海洋及其上空大气中有机磷酸酯的研究进展

基于全球海洋及其上空大气中关于有机磷酸酯（OPEs）的数据，分析了目前OPEs在全球海洋及其上空大气的分布特征、影响因素以及当前研究存在的不足。总结发现，海水中的OPEs主要来自河流输送，且浓度分布特征表现为由近及远、由浅及深逐渐递减。磷酸三（2-氯乙基）酯（TCEP）、磷酸三（1-氯-2-丙基）酯（TCPP）和磷酸三（1，3-二氯异丙基）酯（TDCPP）三种卤化OPEs是海水中主要污染物；输入到海水中的OPEs经过颗粒沉降等作用沉积到海洋沉积物中，随之，沉积物中的OPEs可能反析出或直接累积，在海洋沉积物中形成一个大的OPEs储存库。分析北太平洋到北冰洋表层沉积物中OPEs的浓度发现，从白令海峡到北冰洋，随着纬度的增加OPEs的浓度也普遍增加，且相对于非卤化OPEs，卤化OPEs更易被运输到偏远海域。总有机碳（TOC）与大洋沉积物中OPEs的浓度无相关性，但与近海海洋沉积物中OPEs的浓度呈正相关，TCEP和磷酸三异丁酯（TiBP）为海洋沉积物中主要污染物；海洋上空大气与水体中的OPEs是不可分割的，海洋上空大气中的OPEs一部分通过大气沉降进入海水，一部分继续迁移到更偏远区域，气团来源是影响其分布的主要因素。对比OPEs在全球海洋上空大气中的浓度分布发现，南北半球并无明显差异，TCEP和TCPP是海洋上空大气中主要污染物。     

海洋环境有机磷酸酯的来源、分布与生物地球化学过程

继多种溴代阻燃剂加入《斯德哥尔摩公约》持久性有机污染物黑名单后,有机磷酸酯（organophosphate esters, OPEs）作为替代品,生产和使用量日益增加。研究表明OPEs可通过大气长距离传输、河流输运等方式进入海洋环境,并对海洋生态系统产生一定风险。本文详细梳理了海洋大气、水体和沉积物介质,以及海洋生物体中OPEs的含量水平和分布特征,并探讨了OPEs的海气交换、大气沉降、洋流输运等物理过程,以及生物富集与转化、生物泵耦合和微生物降解等生物地球化学过程。考虑到OPEs仍在大量生产和使用并将持续进入海洋环境,系统的海洋OPEs连续监测和生态风险评估亟待开展。     

高效液相色谱-串联质谱法同时测定海洋沉积物中27种有机磷酸酯

应用广泛且具有毒性的有机磷酸酯(organophosphate esters,OPEs)类阻燃剂,通过水、气输送等多种途径进入海洋环境,可能会导致人类和海洋生物面临潜在的健康风险。因此,建立高效可靠的分析方法对于揭示OPEs在海洋环境中的赋存状况,评估其生态风险具有重要的科学意义。文章建立了同时测定沉积物中27种OPEs的超声提取、固相萃取(SPE)净化以及高效液相色谱-串联质谱(HPLC-MS/MS)检测的分析方法。结果表明:30mL乙酸乙酯(EA)和乙腈(ACN)混合溶剂(体积比为3︰7)的提取效果明显优于单独使用甲醇(MeOH)、二氯甲烷(DCM)、EA和ACN;用5mL EA经LC-C18固相萃取小柱洗脱两次回收率最好;以MeOH和含0.0025%甲酸的水溶液作为流动相时,质谱离子丰度最高。27种OPEs的线性范围为5~500 ng/g (R²>0.99),方法检出限(MDL)范围为0.004~1.250 ng/g,定量限(LOQ)为0.01~4.17 ng/g。三个加标水平(低、中、高)基质加标样品的平均回收率在45%~130%之间,相对标准偏差(RSD)最高11.0%,表明此方法可靠,精密度和灵敏度较高。采用优化的方法分析我国长江口、杭州湾入海口以及东海和黄海交界处海域表层沉积物中OPEs的含量,共检出了21种OPEs,浓度范围为9.83~48.70 ng/g,平均浓度为28.40 ng/g。该方法检测结果高效准确,可用于海洋沉积物中27种OPEs的同时测定。     

台湾东部黑潮区海源碳的沉积物记录与近千年来生产力与气候变化的反演

本文基于对台湾以东黑潮主流区沉积物的粒度和定年，通过解析沉积物总有机碳及其同位素组成获取海源碳变化特征，首次报道了该海区近千年来的初级生产力与气候变化反演结果。研究显示，台湾以东黑潮主流区近千年来的平均沉积速率为34.44 cm/ka，沉积环境较为稳定。另外，台湾以东黑潮主流区沉积物中的总有机碳和总氮含量主要受台湾东部河流输入、海洋初级生产力的沉降过程、成岩作用和粒度效应影响。对沉积物海源碳的定量估算表明，近千年来台湾以东黑潮主流区沉积物中40.02%~73.88%的有机质为海源输入，陆源输送次之。同时，近千年来台湾以东黑潮主流区沉积物记录较好地反映了中世纪暖期、小冰期和现代暖期3个气候变化阶段。1150-1420年期间，沉积物中总有机碳、总氮和海源碳含量缓慢升高，较高的表层海水温度有利于海洋初级生产力水平的升高。1500-1840年期间，较低的表层海水温度和亚洲大陆风尘输送水平使得海洋初级生产力较低，同时台湾地区小冰期较高的降水量有利于台湾东部河流向海输送，增强的水动力条件可能会加强海底沉积物的东移，从而导致该区域沉积物中总有机碳含量的增加。进入现代暖期以来研究区的海水温度逐渐增暖，而东亚季风强度和降水量却表现出波动的年际变化特征，并体现在研究区1930-1950年和1970年期间沉积物的中值粒径、总有机碳和总氮含量的快速波动。     

岚山港临时海洋倾倒区表层沉积物重金属污染分布及影响因素分析

以2009年9月岚山港临时海洋倾倒区表层沉积物监测数据为基础,分析了该倾倒区海域表层沉积物重金属污染分布情况,发现该倾倒区海域表层沉积物重金属Cu、Pb、Zn、Cd、Cr、Hg污染分布大致表现为倾倒区范围内含量高,倾倒区外围含量低的趋势,可能是疏浚物的倾倒造成的这种分布特征。分析了岚山港临时海洋倾倒区表层沉积物重金属含量与有机碳、粒度的相关性,发现重金属含量与有机碳含量具有较高的正相关性,其中Cr与有机碳含量显著相关(P<0.01),重金属含量与粒度(沉积物黏土含量)呈正相关性。     

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。     

海洋沉积物含水率对部分碱金属及碱土金属元素含量的影响及意义

利用电感耦合等离子体光谱仪(ICP-AES)对海洋表层沉积物及上覆海水、海洋沉积物国家标准物质、陆地的水系沉积物及土壤国家标准物质进行检测以对比海洋沉积物含水率对部分碱金属及碱土金属元素分析结果所造成的影响。结果显示海洋沉积物含水率对钠离子影响最大,往往有超过50%的钠离子来自其中所含海水的贡献,而海洋沉积物含水率对钾、钙、镁的影响则较为微弱。因此,研究海洋沉积物化学组分时有必要考虑其所含海水对钠含量的贡献,以期达到不同海洋沉积物化学组分的可比性。     

海洋雾状层的成因及其对海洋碳循环过程的影响

海洋雾状层既是陆源物质进入海底的输送通道,又是海洋水体中沉降颗粒及底部再悬浮颗粒物的停留场所。雾状层物质来源主要有陆源、生源以及海底表层沉积物的再悬浮,不同海区、不同层位的雾状层的物质来源有所差异;雾状层的成因具有复杂性,既有物理作用,又有生物及化学作用,大量研究表明,海底洋流、内波(潮)等物理作用是雾状层形成的主要控制因素。雾状层中碳的存在形态主要有颗粒有机碳(POC)、溶解有机碳(DOC)、胶体有机碳(COC)以及无机碳,雾状层与其上下海水之间、雾状层与海底表层沉积物之间不同形态碳在生物-化学-物理动力系统作用下不断发生物质交换与迁移,对海洋碳循环生物地球化学过程起重要的控制作用,是整个海洋碳循环的一个不可忽视的环节。     

渤海湾氮、磷营养盐在水体和沉积物中的分布特征及其相互关系

近岸海域水体和沉积物是营养盐迁移转化的重要场所。2016年8月对渤海湾水体和沉积物进行采样监测,分析了渤海湾水体和沉积物中不同形态氮、磷的含量,并研究了营养盐在水体和沉积物中的分布特征及其相互关系。结果表明:渤海湾水体中的营养盐在西部近岸地区含量较高,而在离海岸线较远的开阔海域含量较低,表现出一个明显的质量浓度梯度。说明人类活动对近岸海域水体中营养盐含量的贡献较为明显。水体中营养盐主要是以无机态为主,无机氮和无机磷分别占到总氮和总磷的76.65%和76.46%。沉积物中氮、磷营养盐表现出和水体中营养盐含量类似的空间分布特征,但形态主要以有机氮为主,无机磷的含量也仅占到30.42%。这说明夏季渤海湾水体中氮、磷营养盐主要由水中有机体通过同化作用将无机态营养盐合成为有机态营养盐进入沉积物,渤海湾西北海域的富营养化过程是水体中营养盐向沉积物迁移的一个主要驱动力。     

海洋中化学过程的Φ(z/l,x)规律及其应用——Ⅶ.海洋中元素的迁移与失屏参数

海洋中元素的迁移变化规律性及其理论的研究是海洋化学的一个主要任务。石桥雅义和东慎之介曾从宏观角度研究过此问题,认为溶于海水中元素的量主要由如下三个因素决定:(1)元素在地壳中的存在量;(2)元素通过河川进入海洋的难易程度;(3)元素进入海洋后沉积到海底比率的大小。这就是说,影响元素迁移的因素十分复杂,涉及到地球的形成和地壳的组成、岩石的风化作用、雨水的侵蚀溶解、元素的物理-化学特性、(介质)海水的pH与氧化-还原电位、无机和有机悬浮物对溶解元素的吸着作用,海洋生物的活动、以及洋底岩石圈的活动和大气圈的影响等等,直到目前,还只能说是初步了解,许     

厦门邻近海域海洋环境放射性水平及评价

良好的环境质量是厦门成为一个宜居和滨海旅游城市的重要基石。自日本福岛核事故发生和福建省核电站陆续运行之后,厦门邻近海域潜在的核污染风险受到公众和管理部门的关注。本研究测定了2015年2月和8月厦门邻近海域海水和海洋沉积物中主要放射性核素的含量水平,并据此评价了该海域的环境放射性质量状况。结果表明海水中总铀、90Sr、226Ra、137Cs处于我国海洋放射性水平变化范围以内,无明显季节差异,其他放射性核素58Co、60Co、134Cs、110mAg、59Fe、54Mn、65Zn均未检出,海水中90Sr和137Cs的活度最大值远低于国家海水水质标准限值,海洋沉积物中放射性核素活度水平亦在我国海洋放射性水平变化范围以内。利用我国现有的海洋放射性环境质量评价方法对厦门邻近海域放射性质量状况进行分级评价得出其海水放射性质量为2级,海洋沉积物放射性环境质量为1级,均属于安全级别。研究结果表明2015年在厦门附近海域未观测到放射性污染现象。     

Phosphorus regeneration and burial in near-shore marine sediments (the Gulf of Trieste, northern Adriatic Sea)

According to bioassay studies and high dissolved nutrient N/P ratios in the seawater column, phosphorus (P) is thought to control marine productivity in the northern Adriatic Sea. P in near-shore marine sediments of the Gulf of Trieste, the northernmost part of the Adriatic Sea, was investigated using pore water P distributions, and benthic P flux studies under oxic and anoxic conditions. The data show that P regeneration is up to three-fold more extensive in sediments overlain by oxygen-depleted waters and proceeds in parallel with Fe and Mn enhanced benthic fluxes. It appears from the incubation experiments that degradation of sedimentary organic matter is the main contribution to the flux of P at the sediment–water interface, while the release of phosphate adsorbed on the iron oxide surface is of minor importance.It appears that about 50% of P in the Gulf of Trieste is retained within in the sediments, probably bonded to clay minerals and carbonate grains or precipitated as fluoroapatite. In these sediments total P (P_tot) is preserved preferentially over organic C (C_org). P regenerated from surficial sediments contributes about 1/3 of the P that is assimilated by benthic microalgae. The phytoplankton P requirement should be entirely supplied from fresh-water sources. These results suggest that oxygen depletion in coastal areas caused by eutrophication enhances P regeneration from sediments, providing the additional P necessary for increased biological productivity. The development of anoxic bottom waters in coastal areas enhances the recycling of P, exacerbating the nutrient requirement in the area. A geochemical record of P burial in a longer sedimentary sequence revealed an increasing trend of P_tot and organic P (P_org) contents occurring approximately 50 years BP (after 1950), probably due to increasing use of inorganic fertilizers and detergents in the area.     

海南东寨港重金属在多种环境介质中污染状况及评价

分析了东寨港海水、表层沉积物和生物体中重金属Cu、Zn、Pb、Cd、Hg、类金属As的含量及分布特征,并运用单因子指数法、地积累指数法评价了该调查区重金属污染程度。结果表明：东寨港海水中除Pb的含量符合二类海水标准外,其余含量均符合一类海水标准,且远低于渔业水质标准限值;表层沉积物中典型重金属元素含量都符合海洋沉积物质量一类标准,基本属于无污染区;本区湿地沉积物中的重金属含量比岛内及周边区典型红树林湿地略偏高;红树林及暗滩沉积物中重金属比东寨港水底沉积物重金属含量高,表明河口湾潮滩上的红树林区可能是重金属元素的富集区,东寨港目前可能受到了陆源污染的影响;生物体中重金属含量均符合一类标准,符合无公害水产品的要求。     

The reflection of the present distribution of the primary production in the bottom sediments of the Sea of Okhotsk

Using the authors’ data obtained during expeditions to the Sea of Okhotsk during the last decade, the primary phytoplankton production and the distribution of organic carbon and chlorophyll a degradation products (chlorin) in the bottom sediments were studied. Using the authors’ and published data, the spatial distribution of the production and paleoproduction indicators was plotted. The ratios of the chlorin and C_org content in the sediments was considered, and the correlation between these parameters was revealed. It was shown that the average annual primary production of phytoplankton and the paleoproduction indices were maximum in the coastal and upwelling zones and decreased towards the sea’s center. A quantitative correlation was found between the distribution of the present primary production in the photic layer and that of the rates of the accumulation of organic matter buried within the surface sediments. As a result, it was shown that the content of chlorin and C_org in the marine bottom sediments may be used to reconstruct the paleoproduction variability of the past.     

Specific features of temporal and spatial distributions of light hydrocarbons in the Sea of Azov

New data from recent surveys investigating the geochemistry of light hydrocarbons over a 4-year period in the Chernomorneftegaz petroleum license area in the central Sea of Azov are presented in this paper. The distributions of light hydrocarbons in both marine sediments and seawater were studied, and stable anomalies of hydrocarbons detected. Based on complex interpretations of geochemical and geophysical data, it has been shown that migration from the deep part of the sediment cover to the surface (seabed) is the main factor which determines the spatial distribution of hydrocarbons in the modern seabed sediments and seawater. The contribution of microbial and anthropogenic processes is insignificant.     

南海近海海水中放射性总α、总β的研究

本文对南海近海海水中的放射性总α、总β的含量和分布进行了研究。结果表明:南海近海海水中的总α、总β含量,略高于东海,稍低于渤海。南海近海海域的主要放射性物质是铀、钍天然放射系和~(40)K。     

Microbial ecology concerning to the degradation of nucleic acid in the marine environment

This article summarizes the author's current work on microbial degradation of nucleic acid. The aim of this work is to elucidate parts of the saprogenic process in the marine ecosystem through the study of the behavior of nucleic acid-hydrolyzing bacteria inhabiting seawater and sediments.Considerably large population of nucleic acid-hydrolyzing bacteria was found to occur in seawater and sediments. The main genera of these microbes areVibrio spp. in coastal seas, andPseudomonas spp. in the oceanic waters. As a result of microbial attack, nucleic acid components are released into seawater. The properties of extracellular nuclease produced by a marineVibrio sp. are well adapted to the seawater environment; consequently this enzyme has high activity and stability in seawater. By determining nuclease activity in seawater and sediments, the intensities of nucleic acid-hydrolysisin situ were evaluated.Distribution patterns of marine bacteria are also discussed in reference to the occurrence of phytoplankton in seawater.     

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.