS) and La Caldera (LC). A combination of field measurements and laboratory experiments is used: (i) to quantify in situ settling fluxes; (ii) to study the soluble reactive phosphorus (SRP) release or uptake by settling and resuspended particles; and (iii) to discriminate between the biotic and abiotic contribution for such patterns. In general, all suspensions (lake water untreated and lake water enriched with settling and with resuspended matter) in both study lakes release significantly more SRP to the solution when biological activity was suppressed. Biological uptake from settling and resuspended matter is likely to be limited by the bacterial consumption of P. Despite of these similarities, this study has revealed notable differences in the effect of sediment resuspension on SRP dynamics in both study lakes, when simulating natural conditions (biotic and abiotic processes). While in LC, the enrichment of lake water with settling and with resuspended matter did not cause an increase in SRP concentrations in lake water, SRP concentrations in RS at the end of the experiment were significantly higher (probability P < 0.05) in lake water enriched with resuspended matter (3.2 μg/l) than in natural lake water (lower than the detection limit). Accordingly, it is reasonable to expect that sediment resuspension, which occurs more frequently in RS compared with LC, affects drastically the SRP availability in the water column in RS.     

中国北方某湖泊底泥污染分析及重金属潜在生态风险评价

以中国北方某湖泊(以下称A湖)为例,开展了底泥中氮磷污染及重金属生态风险评价研究,探讨多种评价方法的相关性,并分析底泥中氮磷元素向上覆水迁移造成水体富营养化的风险.选取A湖中心区域的10个底泥监测点位数据,对其总氮、总磷及重金属(Pb、Cr、As、Cd、Ni)含量进行分析,并采用有机污染指数法评价总氮污染,单因子指数法...     

Comparative utilization of phosphorus from sedimentary and igneous phosphate rock by major biotic components of aquatic ecosystem

Two laboratory experiments were conducted to evaluate the amount of P utilization from two different types of sparingly soluble phosphate rock by aquatic biotic communities. The first type was Mussoorie Phosphate Rock or MPR (sedimentary in origin) and other was Purulia Phosphate Rock or PPR (igneous in origin). The two trials were with eight different treatment combinations. Among various treatments, fish and Chironomid larvae contributed to some extent in increasing the available sediment phosphate content which in turn increased the soluble reactive phosphate (SRP) of overlying water. Concentration of SRP of overlying water decreased in the treatment with zooplanktons. Depletion of SRP of overlying water due to uptake of orthophosphate by Chlorella was also observed. The sedimentary type phosphate rock proved to be more efficient in releasing phosphate than igneous one.     

Phosphorus fractions in sediment profiles and their potential contributions to eutrophication in Dianchi Lake

Dianchi Lake is a eutrophic lake in southwestern China. Sediment and the bottom water samples were taken from six sites in the east, west, south, north and center of the lake, respectively, in December 2002. Total phosphorus (TP) concentrations in sediments were high and reached a maximum value of 6.66 g/kg. There was a soluble reactive phosphorus (SRP) concentration gradient at the sediment–water interface. In the present study, sediment P was divided into loosely adsorbed P (NH₄Cl-P), redox-sensitive P (BD-P), metal oxides bound P (NaOH-P), calcium bound P (HCl-P), and organic P (Org-P). At three of the six sites selected, the concentrations of different P forms in sediments followed the order: NaOH-P, Org-P>HCl-P>BD-P>NH₄Cl-P in the profile, and in the southern lake the order was HCl-P>NaOH-P, Org-P>BD-P>NH₄Cl-P in the top 15 cm layers of the sediments. The sediment profiles showed that different forms of P had an increasing trend upward toward the sediment surface. There is a considerable potential for release from the sediment into the overlying water and sediment P could be the dominant factor determining the trophic status of the lake if the external load is reduced. An erratum to this article can be found at