GEOCHEMISTRY OF ABYSSAL SEDIMENT IN THE PACIFIC OCEAN

The contents of Fe, Mn, Cu, Co, Ni, Pb and Zn in the seaiment associated with manganese nodules from the Northern Central Pacific Ocean and in their acid-soluble fractions were determined and correlations among the elements and between the trace metals and environmental parameters were discussed. It has been found that the contents of Mn, Cu and Ni in the sediment are one order of magnitude higher than those in the common sediment. As shown in the manganese nodules, they may mainly derive from seabed. The contents of all trace metals in the sediment are obviously governed by Fe-and Mn-oxides, organic matter, seawater depth, particle size and Eh. Multi-element correlation equations were developed for all trace metals. The trace metals in acid-soluble fraction of the sediment were also much higher than ihose of common sediment and negatively correlated with water depth, implying the possible influence of carbonate speciation.     

南黄海中部沉积物微量元素的环境记录研究

通过对南黄海中部E2站位沉积柱样部分微量元素的特征研究,讨论了近200a来与南黄海中部沉积物相关的主要环境气候演变.铅和金、铂族元素显示人类现代工农业活动对环境的影响在南黄海中部沉积物有明显记录;过渡金属元素和不活泼元素的记录显示小冰期(泛指1550～1850年)的结束,气温的升高对南黄海中部沉积区的氧化-还原条件和黄河流域的风化程度产生了影响;黄河的改道对南黄海中部沉积物陆源碎屑的输入产生影响.     

胶州湾水生系统中Pb、Zn 的分布特征及其在生物体中的浓缩

利用在胶州湾采集的47组同站位多介质样品,进行了痕量金属Pb、Zn及其它环境因子的化学成分测试,讨论了胶州湾水-沉积物-生物系统中Pb、Zn的生物地球化学总体特征及其在各介质平面上的分布,揭示了胶州湾水-沉积物-生物系统对陆源物质输入的响应.垂向上表层沉积物是Pb、Zn组分的富集带,该系统中的生物相对于其所处水环境具有显著的富集作用,生物体中Pb、Zn生物浓缩系数分别为36、935;横向上,Pb、Zn在底层水和沉积物介质中的分布主要受控于河口,即高值区分布于胶州湾的各个主要河口区,特别是在沉积物中金属组分浓度的高值区主要集中分布于胶州湾的东部.而孔隙水中Pb、Zn的高值主要分布于水交替较弱的海域,如红岛前缘.但生物体中的痕量金属组分化学场空间分布规律与上述各介质的化学场均不吻合,亦即是生物体中痕量金属组分的浓度与其所处环境中的同名金属组分浓度无关.作者认为,生物对痕量金属组分的富集并不简单地取决于它所处环境介质中同名金属组分的总量,而存在形态上的选择性.通过回归分析揭示了孔隙水对生物体中Pb、Zn的富集贡献较大.     

Influence of halophytes and metal contamination on salt marsh macro-benthic communities

Since an important fraction of the organic matter produced by salt marshes is decomposed in situ, macro-benthic communities are particularly exposed to the trace metals retained by these systems. Yet, few studies have investigated the macro-benthic communities using the between-root sediment habitat of the salt marsh halophytes (salt-tolerant plants), or the effect of trace metal pollution on its population dynamics. In the present study, samples were collected in vegetated and unvegetated sediment, in three salt marshes in the Tagus estuary, for trace metal concentration determination in the sediment and in the halophytes roots, grain size determination and macro-benthic organism identification. Data analysis revealed that the distribution of macro-benthic organisms is mainly determined by metal contamination, metal type and by the presence/absence of halophytes, not by the halophyte species. Five different associations were identified: resistant organisms were associated with the highest concentrations of lead (sediment); tolerant organisms with zinc, copper (sediment and roots) and lead (roots); cadmium in the sediment with a lack of macro-benthic life; sensitive organisms with low levels of metals except for cadmium in the roots; and macro-benthos typical of intertidal mudflats with unvegetated areas with low metal contamination.     

Spatial and seasonal variations in depth profile of trace metals in saltmarsh sediments from Sapelo Island, Georgia, USA

This study was undertaken to elucidate the impact of early diagenetic processes on the accumulation of trace metals in Sapelo Island saltmarsh sediments as a function of time, space and sediment properties. Samples were collected from three sites in summer (May 1997) and winter (January 1998) along a transect from an unvegetated Creek Bank through a vegetated Tidal Levee to the vegetated midmarsh with evident lateral heterogeneity caused by hydrologic regime, macrophytes and microbial and macrofaunal activities. A suite of trace metals (As, Ba, Cr, Co, Cu, Cd, Mo, Ni, Pb, Th, Ti, U, V, Zn and Zr) was analyzed to obtain their depth-distribution at the three sites. Spatially marked differences were observed, that were primarily related to hydraulic flushing of trace metals away from the sites in high-energy regimes, rapid downward mixing and reworking of sediment via bioturbation, and below-ground degradation and production of Spartina biomass. Although sulfate reduction and the formation of acid volatile sulfide and pyrite were dominant processes throughout the marsh, the trace metal scavenging role of sulfides was not apparent. However, possible sulfurization of organic matter, leading to enhanced trapping of trace metals with organic carbon, may have played an important role in sequestration of trace metals.No similarity was observed visually between the depth trends of trace metals and sediment properties (grain size, iron-oxyhydroxide content, acid volatile sulfides and pyrite content) that are known to play a major role in trace metal partitioning. Only organic carbon content closely followed the trace metal profiles at all the three sites. Minor variation in depth-integrated sediment trace metal content was observed seasonally at each of the three sites. Furthermore, the depth trend of profiles of individual trace metals also did not vary significantly over the seasons either.     

海洋沉积物的顺序淋滤萃取分析研究现状与发展趋势

在过去几十年里,为了探索海洋沉积物中元素的赋存形态,发展了很多分离沉积物中不同元素结合态的淋滤萃取方法。这些方法对于了解沉积物中微量元素的来源、迁移、分散、活动、生物化学及物理化学行为等特征具有重要的意义,并且在海洋地球化学和海洋环境污染研究中已得到广泛应用。本文综合论述了海洋沉积物的顺序淋滤萃取分析方法的研究进展,介绍了两种影响较大的方法,对其选用的萃取试剂以及分析流程进行了详细讨论,并比较了方法的优点和不足。     

The distribution of zinc,nickel, manganese,cadmium, copper,and iron in some surface waters from the world ocean

Determinations of Zn, Ni, Mn, Cd, Cu, and Fe have been carried out on 51 near-shore and 38 open-ocean surface seawaters from various regions of the World Ocean.The concentrations of the trace metals have been established in the open-ocean waters, and have been used as “baselines” to evaluate trace-metal enhancement in near-shore regions. The factors by which the trace metals are enriched in near-shore regions vary from one element to another and, according to the highest concentration factors found, decrease in the order Zn = Mn > Cd = Cu = Ni.These elements exhibit differences in their distributions between near-shore and open-ocean waters, and they have been divided into two types on this basis: Type I, in which the largest number of samples in both shelf and open-ocean waters lie in the same concentration range. Zinc, cadmium, and copper are Type I elements. Type 2, in which the largest number of samples of near-shore waters lie in a higher concentration range than the largest number of samples of open-ocean waters. Nickel and manganese are Type 2 elements.The concentrations of Mn, Cd and Zn are similar in open-ocean surface waters from the South Atlantic and Indian Ocean, but Cu and Ni have higher concentrations in the former ocean.There is considerable variation in the concentrations of the trace metals in near-shore surface waters from various regions of the World Ocean. These variations are discussed in detail.     

Adsorption–desorption reactions and bioturbation transport of Ra in marine sediments: a one-dimensional model with applications

The distribution of trace metals in sediments and their exchange between sediments and overlying water is governed by multiple processes including molecular diffusion, bioturbation (porewater advection, porewater mixing, and particle mixing), chemical reactions and adsorption–desorption. To understand these processes and their relative contributions, a one-dimensional model was built, which includes bioturbation and adsorption–desorption processes, to describe the transport of ²²⁴Ra. Because ²²⁴Ra is adsorbed on MnO₂, ²²⁴Ra may serve as a proxy for trace metal transport. Three sites were sampled and both dissolved and adsorbed ²²⁴Ra were analyzed and modeled to understand the transport and exchange processes. It was found that particle transport of adsorbed ²²⁴Ra followed by desorption at the sediment/water interface typically represents the dominant flux. We have further been able to define conditions where the porewater transport for adsorption reactive metals like ²²⁴Ra (and other metals) may be out of the sediments whereas the active scavenging of ²²⁴Ra from the water column at the sediment water interface via adsorption reactions can result in a flux of ²²⁴Ra into the sediment. These processes are both predicted by the model and observed in sediment samples.     

南黄海表层沉积物微量元素地球化学特征

分析了在南黄海采集的295个站位的表层沉积物样品的微量元素含量和500个站位的粒度参数,研究了南黄海沉积物微量元素含量、平均粒径和判别函数的分布特征及微量元素、沉积物类型和平均粒径的相关性。南黄海沉积物微量元素分布由于物质来源和与沉积物类型相关性的不同,表现出明显不同的分布规律:Sr分布与黄河、长江和生物碎屑碳酸盐的贡献有明显关系;Ba分布与黄河、锦江物质供给有关;东部Rb元素分布反映了韩国河流沉积物对南黄海东部的影响;Co分布反映了长江物质的运移方向。Ba和Cu与沉积物类型相关性不明显,不受沉积物粒度控制;Sr、Co、Rb则可以用于区分黄河、长江和韩国河流沉积物的来源。     

Adsorption–desorption reactions and bioturbation transport of 224Ra in marine sediments: a one-dimensional model with applications

The distribution of trace metals in sediments and their exchange between sediments and overlying water is governed by multiple processes including molecular diffusion, bioturbation (porewater advection, porewater mixing, and particle mixing), chemical reactions and adsorption–desorption. To understand these processes and their relative contributions, a one-dimensional model was built, which includes bioturbation and adsorption–desorption processes, to describe the transport of ²²⁴Ra. Because ²²⁴Ra is adsorbed on MnO₂, ²²⁴Ra may serve as a proxy for trace metal transport. Three sites were sampled and both dissolved and adsorbed ²²⁴Ra were analyzed and modeled to understand the transport and exchange processes. It was found that particle transport of adsorbed ²²⁴Ra followed by desorption at the sediment/water interface typically represents the dominant flux. We have further been able to define conditions where the porewater transport for adsorption reactive metals like ²²⁴Ra (and other metals) may be out of the sediments whereas the active scavenging of ²²⁴Ra from the water column at the sediment water interface via adsorption reactions can result in a flux of ²²⁴Ra into the sediment. These processes are both predicted by the model and observed in sediment samples.     

Influence of sample manipulation on contaminant flux and toxicity at the sediment-water interface

Toxicities of sediments from San Diego and San Francisco Bays were compared in laboratory experiments using sea urchin (Strongylocentrotus purpuratus) embryos exposed to pore water and at the sediment-water interface (SWI). Toxicity was consistently greater to embryos exposed at the SWI to intact (unhomogenized) sediment samples relative to homogenized samples. Measurement of selected trace metals indicated considerably greater fluxes of copper, zinc, and cadmium into overlying waters of intact sediment samples. Inhibition of sea urchin embryo development was generally greater in sediment pore waters relative to SWI exposures. Pore water toxicity may have been due to elevated unionized ammonia concentrations in some samples. The results indicate that invertebrate embryos are amenable to SWI exposures, a more ecologically relevant exposure system, and that sediment homogenization may create artifacts in laboratory toxicity experiments.     

罗纳河中悬浮物质的痕量元素的研究

于1989年5月－1990年4月间,在罗纳河下游近河口处进行每月一次为期间个月的样品采集工作,并且样品用HNO3－HF－HCIO4湿法消化后,用原子吸收分光光度法测定了悬浮颗粒物中的Co,Cr,Cu,Mn和Pb含量。结果表明,在不同月份之间悬浮物中的痕量元素组成具有显著地差别,其中一些元素的浓度随流量的增加而减少,而另外一些似乎与流量之间没有显著的关联。在稳定体系的假设下,所估计的人文活动对痕量元素的贡献可占观测浓度的10％－50％。当与其它河流对比时,发现罗纳河中的颗粒态痕量元素的浓度明显高于那些受人文活动影响较小的体系,而与北美的河流系统接近,表明罗纳河流域的人文活动对河流中颗粒态痕量元素的影响是显著的。     

黄河口新生湿地沉积物中的金属元素及其环境指示意义

通过对黄河口新生湿地沉积物岩芯中常量元素、稀土元素以及重金属分布特征的研究,探讨了滨海湿地沉积物中金属元素的环境指示意义。结果表明,大部分金属元素的分布模式类似,均在40 cm左右出现明显的低值区,这主要是由黄河携带而来的大量陆源物质的输入造成的。沉积物粒度组成以及有机质含量对金属元素的分布影响显著。常量元素中,Na₂O与其他元素变化趋势相反,反应了潮汐对滨海湿地的侵蚀作用;黄河口新生湿地沉积物单个稀土元素的含量大小顺序与黄河沉积物和渤海沉积物基本一致,稀土元素总量则高于黄河沉积物而低于渤海沉积物,表明黄河口湿地沉积物具有河流泥沙和海水颗粒物双重来源,而轻重分异比的变化则反映了物质输入的改变;而在较高的有机质和粘土含量的影响下,黄河口新生湿地沉积物中重金属发生了明显的富集。     

Distribution of silver, mercury, lead, copper and cadmium in central puget sound sediments

Distributions of five of the more toxic heavy metals have been assessed for Puget Sound sediments. Twenty-one Kasten cores were collected for the study. Analysis by Zeeman-corrected graphite-furnace atomic absorption spectroscopy has made possible the accurate and precise determination of silver and cadmium in Puget Sound sediment cores for the first time. Data show that Puget Sound is moderately impacted by anthropogenic Ag, Hg, Pb and Cu. No enrichment of Cd was found. The study also indicates that Puget Sound is quite well mixed with respect to the residence time of particle-bound metals. Toxic metal accumulation sites in the central Sound are determined almost exclusively by grain size, rather than proximity to sources. Estimates are made of trace metal fluxes to the sediments as a function of sediment type and areal distribution.     

太湖北部沉积物微量元素垂直分布特征及指示意义

分析了太湖北部柱状沉积物微量元素含量,以深层沉积物作背景样品,揭示了重金属垂向变化特征及指示意义。中深层沉积物中重金属Pb、Cu、Ni、Cr与Li呈显著正相关,反映了沉积物来源为流域基岩风化产物;表层沉积物中重金属Cu、Ni、Cr与有机碳具有良好正相关性,表明了沉积物受近年来环湖工农业活动影响。中深层沉积物与流域基岩在稀土特征上表现出亲源性;而表层沉积物稀土特征反映了人类活动的影响。     

Historical contamination of PAHs, PCBs, DDTs, and heavy metals in Mississippi River Delta, Galveston Bay and Tampa Bay sediment cores

Profiles of trace contaminant concentrations in sediment columns can be a natural archive from which pollutant inputs into coastal areas can be reconstructed. Reconstruction of historical inputs of anthropogenic chemicals is important for improving management strategies and evaluating the success of recent pollution controls measures. Here we report a reconstruction of historical contamination into three coastal sites along the US Gulf Coast: Mississippi River Delta, Galveston Bay and Tampa Bay. Within the watersheds of these areas are extensive agricultural lands as well as more than 50% of the chemical and refinery capacity of the USA. Despite this pollution potential, relatively low concentrations of trace metals and trace organic contaminants were found in one core from each of the three sites. Concentrations and fluxes of most trace metals found in surface sediments at these three sites, when normalized to Al, are typical for uncontaminated Gulf Coast sediments. Hydrophobic trace organic contaminants that are anthropogenic (polycyclic aromatic hydrocarbons, DDTs, and polychlorinated biphenyls) are found in sediments from all locations. The presence in surface sediments from the Mississippi River Delta of low level trace contaminants such as DDTs, which were banned in the early 1970's, indicate that they are still washed out from cultivated soils. It appears that the DDTs profile in that sediment core was produced by a combination of erosion processes of riverine and other sedimentary deposits during floods. Most of the pollutant profiles indicate that present-day conditions have improved from the more contaminated conditions in the 1950-1970's, before the advent of the Clean Water Act.     

Distribution and sources of heavy metals in the sediment of Xiangshan Bay

Heavy metals in the surface sediments and sediment core from the Xiangshan Bay, a mariculture base on the coast of the East China Sea, were determined by inductively coupled plasma mass spectrometry(ICP–MS) in order to evaluate their levels and sources. The results showed that the levels of Cu, Pb, Zn, and Cr in the sediments of the bay have been generally influenced by anthropogenic inputs since the founding of the People's Republic of China. In particular, Cu and Zn were polluted to some extent, as evidenced by high enrichment factors. Organic matter, grain size, wastewater discharge, and low energy hydrodynamic environment played dominant roles in the heavy metal enrichment in the sediments. The ratio of terrigenous source to marine biogenic deposit of trace metals in the sediments was calculated, revealing that terrigenous inputs were the main source of Cu, Pb, and Zn, while biological pellets contributed much more to the enrichment of Cr and Cd. Considering the influence of biological sources on the enrichment of Cd and Cr, and the fact that the sediment has been polluted by Cu and Zn, the development of mariculture and discharge of wastewater into the Bay should be restricted.     

Influence of soluble sewage material on adsorption and desorption behavior of cadmium,cobalt, silver and zinc in sediment-freshwater,sediment-seawater systems

The effect of varying concentrations of soluble sewage material in river water on the sorption of Ag, Cd, Co and Zn by suspended freshwater sediments has been studied. Comparison with unpolluted natural sediment systems show that the sorption processes for trace metals are often strongly modified when the river water contains sewage materials.     

Geochemical signature as paleoenvironmental markers in Holocene sediments of the Tinto River estuary (Southwestern Spain)

High absolute concentrations of metals associated to sulfide deposits located at the river source (Fe, Cu, Zn, Pb, Cd, and As) have been determined from the study of major and trace element concentrations in sediment samples obtained in two vibracores in the Tinto River estuary. In most cases, the enrichment factor (EF) for these metals is over 2. Cu, Zn and As have much higher EF, over 10 in surficial samples. Fe oxy-hydroxide precipitation in high-chlorinity zones and its scavenging effect on metals is the main control process on the chemical composition of sediment. Vertical evolution of the sedimentary and geochemical characteristics of the cores show that the estuary has undergone a process of progressive shallowness and a relative increase in acidic river water volume with respect to seawater. This effect has originated a downstream displacement of acid mixing processes affecting the estuary, which is reflected in higher metal concentrations in sediments of the outer zones of the system.     

黄、渤海几种溶解态痕量金属(Cu、Ni、Co、Zn)分布特征及其影响因素

海水中的痕量金属在海洋生物地球化学循环中至关重要。本研究在严格采用痕量金属洁净(trace-metalclean)采样和分析测试技术的前提下,于2016年7月采集了渤海与黄海表、底层海水水样,获得黄、渤海几种痕量金属(Cu、Ni、Co、Zn)的空间分布特征。研究结果显示,黄、渤海海水中痕量金属的空间分布具有近岸高、远岸低的特点,体现了人类活动对近岸海域的影响,而其在局部海域的分布则受到沿岸流、冷水团、沉积物再悬浮过程以及生物过程等因素的影响。Cu、Ni、Co在黄、渤海海水中的分布特征较为类似,平均浓度由高到低依次为渤海北黄海南黄海,而溶解态Zn的分布则与其他几种金属不同,在黄、渤海平均浓度类似,整体偏低,具有其特殊性。本研究测定的几种痕量金属在黄、渤海海水中的浓度较以往报道数据偏低,其中易污染的痕量金属Zn的浓度更是低近1—3个数量级,体现了痕量洁净采样和测试方法的重要性。