海洋生物体中痕量金属分析方法的实验室间分析互校

本文介绍了我国首次海洋生物体中痕量金属分析方法的实验室间互校结果。38个实验室分别参加了铜、铅、锌、镉、铬、硒、砷和汞8种元素,共22个分析方法的分析互校。互校结果表明,除了铅的分光光度法外,其余21个分析方法均能获得准确可比的分析结果。     

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。     

Trace metal-binding proteins in marine molluscs and crustaceans

Some marine invertebrates, such as the American oyster, Crassostrea virginica, the blue crab, callinectes sapidus and the American lobster, Homarusamericanus, concentrate trace metals in their tissues. The occurrence of metallothionein, a low molecular weight, sulfur-containing metal-binding protein, has been correlated with elevated levels of trace metals in these organisms. It is our hypothesis that, whilst metallothioneins are involved in the sequestration of elevated levels of trace metals, they primarily function in regulating normal metal metabolism. In this paper we describe recent field and laboratory experiments designed to examine how oysters, blue crabs and lobsters manage accumulated cadmium, copper and zinc. The possible rôles of metallothionein, as well as the tissue distribution of metals, are emphasized. Metallothioneins were found in all animals we examined; concentrations of metallothioneins and the the amount of bound trace metals are related to time of exposure. We have also demonstrated that the laboratory developed metallothionein models for blue crabs and lobsters may be useful in predicting the partitioning of trace metals in animals living in environments polluted with trace metals.     

Dissolved trace metals in the Western Mediterranean Sea: total concentration and fraction isolated by C18 Sep-Pak technique

An investigation of trace metal distributions in the Western Mediterranean Sea was carried out during the RRS Discovery cruise (July 1993) in which a transect from the Strait of Gibraltar to the Strait of Sicily was conducted. Organically complexed dissolved trace metals and their total concentrations were measured to investigate the end-members and to predict the environmental capacity of the Mediterranean for potential toxic metals. The distribution of trace metals can be accounted for by the mixing of several end-members and by some atmospheric inputs to the surface water. For Pb and Fe, the effects of the atmospheric inputs are more pronounced than for the other metals. Due to the rapid exchange of water masses, the Western Mediterranean may have the ability to assimilate the increased external inputs for some trace metals such as Cu, Cd, Ni and Zn. But the external inputs for Pb and Fe exceed the removal capacity of the Western Mediterranean and these elements may accumulate in the water column of the western basin. The C18 Sep-Pak technique and direct determination by DPASV were used to determine the amount of trace metal–organic complexes. The C18 Sep-Pak column isolates only a small fraction of trace metals except for Cu. The maximum hydrophobic fractions for the studied trace metals, except for Cd and Pb, which are not detectable, were found in the subsurface layer at all stations. This maximum may well be linked to picoplankton activity and the picoplankton, prochlorophytes may have an important role in the speciation of dissolved Cu as well as Synechococcus. These organic ligands for Cu were produced at the maximum of biological activity in the Western Mediterranean basin and seem to be accumulated at halocline level by Mediterranean hydrodynamic characteristics. However, direct determination by DPASV showed that the major part of Cu, Cd and Pb, complexed by organic materials, was not isolated by C18 Sep-Pak technique.     

Nutrient Limitation in Macroalgae (Ulva and Enteromorpha) from the Rías Baixas (NW Spain)

Abstract.  Photosynthesis and growth rates in samples of two green seaweeds ( Ulva and Enteromorpha ) were monitored in the laboratory. The macroalgae were collected every 15 days from four coastal embayments in Galicia (NW Spain). Ulva samples were found to be nutritionally limited, particularly in summer. The physiological activity of Enteromorpha did not appear to be as affected by nutrient scarcity, although it may have suffered from phosphorus limitation. The subsistence quotas, critical concentrations and storage capacity for N and P in Ulva were comparable to those obtained by other investigators in similar studies. The trace metals analysed apparently did not negatively affect the macroalgae at the measured concentrations; one explanation is that many of these metals function as essential micronutrients. The complex physiological interactions between metals and nutrients, however, may complicate interpretation of the results.     

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.     

Trace metals in selected organisms from the Adriatic sea

Extensive surveys were made to establish the concentrations of several metals (Zn, Cd, Pb, Cu and Hg) in various marine organisms from different parts of the Adriatic Sea in the period from 1979 to 1985. The results obtained are based on analyses which were performed in conjunction with carefully tested procedures. Proper sampling, sample storage, treatment of samples and final analytical determination has excluded artefacts which would influence the accuracy, or cause contamination and/or trace metal losses.The metal concentrations in shellfish from the coastal areas of the Adriatic Sea are in the range of the lowest values obtained for similar organisms from other localities throughout the Mediterranean Sea. Special attention has been paid to the anthropogenic influence on trace metal concentrations in organisms living in the vicinity of domestic sewage and/or industrial waste-water outflows.     

Trace metals (Cd, Cr, Cu, Fe, Ni, Pb, and Zn) in feathers of Black-browed Albatross Thalassarche melanophrys attending the Patagonian Shelf

We investigated the concentrations of cadmium, chromium, copper, iron, nickel, lead and zinc among feather tissues in sexes of Black-browed Albatross Thalassarche melanophrys killed in longliners off Argentina in 2005. We found no different metal concentration with sex for cadmium, copper, iron, lead and zinc in feathers of adult birds, though there were significant body-size differences between sexes. However, the concentrations of trace metals differed significantly among the type of feather within individual bird. The mean concentrations of copper, iron, and zinc in breast feathers of T.?melanophrys were lower than those reported for the species from Georgias del Sur/South Georgia, the southern Indian Ocean and for other seabirds' worldwide. While cadmium fall within the known range of concentrations for bird feathers lead were not. Our results may be indicating that level of pollution in Patagonia may not be as negligible as previously thought at least for some trace metals.     

Biological control of trace metal residence time and speciation: A review and synthesis

The recent literature on control of trace metal concentrations and speciation was reviewed. The dominant mechanism in control of concentration for most metals appears to be adsorption on biologically produced particulate matter. Some proportion of the metals removed from the surface waters by this mechanism are put back into solution in deeper water by bacterial decomposition of the particles; as a result, many trace metals display distributions in the water column resembling those of the inorganic nutrients. The residence time, as classically defined, cannot be calculated with sufficient accuracy to provide useful information. Since the main method for removal of trace metals from surface waters appears to be physical and biological, rather than strictly chemical, speciation studies in homogeneous systems, particularly those systems which are completely inorganic, appear unlikely to furnish useful information on actual species distributions in the oceans.     

Heavy metal analyses in the marine environment - approaches to quality control

The validity of analyses of elements in the femto- and picomolar ranges in waters and sediments can be assessed on the basis of several criteria: an evaluation of the chemical technique; the use of primary standards and intercalibration exercises; and chemical and geochemical coherence of the results. Herein are reported analyses of ruthenium, platinum, palladium, rhenium, iridium and gold in oceanic samples. The gold concentrations in surface seawaters, at least 25 times less than those previously reported, are in accord with the concentrations of their periodic table neighbors as well as with crustal and sedimentary contents. The remarkable concentration of rhenium in seawater, in relation to its very low crustal abundance, can be explained by the inertness of the perrhenate ion.     

南海表层水中的溶解态Cu,Pb, Zn,Cd

于1998年“南海海洋环境调查”外业工作期间在南海的各个站位,按照严格的防沾污措施采集了106个表层海水样品.采用溶剂萃取-石墨炉原子吸收法对样品中的痕量重金属Cu,Pb,Zn,Cd含量进行了分析测试.测得各重金属的平均值如下:Cu 0.100 μg/dm3,Pb 0.060μg/dm3,Zn 0.086 μg/dm3,Cd 0.007μg/dm3,接近世界大洋水的浓度水平.各重金属的空间分布呈现出海区周边含量高于中央,浓度有自近岸向远海逐渐减小的趋势.相关分析的结果表明各重金属夏季相关性优于冬季,Cu与Cd存在良好的正相关关系,并且首次在南海表层水发现Cu,Cd与营养盐的相关关系.将重金属浓度值作数理统计分析,得到它们在南海的基线值.     

The influence of organic matter and atmospheric deposition on the particulate trace metal concentration of northwest Atlantic surface seawater

Particulate trace metals (PTM), organic carbon (POC), and organic nitrogen (PON) were measured in a series of surface bucket samples collected between the New England coast of the United States and Bermuda. PTM concentrations were lower or equivalent to the lowest PTM concentrations reported in the literature. Examination of the relative variations in PTM with respect to particulate aluminum and carbon led to the conclusion that organic matter was the probable regulator of PTM abundance in open-ocean surface waters and was important in this respect for continental shelf and slope waters as well.Enrichment factors of trace metals relative to their crustal abundances were found to be similar in the atmosphere sampled in Bermuda and in Sargasso Sea surface water particulate matter. A simplistic vertical flux model was constructed which showed atmospheric input of trace metals to the Sargasso Sea to be of the same approximate magnitude as the rate of removal of PTM from the mixed layer by sinking in association with POC. Essentially all of the particulate Al, Fe, and Mn in the Sargasso Sea mixed layer was attributed to aeolian sources. The fate of other atmospherically derived trace metals in the Sargasso Sea mixed layer was suggested to be a function of their solubility in seawater.     

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.     

Comparison of sampling devices for trace metal determinations in seawater

The results of an intercomparison of three types of sampling device and three types of hydrowire, used for the collection of seawater samples for trace metal analysis, are presented. These devices were intercompared in an international experiment involving member states of the Intergovernmental Oceanographic Commission through the collection of mid-depth North Atlantic water samples at Panulirus Station near Bermuda. Of the commercially available sampling devices, modified GO-FLO samplers appear to yield the lowest concentration seawater samples with modified Niskin samplers having only slightly inferior capability. Both unmodified GO-FLO and Hydro-Bios samplers have similar, but generally poorer, abilities for the collection of uncontaminated samples. Of the three hydrowires intercompared, plastic-coated steel yields the lowest concentration samples for most metals. Kevlar and stainless-steel hydrowires appear to cause only slight contamination for some metals. Overall, the impression is obtained that differences between the levels of metals in the ocean reported by different laboratories is predominantly due to analytical, rather than sampling errors or artifacts.     

台湾北部近岸海域柳珊瑚体内金属累积的研究

自台湾北部和平岛沿岸海域及淡水河出海口海域，采得软木软柳珊瑚(ubergorgia suberosa)、扁刺柳珊瑚(Echinogorgia complexa)、网刺柳珊瑚(Echinogorgia reticulata)和1未定种柳珊瑚等4种柳珊瑚目样品。检测体内18种金属含量。其中以Ca、Zn、Cu、Al、Fe及Mn含量较高．体长较长的珊瑚。体内金属累积量则相对较高，尤其以Cu及Zn的趋势最为明确。经统计分析。显示4种珊瑚体内金属含量彼此间无群组相关性存在，呈现多变、无规则性的分布。本研究与大堡礁及委内瑞拉附近海域同一目珊瑚(Gorgonacea)中相同金属分析值进行比较结果Cd、Pb及Ni含量彼此差异不大，但Cu的含量则以台湾北部珊瑚体内较高。     

Dissolved Cu, Pb, Zn and Cd in the South China Sea surface waters

The understanding of the distribution of trace heavy metals in the world ocean has greatlyimProved in the past decades. But most of the data are of vertical profiles of certain stations(Bruland, l980; Paul et al., l992; RObert et al., l990) and large--scale study of temporaland spatial variability of trace heaVy metals in the ocean is rather few. In fact, affected by ver-tical mixing by upwelling or convection, biogenic removal, atmospheric fallout and continentalinput frorn rivers, the dist…     

Eelgrass (Zostera marina L.) as an indicator organism of trace metals in the Limfjord,Denmark

The concentrations of Pb, Cu, Cd and Zn were determined in above- and belowground parts of eelgrass (Zostera marina L.) at forty stations in a shallow, brackish water area (the Limfjord, Denmark). The concentrations of the trace metals were significantly elevated near the cities of Aalborg (Pb, Cu) and Struer (Cd). Trace metal concentrations in above and belowground parts of eelgrass were log-normal distributed and the concentrations of Cd, Cu and Zn in aboveground parts were significantly higher than in belowground parts. Furthermore, a significant correlation between trace metal concentrations in above- and belowground parts was found. The background level of trace metal concentrations in eelgrass in the Limfjord was estimated.The application of eelgrass as a monitoring organism is discussed; it is suggested that the concentration of some trace metals in above- and belowground parts of eelgrass may be used as a measure of the bioavailable fraction of these trace metals in ambient and interstitial water (sediment), respectively.     

Analytical intercomparison results from the 1990 Intergovernmental Oceanographic Commission open-ocean baseline survey for trace metals: Atlantic Ocean

“Dissolved” (< 0.4 μm filtered) and “total dissolvable” (unfiltered) trace element samples were collected using “clean” sampling techniques from four vertical profiles in the eastern Atlantic Ocean on the first IOC Trace Metals Baseline expedition. The analytical results obtained by 9 participating laboratories for Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, and Se on samples from station 4 in the northeast Atlantic have been evaluated with respect to accuracy and precision (intercomparability). The data variability among the reporting laboratories was expressed as 2 × SD for a given element and depth, and was comparable to the 95% confidence interval reported for the NASS seawater reference standards (representing analytical variability only). The discrepancies between reporting laboratories appear to be due to inaccuracies in standardization (analytical calibration), blank correction, and/or extraction efficiency corrections.Several of the sampling bottles used at this station were not adequately pre-cleaned (anomalous Pb results). The sample filtration process did not appear to have been a source of contamination for either dissolved or particulate trace elements. The trace metal profiles agree in general with previously reported profiles from the Atlantic Ocean. We conclude that the sampling and analytical methods we have employed for this effort, while still in need of improvement, are sufficient for obtaining accurate concentration data on most trace metals in the major water masses of the oceans, and to enable some evaluation of the biogeochemical cycling of the metals.     

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。     

海洋沉积物孔隙水中痕量金属元素的测试分析方法

孔隙水是沉积物-海水界面链接沉积物颗粒和上覆水体的一个重要过渡相态,针对其研究可更好地了解痕量金属在固-液界面的早期成岩过程。近年来,针对孔隙水中痕量元素研究的方法较为匮乏,为此建立了一种分析测定海洋沉积物孔隙水中7种痕量金属元素(Mn、Cu、Zn、Ni、Cd、Co、Pb)的方法,该方法使用Nobias PA1树脂进行富集分离,再使用电感耦合等离子体质谱(ICP-MS)进行测试,可针对孔隙水中的痕量金属元素进行准确分析。通过实验结果发现该方法最优实验条件为: Nobias PA1树脂富集时的pH值为5.5~6.0,洗脱酸浓度为1.3 mol/L硝酸,体积为1 mL。同时,样品需进行紫外消解4 h以上以分解有机络合物,该消解步骤对Cu和Co这两种元素尤其重要。该方法通过加标回收获得Mn、Cu、Ni、Co和Pb的回收率在92%~100%, Zn和Cd的回收率分别为72%和82%; Mn、Cu、Zn、Ni的方法检出限范围为0.03~0.53 nmol/L, Cd、Co、Pb的方法检出限范围为2.66×10^-3~8.60×10^-3 nmol/L,满足孔隙水中痕量金属浓度的测试需求。同时,根据检出限计算的结果显示,孔隙水样品只需1 mL,即可应用该方法进行测试。应用该方法测试了一根采集于北黄海中部沉积物短柱的孔隙水样品,测试结果显示其垂相分布合理、较符合早期成岩过程规律。此研究为分析海洋沉积物孔隙水中痕量金属元素提供了一种准确而简便的方法。