Chemical forms of minor metallic elements in the ocean

In order to clarify the chemical forms of minor metallic elements occurring in the ocean, a new method of separation of organic compounds of metals in sea water by using XAD-2 resin was contrived. By applying the new method of determination, it is found that, (1) More than 80 % of V, Fe, Cd and Cu dissolved in sea water are present in organic forms regardless of the depth; (2) A most part of Co and Pb are present in organic forms near the surface, but they change into inorganic forms in the deep layer up to 50 to 60%; (3) Of the total amounts of dissolved Al, Ni, Zn, Ag, Mo, and U, less than 30 % are present in organic forms in sea water anywhere in the ocean; (4) Up to 45% of Se is in organic forms.     

Determination of conditional stability constants of organic copper and zinc complexes dissolved in seawater using ligand exchange method with EDTA

To clarify the nature of organic metal complexes dissolved in seawater, a ligand exchange reaction between ligands of natural origin and an aminopolycarboxylic acid (EDTA) was used to determine the conditional stability constants of organic metal complexes. The results indicate that more than two organic molecules complexed with copper and zinc exist in surface seawater. It is found that the conditional stability constants of these naturally-occurring organic metal complexes are 1–3 orders of magnitude higher than those of EDTA-Cu and EDTA-Zn complexes. These estimates of the conditional stability constants for the dominant species of organic copper and zinc complexes are 10^11.8 and 10^9.3, respectively, at pH 8.1. The results indicate that these naturally-occurring organic metal complexes are stable species and not easily dissociated or displaced with others in the marine environment.     

Chemical forms of chromium in natural water

The interaction of chromium (III) with humic substances obtained from pond sediment was experimentally studied using electrophoresis combined with ultrafiltration. The results show that within the neutral pH range chromium (III) in the presence of humic substances and some organic acids forms uncharged and/or negatively charged organic complexes of various molecular weights. A part of the chromium(III)-humic or -fulvic acid complexes having a negative charge was of lower molecular weight. Chromium (III) spiked in fresh water exists as various soluble anionic and/or uncharged species, and the molecular weights of these anionic complexes correspond to those of chromium(III)-humic and -fulvic complexes. These complexes may remain as stable dissolved forms for 10 days. The significance of the occurrence of chromium(III)-organic complexes in natural water in the geochemical cycle of chromium in the hydrosphere is discussed.     

Determination of surfactant activity and anionic detergents in seawater and sea surface microlayer in the Mediterranean

The study of the physico-chemical properties and the determination of different classes of organic substances in the sea are of substantial interest and importance for understanding biogeochemical processes in the sea. The preferable method should be sensitive enough for direct measurement without pretreatment procedures in order to avoid changes in the composition of organic substances initially present in the sample.Surfactant activity data are presented here as measured by electrochemical methods during 1979, 1980 and 1981 in samples from open waters of the Western Mediterranean, and in a few characteristic coastal areas of the Adriatic Sea with different biological activity and different influence of man's activities. Data on sea surface microlayer samples collected during 1977, 1978 and 1981 at different locations and seasons in the Rijeka Bay, which is an integral part of the Adriatic Sea, are presented and discussed in more detail.It was found that the type and concentration of natural surface active material vary within different Mediterranean regions and along the depth profile of the water column.Petroleum hydrocarbons and detergents were found to be prevalent pollutants responsible for high surfactant activity values. Pollution effects are most pronounced in the sea surface microlayer.Electrochemical methods are proposed for research and monitoring of surface-active substances in the sea.     

海水中铀与碱式碳酸锌的反应级数及活化能

目前国外对碱式碳酸锌吸附海水中铀的报导较少,对其吸附海水中铀的反应级数及活化能测定的报导尚未见到。本文试图用三颈瓶反应器及分光光度法,测定海水中铀与碱式碳酸锌的反应级数及活化能,并获得较满意的实验结果。     

Effects of ligand speciation on determinations of the complexing abilities of strong ligands in natural waters

The presence of organic ligands (L) whose conditional stability constants (K_ML) are strong enough to allow them to form complexes with copper has been reported in oceanic waters. However, there is no general agreement on the distributional characteristics of such strong ligands in the water column. We present that these inconsistencies are derived from not only different analytical methods employed for their detection but also different oceanographic conditions. In particular, the nature and quantities of detectable natural ligands are affected by what kind of form the ligands are presentin situ in different marine environments, that is, chemical speciation of natural ligands (ligand speciation), which depends strongly on the variations in concentrations of coexisting trace metals. Using published data from observations in the laboratory and the field, we provide limits to the ranges of conditional stability constants of organic ligands for copper, zinc and cadmium that are detectable by the extensively used direct metal-titration method. For example, our model indicates that organic ligands for copper with log K_CuL(Cu)>12.4 in surface water and with log K_CuL(Cu)>9.9 in deep water might not have been detected because stronger ligands had formed complexes with ambient metalsin situ at a station in the North Pacific. The estimation suggests that there is a basinscale difference in speciation of natural organic ligands and, moreover, that this difference influences metal speciation. It is postulated that comparisons of the occurrence and levels of organic ligands might not be possible among spatially and temporally different observations without reconciliation of the effects of speciation of the ligands, even if an identical method is used in every case.     

A comparison of iron limitation of phytoplankton in natural oceanic waters and laboratory media conditioned with EDTA

The solubility of iron in oxic waters is so low that iron can be a limiting nutrient for phytoplankton growth in the open ocean. In order to mimic low iron concentrations in algal cultures, Ethylenediaminetetraacetate (EDTA) is commonly used. The presence of EDTA enables culture experiments to be performed at a low free metal concentration, while the total metal concentrations are high. Using EDTA provides for a more reproducible medium. In this study Fe speciation, as defined by EDTA in culture media, is compared with complexation by natural organic complexes in ocean water where Fe is thought to be limited. To grow oceanic species into iron limitation, a concentration of at least 10⁻⁴ M EDTA is necessary. Only then does the calculated [Fe³⁺] concentrations resemble those found in natural sea water, where the speciation is governed by natural dissolved organic ligands at nanomolar concentrations. Moreover, EDTA influences the redox speciation of iron, and thus frustrates research on the preferred source of Fe-uptake, Fe(III) or Fe(II), by algae. Nowadays, one can measure the extent of natural organic complexation in sea water, as well as the dissolved Fe(II) state, and can use ultra clean techniques in order to prevent contamination. Therefore, it is advisable to work with more natural conditions and not use EDTA to create iron limitation. This is especially important when the biological availability of the different chemical fractions of iron are the subject of research. Typically, many oceanic algae in the smallest size classes can still grow at very low ambient Fe and are not easily cultivated into limitation under ambient sea water conditions. However, the important class of large oceanic algae responsible for the major blooms and the large scale cycling of carbon, silicon and other elements, commonly has a high Fe requirement and can be grown into Fe limitation in ambient seawater.     

基于连续沥取的富钴结壳成因机制的探讨

根据连续沥取实验结果及相关文献,富钴结壳的生长可用一个双阶段胶体-化学吸附模型来说明.第一阶段是混合胶体的形成及元素的清除与富集,富氧的底层水与缺氧、富Mn2＋的中层水体混合,Mn2＋被氧化而形成MnO2胶体,并与水柱中的Fe（OH）3、Al（OH）3、SiO2、Ti（OH）4等胶体形成多种混合胶体[MnO2-Fe（OH）3、Fe（OH）3-Ti（OH）4和Fe（OH）3-Al（OH）3-SiO2],后者根据各自的表面物理化学特征吸附和富集不同的元素;第二阶段是混合胶体的沉积及富钴结壳的生长,第一阶段形成的混合胶体在海山基岩上以氧化物或氢氧化物的形式沉积,吸附的元素结合进矿物点阵,然后通过自催化或自反馈的方式生长.在富钴结壳生长中,生物起着重要的作用,包括为富钴结壳的生长提供大量的成矿物质、对Mn2＋的催化氧化作用及在铁锰胶体的沉淀及富钴结壳壳层的生长过程中的媒介作用.     

Hydrophysical and hydrochemical investigation on abiotic media of the Bay of Burgas

The results of field measurements in the Bay of Burgas (Bulgaria) are presented. The velocities and patterns of sea currents, the variation of the concentration of suspended organic matter, and the concentrations of mercury, copper, zinc, lead, and hydrocarbon in the water have been determined. The results show that the bay is polluted with heavy metals, which is especially dangerous since a cyclonic current exists there. Its pattern is revealed herein. Pollution accumulates in the water and is transported by currents longshore, producing a dangerous influence on the water ecosystems.Translated by mikhail M. Trufanov.     

Metal-organic complexes in seawater pumped up from under the ground

Metal-organic complexes of transition elements removed by Amberlite XAD-2 resin from seawater pumped up from under the ground were determined. The proportions of iron, copper and zinc retained on the resin to dissolved forms of these metals were about 70, 40 and 5%, respectively, while manganese, cobalt and nickel were not retained on the resin. These results suggest that although iron may be retained in colloidal form, a significant fraction of copper is present in some organic form(s).     

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。     

应用六氯化苯测年法对厦门港现代沉积速率的测定

岩芯柱样用静力岩芯采样器于1986年采自福建省厦门港一九龙江口海域。通过对这些岩芯柱样中六氯化苯(BHC)的垂直分布状况和生物扰动类型的分析,应用 S_R=D_(BHC-D_(mix)/Y的计算模式,获得了这些岩芯的现代沉积速率数据。将这些数据、方法与原理完全不同的~(210)Pb放射性同位素测年法同岩芯测年数据比较,其结果在数据和数量级上有一定可比性。初步认为,再经进一步探索和改进,BHC测年法有可能应用于近岸河口港湾几十年来现代沉积速率的测定而与其它测年法互为补充。     

Organic chemistry of seawater particulates - concepts and developments

Organic chemistry of particulates has recently been developed with the increasing quality of analytical methods. Because of the low organic content in deep sea, most of the studies were dealing with the euphotic layer. So we have very little information about the purely detrital material. Particulate organic carbon range from about 100 μg/1 in the surface layer, to 5–30 μg/1 in deep sea. Total particulate organic carbon in the world ocean must be about 2 · 10¹⁶g.It is important to obtain more detailed information about this enormous quantity of organic matter, the relative stability of which suggests that it could be used as a geochemical tracer. The distribution of particulate organic carbon exhibits regional variations, especially in surface waters, and a sharp vertical gradient of limited extent down to 200–300 m.At this depth, the deep water situation is reached with a quite constant carbon concentration disrupted only by pronounced increases associated with particular water masses. Though particles are generally recovered by filtration on 0.45 μ pore size filters, many smaller particles are present in sea water. The dialysis of seawater demonstrated a recovery of non dialysable material of about six times the amount recovered by filtration. While we have to take into account the existence of soluble high molecular substances, it seems possible for a great part of them to be in the colloidal state. If we except the biological processes, most of the chemical reactions occurring in the sea must concern this fraction. The detritus are for the most part too inert to play an important role in chemical reactions, while the strictly dissolved compounds are rapidly degraded by organisms. This colloidal fraction is thus responsible for the metals fixation, aggregation and sedimentation processes. It has been proved that it plays a very important role in the fixation of pesticides and hydrocarbons and must be considered in all the studies dealing with pollution.Some works on the origin of suspensions, showed that they can be formed by bubbling. Large organic active molecules adsorb to bubbles and produce monomolecular film which may be aggregated into insoluble organic particles; the agitation results in a semi-stable colloidal suspension of organic materials.It is highly probable that most of the organic matter in the deep sea is in the form of heteropolycondensed molecules, containing important carbohydrates and protein chains. These molecules are in a colloidal state in the supposedly dissolved material, which can be adsorbed on, or aggregated with particles by physical or biological processes.     

胶体的来源和胶体有机碳浓度对其自身菌群生长的影响

利用错流超滤技术分离厦门湾东南部海域、九龙江河口及九龙江水体中的胶体,并利用实验室模拟培养实验研究了胶体的来源和胶体有机碳（COC）浓度对其自身茵群生长的影响．结果表明,不同来源的3种胶体对自身菌群均有不同程度的促进作用,而且其依序为海洋胶体〉河口胶体〉河流胶体．海洋胶体和河口胶体中自身菌群的相对增长率的平均值Y1、Y2与CCOC之间呈正相关关系;而河流胶体中自身茵群的平均相对增长率Y3与CCOC却呈负相关关系．     

Temporal variations in the deep-water colonization rates of small benthic foraminifera: the results of an experiment on Cross Seamount

Modern benthic foraminifera are important remineralizers of organic matter and a link between surface-ocean production and life in the deep sea. Assemblages of benthic foraminifera are preserved in the fossil record, providing clues to paleoceanographic conditions. These clues can be fully interpreted only when our knowledge of the biology and ecology of modern species is more complete. To study factors influencing foraminiferal colonization rates, artificial substrates were placed on Cross Seamount (18°40′N, 158°17′W) for 1 to 42 months between 1989 and 1994. The colonization rates of benthic foraminifera onto different substrates (five mineral types were used) at four water depths (800, 975, 1285 and 2000 m) were determined. Both calcareous and agglutinated foraminifera inhabited these artificial substrates at different rates. Many of the agglutinated forms colonized at a uniform rate through time. The colonization rates of other foraminifera, primarily calcareous forms, were not constant through time, nor could the variability be attributed to the controlled variables (water depth and substrate composition). Instead, these temporal variations in colonization rate corresponded with shifts in surface ocean conditions and export fluxes in the central Pacific. Other ecological observations are also presented, including size- and spatial-distributions.     

用于海洋环境科学的一种新方法--影响因子分析法

用影响因子法对象山港海域叶绿素a与海水理化因子之间关系分析,结果表明：水温、溶解氧(DO)、气温、盐度、化学耗氧量(COD)因子为叶绿素a浓度变化的重要有效影响因子,其中水温、溶解氧因子占主导地位。由于该海域的富营养化,N、P和Si营养盐已经不再是影响浮游植物生长的有效因子。在特定海域资料有限的情况下,影响因子法比普通的相关和灰色系统分析更具有透明性,能够有效剔除无效因子,定量表达各理化因子对叶绿素a的影响程度。用影响因子法可以明确地判断出特定海域各海水理化因子对叶绿素a影响的主次程度及其有效性,从而定量确定出影响叶绿素a浓度的主要因子。     

Correcting the errors from variable sea salt retention and water of hydration in loss on ignition analysis: Implications for studies of estuarine and coastal waters

The standard technique of determining the concentrations of total suspended solids (TSSs), particulate inorganic matter (PIM), and particulate organic matter (POM) by filtration with glass fiber filters is subject to an error or bias from sea salt plus water of hydration retention, when applied to saline waters. The sea salt plus water of hydration retention by the filters occurs even after washing the filter with 300 ml of deionized water, a greater volume than any wash recommended in the literature. We determined that the mass retention on a glass fiber filter, at a given salinity, is essentially constant, no matter the volume of seawater passed through the filter. We also determined that the sea salt plus water of hydration retention on glass fiber filters is directly proportional to the salinity of the seawater filtered. Sea salt plus water of hydration retention causes an overestimate of TSS; sea salt retention causes an overestimate of PIM; volatilization of water of hydration causes an overestimate of POM. Thus a correction curve is required for sea salt and water of hydration errors in the determination of TSS and PIM. Corrected POM comes from the difference between the two. Also, filter blanks (procedural control filters), run with deionized (DI) water rather than the seawater sample, are required to correct for possible filter mass loss during the analysis. We demonstrate correction curves for sea salt plus water of hydration retention for Whatman GF/F filters, 47 mm diameter, utilizing the methods of the APHA Manual, Standard Methods for the Examination of Water and Wastewater. Application of other glass fiber filter types or an analytical technique differing significantly from that employed here requires a different correction curve for retention of sea salt and water of hydration. These methods can be used to reanalyze older data on PIM, POM, and TSS.We apply these corrections to PIM and POM data from the northern Gulf of Mexico and examine the interactions of these filter corrections with corrections for structural water volatilization from suspended clay minerals in the determinations of PIM and POM. We analyze published data on PIM and POM determinations and their application to remote sensing. We conclude that sea salt and water of hydration retention on filters has an adverse effect on remote-sensing algorithms inverting radiance reflectance to estimate concentrations of suspended matter.     

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。     

Bioaccumulation of heavy metals by bivalves from Limski Kanal (North Adriatic Sea). II. Copper distribution between oysters, Ostrea edulis, and ambient water

Accumulation of copper was studied between June 1979 and June 1980 in the oyster Ostrea edulis Linnaeus, cultivated in the Limski Kanal, on the Istria Peninsula (Yugoslavia).The copper distribution in different organs of oysters of the same age was compared with concentrations of copper existing in different physicochemical forms in ambient sea water, i.e., dissolved Cu in labile complexes determined at the natural pH of 8; ‘total’ dissolved Cu determined after acidification to pH 2; and Cu bound to suspended particles with a diameter above 0.45 μm. Copper concentrations in the water were determined by differential pulse anodic stripping voltammetry (DPASV) and in analyses of biotic material, graphite furnace atomic absorption spectrometry (GFAAS) was applied.Significant correlations have been found between copper complexed with dissolved organic ligands and its concentration in the soft part of the oyster. Copper contents increase gradually with the weight of the organs until enhanced gametogenetic activity of the oysters occurs. Thereafter the correlation factor between copper contents and the size of body parts varied significantly with the season.     

A comparison of two voltammetric techniques for determining zinc speciation in Northeast Pacific Ocean waters

Two independent voltammetric techniques, differential pulse cathodic stripping voltammetry (DPCSV) and differential pulse anodic stripping voltammetry (DPASV), determined that 95% of the dissolved zinc is organically complexed at two depths (60 and 150 m) within the surface euphotic zone at an open ocean station in the Northeast Pacific. Average values for the concentrations of the natural zinc-complexing organic ligands (C_L) obtained from duplicate determinations at these two depths by DPCSV versus DPASV are in excellent agreement: 1.60 ± 0.01 versus 1.76 ± 0.03 nM at 60 m, and 2.14 (n=1) versus 2.22 ± 0.06 nM at 150 m. Average values for the conditional stability constants (with respect to free Zn²⁺) of the natural zinc-organic complexes (log K^′_ZnL) from duplicate determinations at both depths by DPCSV versus DPASV are 10.3 ± 0.2 versus 11.2 ± 0.2. Additional research is required to assess the significance of the difference in the conditional stability constants determined by these two techniques. These results confirm recent observations that strong zinc complexes formed with an organic ligand class existing at nanomolar concentrations dominates zinc speciation in the North Pacific.