东海特定海区表层沉积物中磷的形态、分布及其环境意义

对国家海洋局第二海洋研究所1998年5月调查过程中采集的长江口外东海特定海区表层沉积物综合运用了EDEX、ASPILA和李悦方法进行了系统的总磷及其磷赋存形态分析。把磷分为5种赋存形态：吸附态、铁结合态、钙结合态、碎屑态和有机态。同时，结合其他沉积物性质和化学组分以及海水环境特征，讨论了磷的地球化学特征及其环境意义。研究表明，表层沉积物中总磷(TP)、有机磷(0P)和铁结合态磷(Fe—P)的含量主要受控于物质来源；吸附态磷(Ad-P)与Fe—P和0P同属于沉积物中生物可利用磷范畴，其在沉积物中的循环主要与铁氧化物有关，钙结合态磷(Ca—P)主要来源于海洋浮游生物。     

长江口及毗邻海区沉积物中磷的分布特征

于2006年6月和2007年4月在长江口及毗邻海区采集了表层沉积物样品,利用水淘选法对沉积物进行了粒径分级,并采用改进后的SEDEX方法对沉积物样品及分粒级沉积物样品进行了磷形态分析。结果表明,2006年6月和2007年4月长江口及毗邻海区沉积物总磷变化分别为12.56~19.64μmol/g和8.99~19.91μmol/g,其中碎屑磷是磷的主要存在形态。可交换态磷、铁结合态磷、有机磷、自生磷灰石磷及难分解有机磷在长江口外的平面分布比较一致,均在紧邻长江口门外、杭州湾外的条状带出现了含量的高值,而在口门内及口门外河口靠海一侧碎屑磷含量较高。不同形态磷在不同粒径沉积物中的含量不尽相同:有机磷、自生磷灰石磷以及难分解有机磷是小于8μm粒级沉积物中磷的主要组成部分,而且其在总磷中所占比例随沉积物粒径的增加而下降;碎屑磷则主要集中在粗沉积物中,为32~63μm及大于63μm粒级沉积物中磷的主要贡献者。沉积物的粒度分异以及各形态磷在不同粒径沉积物中含量的差异,共同影响着河口沉积物中磷的分布。     

基于水淘选分级的长江口及邻近海域表层沉积物中磷的形态分布和迁移转化

磷是一种重要的生源要素,在河口、边缘海的初级生产中发挥重要作用,了解沉积物中磷的形态分布和迁移转化有助于深入了解该区域生态系统动力学。于2013年3月在长江口及邻近海域采集了表层沉积物样品,利用水淘选方法对沉积物进行了分级,并采用化学连续提取法分析了未分级和分级沉积物样品中的6种磷形态含量:可交换态磷、活性有机磷、铁结合态磷、自生磷灰石磷、碎屑磷和难分解有机磷,讨论了该区域沉积物中磷的形态分布、选择性输运过程和迁移转化。沉积物中总磷含量在14.0~18.4 μmol/g,其中碎屑磷是其主要成分,占54.5%,其次是有机磷和难分解有机磷,分别占到15.1%和13.1%。不同粒级沉积物中磷形态含量不同,可交换态磷、活性有机磷、铁结合态磷、自生磷灰石磷和难分解有机磷随粒级增加含量逐渐降低,而碎屑磷主要集中在粗粒级（大于32 μm）沉积物中。基于各粒级磷形态的质量分布,发现小于32 μm粒级的沉积物中各磷形态含量从长江口向浙闽沿岸逐渐增加,向外海方向逐渐减小,而大于32 μm沉积物的变化趋势与此相反,体现了不同形态磷的选择性输运。随粒径增大,总有机碳对有机磷比值（TOC/Or-P）先降低后升高,在大粒级沉积物中,TOC/Or-P比值较高主要是因为陆源有机碳贡献较高,而在小粒级沉积物中,主要是由于有机磷的迁移和转化更为活跃,体现了细颗粒物中有机磷相对有机碳的优先分解。本研究表明,从分级的角度可以对河口、边缘海的磷循环有一个更全面的认识。     

长江口及毗邻海区沉积物中磷的分布特征长江口及毗邻海区沉积物中磷的分布特征

于2006年6月和2007年4月在长江口及毗邻海区采集了表层沉积物样品,利用水淘选法对沉积物进行了粒径分级,并采用改进后的SEDEX方法对沉积物样品及分粒级沉积物样品进行了磷形态分析。结果表明,2006年6月和2007年4月长江口及毗邻海区沉积物总磷变化分别为1256~1964 μmol/g和899~1991 μmol/g,其中碎屑磷是磷的主要存在形态。可交换态磷、铁结合态磷、有机磷、自生磷灰石磷及难分解有机磷在长江口外的平面分布比较一致,均在紧邻长江口门外、杭州湾外的条状带出现了含量的高值,而在口门内及口门外河口靠海一侧碎屑磷含量较高。不同形态磷在不同粒径沉积物中的含量不尽相同：有机磷、自生磷灰石磷以及难分解有机磷是小于8 μm粒级沉积物中磷的主要组成部分,而且其在总磷中所占比例随沉积物粒径的增加而下降;碎屑磷则主要集中在粗沉积物中,为32~63 μm及大于63 μm粒级沉积物中磷的主要贡献者。沉积物的粒度分异以及各形态磷在不同粒径沉积物中含量的差异,共同影响着河口沉积物中磷的分布     

北部湾北部沉积物中磷的地球化学行为研究

对2006年7月北部湾北部海区调查过程中采集的表层沉积物运用SEDEX方法进行了系统的总磷及其磷赋存形态分析.把磷(P)分为6种赋存形态:弱吸附态(Ads-P)、铁结合态(Fe-P)、自生磷灰石及钙结合态(Ca-P)、碎屑态(De-P)、有机态(OPS)及硅酸盐态(SIF-P).结合上覆水的环境参数,讨论了磷的地球化学行为特征.研究表明,沉积物是上覆水体颗粒磷(PP)的汇,而不是上覆水体溶解态总磷(DTP)的源,沉积物中的P具有保守性;TPS、Fe-P和OPs具有亲大陆性;盐度(S)是影响Fe-P、OPS、SIF-P的含量变化的重要因子;Ca-P、De-P、SIF-P是沉积物中的"惰性磷",Ads-P、Fe-P、OPS为沉积物中的"活性磷";海区P的主要循环路径可以描述为:PP (←→)OPS→SIF-P →Fe-P→IPS.     

南沙群岛海域表层沉积物中磷的形态分布特征

根据2002年56月南沙群岛海域调查时采集的表层沉积物样品,分析了磷的含量并把磷分为总磷(PT)、无机磷(PIN)、有机磷(POR)、非磷灰石结合态磷(PNAI)、磷灰石结合态磷(PAI)5种赋存形态。利用EPM-810Q电子探针测试沉积物的化学成分,讨论了沉积物中磷的形态和分布以及沉积物的地球化学特征与环境的意义。结果表明,调查海区表层沉积物中磷灰石结合态磷与无机磷的含量变化主要受控于生物活动,它们具有同源关系,同属可被生物利用而再次进人生物地球化学循环的磷。沉积物中的总磷和有机磷与FeO显著相关。沉积物中磷灰石结合态磷与CaO显著相关,它的来源和输入方式受控于水体中碎屑颗粒沉积作用的影响。     

长江口及邻近海域沉积物再悬浮对水体磷酸盐的影响的模拟研究

以长江口及邻近海域为研究区域,采用改进后的SEDEX法对沉积物中各形态磷的含量进行了分析,并通过模拟实验探讨了沉积物再悬浮对上覆水体磷酸盐浓度的影响。结果表明:碎屑磷（De-P）是沉积物磷的主要赋存形态,占总磷（TP）的50%以上;其次是可提取态有机磷（Or-P）和非活性有机磷（Re-P）;生物可利用磷（BAP）占总磷的比例约为21%,可提取态有机磷（Or-P）是生物可利用磷（BAP）的主要存在形态。沉积物再悬浮时,水体磷酸盐的浓度显著升高,说明沉积物再悬浮会引起沉积物中磷的释放;水体磷酸盐浓度升高主要源于沉积物中磷的释放,而间隙水的贡献较低。沉积物发生再悬浮时,厌氧条件相对于好氧条件,更有利于沉积物磷的释放。     

花鸟山外海域几种形态磷在柱状沉积物中的分布及环境意义

综合运用 SEDEX化学法、ASPILA化学法和 XRF仪器分析法 ,对在东海赤潮多发区花鸟山外海域采集的柱状沉积物进行了总磷及其不同形态磷含量的系统分析。研究表明 ,总磷及其不同形态磷在沉积柱垂向上的分布有一定的变化规律。在采样深度范围内 ,总磷 (TP)、有机磷 (OP)和铁结合态磷 (Fe - P)的含量自下而上增高 ,而吸附态磷 (Ad - P)、自生钙结合态磷 (Ca- P)与碎屑态磷 (De- P)的含量向上递减。样品柱具有较均匀的粒度及矿物、化学组成 ,基本可以排除沉积物质来源和沉积环境变化对沉积物中磷含量的影响 ,而且也不能仅仅用早期成岩作用来解释磷的上述行为。不同形态磷在柱状沉积物中的分布规律 ,在一定程度上反映了近年来陆源区环境污染加剧的趋势。     

长江口滨岸潮滩沉积物中磷的存在形态和分布特征

通过对长江口滨岸潮滩表层及孔样沉积物中磷形态分析，揭示了潮滩沉积物中磷的存在形态及其分布特征。分析结果表明，潮滩沉积物中磷主要有可溶性磷（DP）、铁结合磷（Fe-P)、铝结合磷（Al-P)、钙结合磷（Ca-P)和有机磷（OP）5种，其中以钙结合磷（Ca-P)和有机磷（OP）为主。研究发现各形态磷的含量分布与水体沉积环境与沉积物粒度关系密切，并受沿岩污水排放及近岸养殖排污等人为活动的影响。     

长江口和浙江近岸海域表层沉积物中颗粒磷的形态分布和影响因素

研究长江口和浙江近岸海域的水团流向、缺氧程度、潮汐作用以及养殖活动对表层沉积物中颗粒磷赋存形式的影响,对东海生态环境的可持续发展有着重要的意义。长江口以北和浙江近岸泥质区各存在一个缺氧中心,杭州湾属于强潮区,而象山港遍布养殖场。2018年8—9月在上述4个海域分别采集表层沉积物,采用SEDEX方法进行了颗粒磷的形态划分和含量测定。研究结果表明：在长江口外北部缺氧区和浙江近岸泥质区的南部缺氧区,由于沉积物-水界面的还原环境可以活化铁结合态磷,使之转变为生物可以直接利用的弱吸附态无机磷,因此表现出沉积物中铁结合态磷的低值和弱吸附态无机磷的高值;前者的缺氧程度高于后者,因此其铁结合态磷的含量相应更低。杭州湾和象山港海域均受潮汐作用影响,两者沉积物中磷的分布比较均匀。象山港表层沉积物中铁结合态磷含量均较低,这可能是因为养殖活动造成的水体缺氧通过潮汐活动扩散到整个港底。象山港废弃养殖场沉积物中的碎屑磷和残余有机磷含量显著低于非养殖区,可能是由于养殖活动累积的生物沉积稀释了陆源输入的碎屑颗粒。     

渤海湾表层沉积物磷形态分析

用JEN SEN等(1998)六步分离法对2003年11月和2004年5月渤海湾采集的沉积物样品进行P形态分析,结果表明:沉积物营养盐水平与地理环境有关。总的趋势是沉积物越细,粘土含量越高,营养盐水平就越高。渤海湾表层沉积物磷呈现从潮间带向渤海湾大面站增大的局势,污染近岸高,远岸低。渤海湾表层沉积物中的P主要以FAP和R ef磷为主,FAP占整个P形态的43%以上,R ef占24%以上,其次是L ea-P,此种形态的P平均约占5%左右,最后依次是F e-P、CFAP和L sor-P,这三种形态含量都小于10%以下。这表明渤海湾沉积物中的P的主要来源是陆源输入和污水排入。渤海湾表层沉积物中有一半以上的磷不能被生物利用。     

Geochemical speciation and spatial distributions of phosphorus in surface sediments from the basin of the Marcus-Wake seamounts in the western Pacific Ocean

The concentrations of five forms of phosphorus(P) including exchangeable or loosely adsorbed P(Ex-P), Febound P(Fe-P), authigenic P(Auth-P), detrital P(Det-P), and organic P(Org-P) from the basin among the Marcus-Wake seamounts(19.4°–24°N, 156.5°–161.5°E) in the western Pacific Ocean were quantified using a sequential extraction method(SEDEX) to investigate the distribution and sources of different P species.Concentrations of total P(TP) varied from 14.0 μmol/g to 44.1 μmol/g, with an average of...     

Particle-bound phosphorus along an urbanized coastal plain estuary

The distribution of particle-bound phosphorus in the suspended sediment of the Delaware Estuary was examined with a sequential chemical leaching technique. The phosphorus content of particles was highest in the tidal river (140–250 μmol g⁻¹) near major anthropogenic inputs. Despite this enrichment of river particles with phosphorus, suspended particles within the salinity gradient had a phosphorus content more similar to the world's average. Sequential chemical leaches revealed that particulate phosphorus was associated with organic matter, aluminum oxides, iron oxides, and apatite in all areas of the estuary. However, ‘excess’ particle-bound phosphorus in the tidal river was associated mainly with iron oxides (27%), aluminum oxides (23%), and organic matter (50%). Within the salinity gradient, particulate phosphorus associated with iron oxides, aluminum oxides, and apatite all decreased with increasing salinity. Estuarine mixing was simulated to determine whether the observed decreases in particle-bound phosphorus pools in field samples were due to release into solution. During simulated mixing, particulate phosphorus associated with iron and aluminum oxides decreased, but no change was observed in apatite-bound phosphorus. The results of the mixing study combined with the observed particle-bound phosphorus distributions suggest that phosphate concentrations along the Delaware Estuary may be partially ‘buffered’ by aluminum and iron oxide phases.     

悬浮沉积物对磷酸盐的吸附与释放及藻类对吸附磷的利用

本文用1987年12月采自平度县大泽山水库的水样和沉积物样品,实验研究了悬浮沉积物对磷酸盐的吸附与释放以及藻类对悬浮沉积物吸附磷的利用。实验证明,悬浮沉积物对PO_4—P的吸附相当迅速,24小时即趋于饱和;绝对吸附量随水中原有PO_4—P浓度和沉积物含量增加而增加,相对吸附量也随水中原有PO_4—P浓度的增加而增加,但随沉积物含量的增加而减少;悬浮沉积物的吸磷或释磷,取决于沉积物吸附的磷量与水中溶存PO_4—P浓度两者的相对关系,在吸附释放平衡条件下,二者的数量变化呈对数相关。藻类培养结果表明,悬浮沉积物吸附磷能被藻类直接利用。据此,作者提出应当用总活性磷,而不是溶解无机磷作为浅水型内陆水域有效磷的指标。     

南海北部柱状沉积物中黄铁矿的分布特征和形貌研究

对南海北部陆坡柱状沉积物样品总有机碳、总硫含量,以及其中的自生黄铁矿形貌、含量进行分析．结果显示,沉积物中黄铁矿（FeS2）、总有机碳（TOC）、总硫（TS）的质量分数分别为0～0,71％、0．37％～1．18％、0．04％～0．81％;黄铁矿和总有机碳、总硫的含量随深度加深逐渐增大,达到峰值后不断减少,三者的分布趋势基本一致;扫描电镜下观察到黄铁矿主要以莓球状集合体和八面体微晶形貌产出,局部层位亦发现管状、生物内膜状和立方体状黄铁矿晶体．表明该区浅表层环境为缺氧环境,硫化物主要以黄铁矿形式产出,其成因与有机质的厌氧氧化作用有关,而甲烷的厌氧氧化作用也可能促使自生黄铁矿的加速形成．莓球状黄铁矿占主导亦指示一种强还原性的缺氧微环境．黄铁矿富集的缺氧环境与下伏地层中天然气水合物分解释放的甲烷有关,为天然气水合物在该区的勘探提供一定的科荤依据．     

Phosphorus distribution in the estuarine sediments of the Daliao river,China

The objective of this study was to investigate the phosphorus distribution in the estuarine sediments of the Daliao river, intensively affected by municipal effluent and agricultural activity for about 50 years. Surface sediment samples were taken at 35 sites in the estuarine area and phosphorus species and contents of total P, Al, Fe, and Ca in the sediments were measured. Results showed that the content of total P in the sediments ranged from 230 to 841 mg kg⁻¹, with an average of 549 mg kg⁻¹. Ca–bound P, residual P, Al–bound P, reductant–soluble P, Fe–bound P, and soluble and loosely bound P were averagely 44.5, 21.6, 13.6, 11.7, 8.9 and 0.2% of total P, respectively. With the gradual increase of total P content, Al–bound P, reductant–soluble P, and Fe–bound P generally increased, while the rest species of P did not. This might indicate that anthropogenic P is bound to Al and Fe oxides. Regression analysis showed that Al–bound P and sum of Fe–bound P and reductant–soluble P were correlated to the contents of total Al and Fe, respectively. On the other hand, Ca–bound P was not correlated to the content of total Ca in the sediment, probably suggesting that Ca–P was mainly from authigenic marine origin. Whereas the content of total P in the estuarine sediments of the Daliao river was within the range of total P content for Chinese and worldwide river estuaries as well as coastal sediments, non-calcium apatite phosphorus content in the estuarine sediments of the Daliao river was relatively higher, indicating higher release risk and bioavailability of P in the sediment. On the other hand, the molar ratio of total Fe to total P was 16–34 in the estuarine sediments of the Daliao river, suggesting that iron oxides/hydroxides in the sediments might be able to sequester more phosphorus. Therefore, the accumulation or release of P in/from the estuarine sediments might be dependent on the external loading of P and the estuarine eutrophication may be sustained by the internal bioavailable P pools following the decrease of the external P loading.     

Early diagenetic redistribution and burial of phosphorus in the sediments of the southwestern East Sea (Japan Sea)

This study was carried out in order to understand the early diagenetic redistribution of phosphorus and relevant mass balance in the sediments of the East Sea. In two cruises during May 1993 and October 1995, 11 box cores were collected in the southwestern part of the East Sea. Dissolved phosphorus and iron were analyzed in the porewater from the cores. Sediment samples were analyzed for solid-phase P species and solid-phase Fe oxyhydroxide by sequential extraction.Phosphorus speciation results show that organic P is the major chemical form of phosphorus in young sediments within the upper 50 cm of sediment. However, the authigenic fraction of total P increases with depth, indicating the precipitation of carbonate fluorapatite (CFA) in the sediments. The authigenic CFA (Ca₅(PO₄)_2.6(CO₃)_0.4F) was formed and buried at rates of 11–110 μmol cm⁻² kyr⁻¹. The main source of dissolved phosphorus for the precipitation of CFA is organic P. Dissolved phosphorus, released from the decomposition of organic P, diffuses upward to return to bottom water, or is sorbed to iron oxides in the oxidized sediments. As sedimentation proceeds, the iron oxide-bound P is released in the reduced layer and enters the dissolved phase, which contributes P to the formation of CFA in addition to that contributed by the organic P.The burial flux of reactive P (iron oxide-bound P+authigenic P+organic P) is 0.09–0.53 g P m⁻² yr⁻¹ that accounts for 18–58% of the reactive P arriving at the sediment/water interface. The burial flux of reactive P is high in the upper and lower continental margin sediment. The burial flux of reactive P in the Ulleung Basin sediment is less than those in the continental margin sites by a factor of 6, indicating that the reactive P burial flux is mainly dependent on sedimentation rate.     

过硫酸盐氧化法测定海水中溶解总磷

实验研究在碱性和酸性条件下过二硫酸钾高温氧化四种不同类型含磷标准化合物在海水中的回收率和影响回收率的因素。结果表明 :在碱性条件下过二硫酸钾高温氧化可使海水中非聚磷类化合物完全回收 ,而聚磷类化合物回收率不高 ,延长消化时间聚磷类化合物的回收率有一定提高。除个别化合物外 ,各类含磷化合物在酸性条件下可被定量回收。依此 ,建立酸性过硫酸盐氧化法分解测定海水中溶解态总磷的方法。     

Spatial distribution of sedimentary P pools in a Mediterranean coastal lagoon ‘Albufera d’es Grau’ (Minorca Island,Spain)

The method for the sequential extraction of P proposed by Jensen et al. [Mcglathery, K.J., Marino, R., Howarth, R.W. (1998) Limnol. Oceanogr. 43, 799–810] was used to study the spatial distribution of sedimentary P in superficial sediments of a mesohaline coastal lagoon located in a watershed formed by carboniferous sandstone in the Western Mediterranean (Minorca Island, Spain). Dissolved inorganic phosphate (IP), dissolved organic phosphate (OP), Fe, Ca, Al, and F were analyzed in the extractions to assess adequacy of this method to clay sediments. The elemental composition of the solid phase (Al, Fe, K, Ti, Si, Mg and Ca) was also analyzed to relate concentrations of P pools to the mineral composition. Samples from marine carbonated sediments, rock and some materials of biological origin (tubes of polychaete Ficopomatus enigmaticus, bivalve shell debris) were analyzed for comparative purposes. The sequential procedure allowed to extract almost all sedimentary P from carbonate sediments and biogenic debris, but only 70% of total phosphorus (TP) from clay sediments and rock. Main IP pools in the lagoon were Fe-bound P (16.6% of TP), CaCO₃-bound P mainly from Ficopomatus tubes (12.0% of TP), and detrital carbonate fluorapatite (7.8% of TP). The most abundant P pool was refractory P (20.3% of TP), which appeared associated to the (Fe,K)Al-silicate fraction and to humic P. This indicated that clay–humic–organic P complexes were the main P reservoir in the lagoon. Spatial distribution of P pools reflected differential sedimentation of allochthonous materials, authigenic precipitation of Fe-oxides, and Fe-bound P as well as the differential distribution of organisms such as Ficopomatus.     

末次盛冰期以来冲绳海槽中部沉积物有机碳和磷的地球化学研究

利用元素及同位素地球化学方法研究了冲绳海槽中部沉积物岩芯中有机碳及磷的地球化学特征及影响因素。结果表明,冲绳海槽沉积速率（16.5~32.5 cm/ka）变化小,不是沉积物中有机碳埋藏的重要影响因素。相对于全新世氧化性底水环境,末次盛冰期/冰消期冲绳海槽缺氧底水环境提高了沉积物对有机碳的埋藏效率。冲绳海槽沉积物中各形态磷的相对含量与其他边缘海沉积物中的相似。交换态磷（Ex-P）含量低、变化小。末次盛冰期/冰消期缺氧底水环境下铁氧化物的还原溶解导致铁结合磷（Fe-P）释放以及自生磷矿物（Au-P）的形成。全新世氧化性底水条件有利于铁氧化物的有效再生及对磷的再吸附,但不利于Au-P的保存。总有机碳（TOC）和有机磷（Org-P）之间良好的相关性表明TOC埋藏对Org-P含量的重要控制作用。冲绳海槽沉积物中碎屑磷（De-P）含量低于长江口及东海陆架沉积物中的含量,这与陆源碎屑向外海传输减弱有关。在约9.3 ka BP（岩芯200 cm深度）,TOC、Fe-P、Org-P、De-P以及Fe_HR均出现的极小值可能由物质坡移造成。