两种铁氧化物对无机磷的吸附特征分析

沉积物是海洋生态系统磷循环的载体之一,铁氧化物作为海洋沉积物活性组分的重要部分,对磷在沉积物上的吸附解吸有着重要贡献,进而影响着磷在沉积物-水界面的交换。本文利用自行合成的α-Fe_2O_3和无定形氧化铁,研究了无机磷(以KH_2PO_4为例)在其上的吸附特征,并考察了离子强度等对该吸附过程的影响。结果表明,无定形氧化铁对无机磷的吸附平衡时间较短且吸附量较大,这与其较差的结晶度,较大的比表面积有关。无机磷在氧化铁上的吸附等温线符合Freundlich吸附等温式,研究发现两种铁氧化物的吸附热力学函数均为ΔH~θ0,ΔG~θ0,ΔS~θ0,说明整个吸附过程是吸热、自发、熵增加的过程;随着离子强度的增大,无机磷在两种铁氧化物上的平衡吸附量增加,吸附pH边曲线实验发现,无定形氧化铁对无机磷的吸附量随着pH的升高而减小。     

渤海埕岛海域再悬浮沉积物对磷吸附作用实验研究

通过流通搅拌短期动力学实验,对不同进水磷浓度下,渤海埕岛海域再悬浮沉积物对磷的吸附作用进行了研究.吸附动力学拟合结果表明,实验再悬浮沉积物对磷的吸附符合假二级动力学模型;吸附速率常数k2随着进水磷浓度的升高而减小,且吸附达平衡所需要的时间变长.尽管流通搅拌动力学实验过程,吸附未达到平衡,但通过拟合动力学数据可以得到平衡...     

长江口邻近海域沉积物对磷的吸附作用初步研究

选取长江口邻近海域的沉积物风干研磨后筛分为4个不同粒度的样品(40~80目,80~100目,120~200目及200目以下),考察粒度及磷浓度对动力学吸附的影响,比较了处理方式、介质pH及所含腐殖酸HA对等温吸附的影响。结果发现:(1)沉积物对磷的吸附可用伪二级动力学方程描述,沉积物粒度越小、初始磷浓度越大,对磷的吸附速率越大;(2)等温吸附曲线可用Langmuir-交叉型等温式拟合,磷的吸附量随粒度减小而增加。沉积物经HCl处理之后,对磷的吸附能力增强,沉积物对磷的吸附量与介质中HA的浓度正相关,pH对沉积物吸附磷的影响较为复杂,"稳定pH范围"约为7~9。     

黄河口海域沉积物对重金属的吸附

以黄河口海域表层沉积物为研究对象,研究沉积物对重金属Cu、Pb的吸附特性,将沉积物筛分为4种粒级,探讨粒度、pH值、吸附时间和吸附剂初始浓度对重金属吸附的影响。结果表明:沉积物粒径越小,对重金属的吸附量越大;吸附平衡时间有所差异,但在1.5h均能达到吸附平衡;吸附量均随pH值升高而逐渐增加,但铜的吸附较铅的吸附速度快;铜的吸附量与吸附剂初始浓度呈线性关系,而铅的吸附量在初始浓度较低时变化明显,随初始浓度增加吸附量增加减小;沉积物对铜吸附等温线符合Langmuir型,铅吸附等温线符合Freundlich型,吸附类型存在差异。重金属在沉积物中的吸附规律研究为黄河口海域污染调查及治理提供了科学依据。     

厦门西海域沉积物中碱性磷酸酶活力的分布、动态及其与各形态磷的关系

本文首次对厦门西海域表层沉积物中碱性磷酸酶活力的分布、动态进行了检测和分析，并在同步检测该沉积物各种形态磷含量的基础上对该酶与各形态磷的关系进行了探讨。结果表明，厦门西海域表层沉积物中碱性磷酸酶的活力分布与陆源排污对水体的污染有明显的相关性；酶活力与总磷、总无机磷含量相关性较大，与弱吸附可交换磷相关性不大，与总有机磷含量则呈显著不相关性。并认为，就厦门西海域而言，碱性磷酸酶活力的水平可作为小区域水     

厦门西海域沉积物中碱性磷酸酶活力的分布,动态及其与各形态磷的关系

本文首次对厦门西海域表层沉积物中碱性磷酸酶活力的分布、动态进行了检测和分析，并在同步检测该沉积物各种形态磷含量的基础上对该酶与各形态磷的关系进行了探讨。结果表明，厦门西海域表层沉积物中碱性磷酸酶的活力分布与陆源排污对水体的污染有明显的相关性；酶活力与总磷、总无机磷含量相关性较大，与弱吸附可交换磷相关性不大，与总有机磷含量则呈显著不相关性。并认为，就厦门西海域而言，碱性磷酸酶活力的水平可作为小区域水     

掺杂黏土矿物对沉积物吸持磷能力的影响

通过研究黏土矿物及掺杂黏土矿物后湖泊沉积物磷的吸附/解吸特性,分析了高岭土、膨润土和沸石掺杂于湖泊沉积物后对磷稳定固定化的可行性。试验结果表明:掺杂膨润土稳定固化磷的效果最优,其次是高岭土,但掺杂沸石减小了沉积物对磷的吸附能力。具体结果是,按5%和10%比例掺杂高岭土时,沉积物吸附磷的能力增加,最大吸附量增加17.33%;按20%和40%掺杂时,沉积物吸附磷的能力减小,最大减小了43.31%。掺杂比例小时,高岭土与沉积物之间的阳离子交换过程扩大了空隙,增大了吸附量。达到平衡后,继续掺杂高岭土,引起空隙堵塞,减小了吸附量。掺杂膨润土的比例越大,沉积物吸持磷能力越强,按40%掺杂时,最终吸持率高达81.82%。这与膨润土表面积大、活性成分多有关。沸石由于孔道内被水分子和其他阳离子占据,有效吸附面积减小,对磷稳定化不起作用。     

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。     

黄河口沉积物对磷酸盐的吸附与释放

本文对黄河口典型沉积物进行了吸附磷及释放磷的研究,结果表明黄河口地区浅海沉积物对磷的释放极少.阴离子表面活性剂的存在能降低对磷的吸附能力,溶液pH的增大对吸附量有增大的作用,硝酸盐的存在不影响沉积物对磷的吸附.沉积物吸附大量磷后的再释放是缓慢的.经测定,沉积物吸附/解吸平衡点一般为0.24～4.27μmol/dm3,此值一般高于底层水磷浓度,因此我们推测除粗颗粒样品外,黄河口地区浅海沉积物有向上覆水释放磷的倾向.     

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。     

Phosphorus speciation and availability in intertidal sediments of a temperate estuary: relation to eutrophication and annual P-fluxes

For a better understanding of the phosphorus dynamics and bioavailability in temperate climates, sequential chemical extraction techniques were used to study sediment P-pools distribution and relative importance in a eutrophicated estuary.Results indicate a shift in importance from the iron-bound P fraction to the CaCO₃-bound P fraction with increasing salinity, which suggests a decrease in bioavailable P from the most inner part of the estuary seaward, as the CaCO₃ associated P is believed to be less available for organisms. Salt marsh plants also influence sediment P speciation, through higher organic P fractions (mainly humic acid associated P) when compared to non-vegetated sediments. The ratio of iron-bound P to iron-oxyhydroxides may be used as an indicator of P availability, since it reflects the number of available P sorption sites in the metal oxides. This ratio was lowest in the intermediate zone of the estuary (13.7) when compared to the outer site (29.6) and the upper site (26.1), suggesting saturation of sorption sites. Co-incident with this, the intermediate site is characterized by the occurrence of macroalgal blooms during summer. In the present case, superficial sediments in the Mondego estuary do not show a clear seasonal trend, either in total amounts of exchangeable P or P speciation. Pools of exchangeable P in the surface sediment were 30 times higher than the annual net-export of P (14 ton year⁻¹) from the estuary. The annual P release from the sediment appears diminutive in comparison with the pool-size. Management measures to reduce nutrient input into coastal water systems should therefore consider that phosphorus availability may persist as a result of sediment supply, even after reducing the external point sources.     

东、黄海柱状沉积物中有机磷与无机磷的含量与分布研究

研究了东、黄海海域典型站位柱状沉积物中总磷(TP)、无机磷(IP)及有机磷(OP)的含量及其分布特征.东海、黄海海域3种形态磷的浓度范围分别如下:东海:TP 13.73～19.85 μmol·g~(-1),IP 11.39～16.03 μmol·g~(-1)和OP 2.11～3.81 μmol·g~(-1);黄海:TP 14.44～18.33 μmol·g~(-1);IP 11.79～15.88 μmol·g~(-1)和OP 2.45～2.65 μmol·g~(-1).两海区沉积物中IP/TP和OP/TP变化范围分别为79%～88%和12%～21%.IP是研究海域沉积物中磷的主要存在形式,陆源输入为影响沉积物磷浓度的主要因素.地处长江口附近的E4站和东海中部海区的E6站分别为所有调查站位中各形态磷浓度的最高和最低者.不同海区柱状沉积物中各形态磷浓度的垂直分布特点不同.其分布特征在一定程度上反映了相应历史时段该站位营养盐输入水平、自然条件和人类活动的重大变化.     

河口及莱州湾沉积物中磷的化学形态及其含量

对13个河口站位的沉积物以及莱州湾两个站位的柱状沉积物中的磷的三种基本结合态进行了测定。结果表明：河口沉积物中总磷量与河流污染程度有关。磷的主要存在形态是以磷灰石结合态磷（PAI）存在的无机结合态磷（PIN）。莱州湾的柱状沉积物磷含量以及存在形态在离岸近和表层站位受到河流一定程度的影响，而在深层和离岸远的站位受河流影响的程度降低，各种形态的磷含量已趋于平衡。     

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。     

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.     

Geochemical records of phosphorus in Jiaozhou Bay sediments-Implications for environmental changes in recent hundred years

Phosphorus is a key element and plays an important role in global biogeochemical cycles. The evolution of sedimentary environment is also influenced by phosphorus concentrations and fractions as well as phosphate sorption characteristics of the marine sediments. The geochemical characteristics of phosphorus and their environmental records were presented in Jiaozhou Bay sediments. Profiles of different forms of phosphorus were measured as well as the roles and vertical distributions of phosphorus forms in response to sedimentary environment changes were investigated. The results showed that inorganic phosphorus (IP) was the major fraction of total phosphorus (TP); phosphorus which is bound to calcium, iron and occluded phosphorus, as well as the exchangeable phosphorus were the main forms of IP, especially calcium-phosphorus, including detrital carbonate-bound phosphorus (Det-P) and authigenic apatite-bound phosphorus (ACa-P), are the uppermost constituent of IP in Jiaozhou Bay sediments. Moreover, the lead-210 chronology technology was employed to estimate how much phosphorus was buried ultimately in sediments. And the research showed that the impacts of human activities have increased remarkably in recent years especially between the 1980s and 2000. According to research, the development of Jiaozhou Bay environment in the past hundred years can be divided into three stages: (1) before the 1980s characterized by the relatively low sedimentation rate, weak land-derived phosphorus inputs and low anthropogenic impacts; (2) from the 1980s to around 2000, accelerating in the 1990s, during which high sedimentation rates, high phosphorus abundance and burial fluxes due to the severe human activities impacted on the whole environmental system; (3) after 2000, the period of the improvement of environment, the whole system has been improved including the decreasing sedimentation rates, concentration and the burial fluxes of phosphorus.     

Phosphorus in Bottom Sediments of Pomeranian Bay (Southern Baltic—Poland)

The paper presents the results of determination of inorganic and organic forms of phosphorus in bottom sediments of Pomeranian Bay. The sediments were collected in March and July of 1996. The following characteristics of the sediments were determined: organic matter content, forms of inorganic phosphorus: loosely adsorbed phosphorus and phosphorus bound to aluminium, calcium and iron, as well as total inorganic phosphorus. Pomeranian Bay is a shallow basin, with depth averaging between 12 and 15 m and sandy sediments prevailing. Smaller silt fractions occur only in the vicinity of the wina River estuary and in deeper northern regions of the Bay. Calcium-bound phosphorus is the dominant form of inorganic phosphorus in the Pomeranian Bay. Iron-bound phosphorus is the second most prevailing form, and aluminium-bound phosphorus the third. Loosely bound phosphorus was present in the lowest amounts. Total inorganic phosphorus in the Bay consisted of the four forms listed above, except in estuarine regions where an additional form of phosphorus occurred, most probably occluded phosphorus. High organic phosphorus concentrations were found at the wina River estuary and in the northern part of the Bay (Saßnitz Deep) corresponding to the higher organic matter content of these sediments. Sediments of Pomeranian Bay contained less phosphorus than those from the Gulf of Gda sk or Puck Bay and other parts of the Baltic Sea, suggesting that the amount of phosphorus in the sediments was determined by a number of inter-related factors, such as sediment type, amount of organic matter, the chemical composition of the sediment and oxygen content of near-bottom water.     

海水悬浮颗粒物中不同形态磷的测定

分别采用硫酸过硫酸钾作为氧化剂进行高压消解和用浓度为1 mol/dm³盐酸浸泡提取,然后用磷钼蓝分光光度法测定海水悬浮颗粒物、沉积物中的总磷和无机磷,用差减法得到有机磷。悬浮颗粒物总磷(PTP)和无机磷(PIP)质量浓度分别为(632.4～651.7)×10^-6和(436.6～452.6)×10^-6时,其相对标准偏差小于1.44%。悬浮颗粒物总磷、无机磷和有机磷的回收率分别为97.2%～101.3%,97.8%～100.4%和97.3%～102.3%。所建立的分析方法可用于海水、河口水悬浮颗粒物及沉积物中不同形态磷的测定。     

藻类生长对沉积物上磷迁移转化的影响

通过模拟中肋骨条藻(Skeletonema costatum)和沉积物共存体系,探究了富营养化条件下,藻类与沉积物对无机磷的吸收/吸附作用的相互影响。采用自制的金汞伏安微电极测定了藻与沉积物共存体系中溶解氧(DO)的含量变化,分析了体系中溶解氧含量变化与磷消耗速率以及沉积物中磷形态分布变化之间的关系。结果表明,在本课题研究范围内,共存的藻类与沉积物互相影响彼此对磷的消耗过程,1.0×10^4、5.0×10^4和1.0×10^5 cells/mL三种初始藻密度的中肋骨条藻(Skeletonema costatum)48 h后对磷的吸收百分比分别达54.7%、73.4%、93.8%,添加沉积物后分别降至21.3%、34.1%和51.9%;沉积物对培养基介质中的无机磷的吸附百分比为42.5%,加入三种不同藻密度的藻体后分别降至9.1%、2.8%及0.3%。高密度藻与沉积物共存体系的耗磷速率与体系DO含量呈显著负相关(p<0.05)。体系中DO浓度降低会促进沉积物中Fe-P向水体中释放,从而导致沉积物中铁结合态磷(Fe-P)含量的降低。可交换态磷(Ex-P)、有机磷(OP)和Fe-P是藻类存在时沉积物向水体中较易释放的形态。     

Laboratory Simulation on Phosphorus Releasing near the Water／Sediment Interface in the East China Sea off the Changjiang Estuary

Surface sediment samples taken from the East China Sea off the Changjiang estuary are used as raw materials for phosphorus releasing experiment. It is found that after being thoroughly mixed with seawater for about 10 minutes, phosphorus released from the sediments reaches its maximum value. Adsorption kinetics can be fitted with both Elovich equation and two-constant rate equation. The releasing amount is closely related to the composition of the sediments. Phosphorus release from silty and muddy sediment is higher than from that dominated by sandy composition. For the desorption reaction, iron-phosphorus(Fe-P) is the most active one, with a releasing ratio higher than other phosphorus forms,followed by absorbed-phosphorus (Ad-P) and organic bound phosphorus (OP). All of them can be referred to as bio-available phosphorus. The results demonstrate that phosphorus in sediments can be released into seawater under suitable hydrodynamic conditions, and have a great impact on the nutrition state and primary productivity of marine biosphere.