Distribution of trace and major elements in sediment and pore waters of the Lena Delta and Laptev Sea

Sediment cores collected during the SPASIBA expedition in 1991 were analysed for their trace- and major element concentrations. Leachable (0.1 N HCl) as well as residual concentrations were determined. Fe and Mn were measured in the interstitial waters to characterize redox conditions. Lateral distribution patterns of solid phase Cu, Cd, Ni, Pb and Zn show a small increase in concentration from the Lena Delta in seaward direction. In general concentrations of these metals are very low and similar to natural background values. With some exceptions, solid phase profiles with depth of all investigated elements do not show strong variations. No enrichment of Pb and Zn in surface layers was found. Remobilization processes and transport of particles enriched in Mn are responsible for Mn accumulation in a particular area. Pore-water concentrations of dissolved Mn in the latter sediments are very high (> 700 μM) and suggest strong Mn reduction directly below the sediment-water interface. In contrast to Mn, the depth profiles of Cd show a surface layer with lower concentrations and an increase deeper down the sediment. The C/N ratio in the sediment decreases from 13 in the Lena mouth to 9 in the more marine part of the Laptev Sea. Surface sediments in the Laptev Sea are very uniform and homogeneous and show only small concentration gradients.     

东海季节性低氧海区柱状沉积物中氧化还原敏感元素对沉积环境变化的响应

氧化还原敏感元素(Redox Sensitive Elements，RSE)如V、Cr、Mo、U等，通常在氧化条件下呈溶解态，在还原沉积环境中除Fe、Mn外，RSE被还原成低价态转移至沉积物中富集积累，因此可以利用氧化还原敏感元素在沉积物中的富集情况反演沉积环境的氧化还原状况。本文通过研究东海内陆架季节性低氧海区Zb7沉积柱中氧化还原敏感元素V、Cr、Ni、Cu、Zn、Mo、U的垂直分布、富集特征和比值，探究沉积环境氧化还原状况；发现RSE/Al和富集系数自1978年以来呈增加的趋势，但自2009年开始有所降低，整体RSE富集系数均小于3，未见明显富集。RSE比值V/Cr<2、Ni/Co<5、U/Th<0.75、0.25<(Cu+Mo)/Zn<0.55，以及Mo_EF/U_EF比值主要分布在0.08～0.3倍海水Mo/U值之间，均指示氧化的沉积环境。RSE/Al与Fe/Al、Mn/Al具有显著的相关性，表明RSE在剔除陆源碎屑输入后，主要通过与Fe、Mn氧化物结合进入沉积物，也指示氧化的沉积环境。研究结果与该区域溶解氧历史数据反映的季节性低氧结果不一致，可能与RSE在夏季季节性低氧时，沉积物中的富集信号在秋冬季溶氧水平恢复后缺失有关。尽管RSE不能有效指示东海季节性低氧环境，但Zb7沉积柱RSE在1978年后富集程度的增加以及2011年后的降低，在一定程度上反映了该区域自1978年后季节性低氧程度加重，2009年后又有所缓解的变化趋势。     

Phosphorus and metals bound to organic matter in coastal sediments - An investigation of complexes of P,Cu, Zn,Fe, Mn,Ni, Co and Ti by inductively coupled plasma-atomic emission spectrometry with sephadex gel chromatography

Phosphorus and metals bound to organic matter were separated from coastal sediments of Harima Sound in Seto Inland Sea, Japan by extraction with NaOH and fractionated by Sephadex G-25 chromatography. Phosphorus and metals were determined in the eluates by a multi-channel, inductively coupled plasma-atomic emission spectrometer. Phosphorus and Cu, Zn, Fe, Mn, Ni, Cr, Co and Ti bound to organic matter with high molecular weights (OMHMW) (MW ? 5000) were found to be present in the sediments, but no Mo or V were found. The technique provides minimum estimates of the amounts of P and metals bound to organic matter. These organic complexes show surface enrichment in a sediment core (0–20 cm) and their contents decrease with depth. Also, the amounts of eighteen elements, namely: P, Fe, Mn, Zn, Cu, Si, Al, Ti, Pb, Co, Ni, Cr, Mo, V, Na, K, Ca and Mg, in H₂O, ammonium acetate at pH 7 and 5, hydrogen peroxide, hydroxylamine hydrochloride and hydrogen fluoric acid soluble fractions have been determined with a selective chemical leaching technique for the ²¹⁰Pb-dated sediment core sample. Considerable amounts of P (6–19%) and Cu (5–21%) were associated with organic matter, in contrast to other metals such as Fe, Mn, Zn, Ni, Cr, Co and Ti which were associated with sulfide and silicate.     

Geochemistry of eastern Mediterranean sediments: Primary sediment composition and diagenetic alterations

Two cores recovered in the eastern Mediterranean were analysed for major, minor and trace elements. The primary chemical composition of the sediment is different at each location, probably because the lithological sources and the relative biogenic contributions differ.

Carbonates are important for the concentration of Ca, Mg and Sr, whereas aluminosilicates determine the concentration of Si, Al, K, Li, Y and Be, and to a lesser extent that of Fe, Cr, Ti, Mg, Zn and Zr. In sapropels, organic carbon and sulphur seem to be closely related. Bromine, Mo, P, Fe, V, Cu, Zn, Co, Ni and Cr are closely associated with organic and sulphidic compounds. The concentration versus depth profile for organic carbon in two sapropels points to a rapid establishment of conditions that gave rise to sapropel formation, followed by a gradual transition back to “normal” conditions.

The primary composition is overprinted by diagenetic processes. Sulphate-reducing conditions occurred during and just after sapropel deposition. A progressive oxidation front mechanism, which became active after sapropel deposition, is responsible for additional major geochemical changes. This diagenetic phenomenon has strong implications for the chemistry of Fe, Mn, Ni, Co, Zn, Cu, Cr, V, U, As and Sb.     

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.     

Elemental mass-balance of material carried by major world rivers

An estimate of average river particulate matter (RPM) composition was bàsed on analyses of more than 40 elements in the Amazon, Congo, Ganges, Magdalena, Mekong, Parana and Orinoco rivers, to which were added literature data for 13 other major world rivers, covering the whole spectrum of morphoclimatic features. Geographic variations of major elements in RPM are mostly linked to weathering types and to the balance between weathering rate and river transport. As a result of chemical erosion, Al, Fe and Ti are enriched in RPM with respect to the average parent rock, while Na, Ca, Mg and Sr are strongly depleted. These figures are directly related to the relative importance of dissolved and particulate transport in rivers; this has been computed for each of 40 elements. In order to study weathering on a global scale, the total observed elemental fluxes (dissolved + particulate) have been computed and compared to theoretical ones. The latter were derived from the elemental content in the average parent rock and the total quantity of weathered material, computed from the Al ratio in RPM and in parent rock. Observed and theoretical fluxes are balanced for the less mobilized elements (rare earths, Co, Cr, Cs, Fe, Mn, Rb, Si, Th, Ti, U and V) for which no enrichment relative to Al is noted in RPM, and for B, Ba, Ca, K, Mg, Na, Sr which are relatively depleted in RPM due to their high dissolved transport. Additional fluxes have been found for Br, Sb, Pb, Cu, Mo, Zn and are possible also for Ni and P. This is reflected by marked enrichments in RPM relative to Al for the poorly or moderately dissolved transports (Pb, Cu, Zn). Several hypotheses involving either the natural origin (volcanic dust, marine aerosols, geochemical fractionation) or the artificial origin (worldwide pollution) are discussed to explain these discrepancies, assuming river transport and weathering either to be in a steady state on a global scale or not. However, none of them can fully account for these additional fluxes. It is most likely that these excesses have multiple origins, anthropogenic or natural or both. The comparison between RPM and deep-sea clay compositions emphasizes the prime influence of river input on oceanic sedimentation of Si, Al, Fe, Ti, lanthanides, Sc, Rb, V, etc. A few elements such as Zn, Sb, occur in excess in RPM as compared to deep-sea clays; in order to balance this excess, a remobilization of these elements out of the sediment can be considered. Finally, the enrichment of Co, Cu, Mn and Ni in deep-sea clays compared to RPM is discussed and attributed to several sources and processes.     

Accumulation Properties of Major and Trace Elements of the Subcolloidal Fraction of Bottom Sediments in the Marginal Filter of the Razdolnaya River (Amur Bay,Sea of Japan) under the Influence of Increased Runoff

Oceanology - The study reveals the distribution of contents of major (Si, Al, Fe, Mn) and trace elements (Ga, V, W, Th, Mo, U, Be, Y, Cd), Сorg, and clay minerals in the subcolloidal fraction...     

The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O₂H₂S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH₂S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe²⁺) and manganese (Mn²⁺) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO₃). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin.     

Vertical distribution of trace elements in the surface waters offshore Nova Scotia

Concentrations of the trace elements Fe, Al, Mn, Cu, Cd, Zn and Ni were measured in shallow vertical profiles (maximum depth 500 m) off the Scotian Shelf in the western North Atlantic. The distributions of the trace elements show variations with depth, the most consistent of which are for Fe and Zn. A minimum concentration near the surface followed by an increase with depth is attributed to in situ mechanisms.     

Elemental composition of zooplankton in the Kara Sea and the bays on the eastern side of Novaya Zemlya

The chemical composition of zooplankton in the Kara Sea Basin has been studied. Independent samplings of the open sea and the Blagopoluchie and Tsivol’ki bays of Novaya Zemlya testify to the similarity of the distribution pattern of all the studied elements. The chemical composition of samples is predominated by organic carbon (49.5 ± 4.8% of dry weight). The other most important constituent elements are Na, P, S, K, Mg, and Ca. Their average total concentrations are 4.82 ± 0.1%. From an analysis of the composition of major and trace elements of zooplankton in the Kara Sea and the bays of Novaya Zemlya, three groups of elements have been specified: with similar (С_org, K, S, P, Al, Ti, Sc, Cd, Se, Cs, and Rb), lower (Na, Ca, Mg, Fe, Mn, Zn, Sr, Ba, B, Cu, Pb, Cr, Ni, V, Co, Sb, Mo, Ag, Be, Ga, and Hg), and higher (Li, As, and U) contents compared to their mean concentrations in ocean zooplankton.     

A study of the geochemistry of suspended particulate matter in coastal waters

The concentrations of Si, Al, Ti, Fe, K, Ca, Mg, P and Mn, before and after chemical leaching, in particulate matter from waters off the west coast of Scotland have been measured in vertical profiles at two seasons. The distribution of Si and Ca are shown partly to reflect temporal changes in biological production in different waters. The distributions of Al, Ti, Fe, K and Mg have been used to distinguish different sources and types of suspended alumino-silicates, and to trace probable circulation patterns in the water mass.While Si and Ti contents of the particulate matter are unaffected by mild chemical leaching, large amounts of other elements, notably Mg, K and Al, can be removed by this treatment. Presumably, these losses indicate preferential release of these elements from octahedral and interlayer sites in clay mineral lattices.The distribution of particulate P covaries with non-silicate Fe in the surface waters, while in bottom waters, high concentrations of particulate Fe and Mn are associated. The relationship of Fe and P is considered to be due to the presence of particulate ferriphosphates derived from runoff. The particulate Mn and Fe in deep waters is produced by the precipitation of dissolved metals released from bottom sediments by diagenesis.     

红树植物红海榄叶化学组成研究

对红树植物红海榄叶的基本化学成分水分,灰分,灰分中酸不溶物,灰分中S(SO42-),粗蛋白,粗脂肪等及氨基酸和微量元素的组成和含量进行了系统的分析测定。其基本化学组成各成分含量分别为:水分(69.18%),灰分(3.04%),灰分中酸不溶物(0.094%),灰分中S(SO42-)(0.052%),粗脂肪(7.75%),粗蛋白(7.14%);测得了红海榄叶中17种氨基酸,其总含量为10.7mg/g,其中人体必须氨基酸有7种,占所含氨基酸总量约26%;采用全谱直读等离子体原子发射光谱仪对红海榄叶进行了31种微量元素的分析测定,测得了其中18种元素的含量,红海榄叶中含有丰富的人体必须的矿物质元素。     

Processes affecting the behavior of dissolved aluminum in estuarine waters

Although it is well-known that reactions occur within estuaries to alter the flux of dissolved aluminum from rivers into the oceans, the nature and relative importance of these reactions are not well defined. In this study we show that sediment-water interactions can have a significant influence on dissolved Al distributions in estuaries. Undisturbed sediments will act as a sink for dissolved Al because of diffusion across the sediment-water interface and reaction of Al within the sediment. Resuspension of sediments will cause a release of dissolved Al into relatively Si-depleted estuarine waters.Flocculation of colloidal material may cause a net consumption of dissolved Al in estuaries. Our results indicate, however, that this process may not, in many cases, be the primary cause for curvature in Al-Cl^? profiles. An alternative model, whereby Al is displaced from organic matter complexes and adsorption sites in the estuarine zone and reacts with Si and cations in solution, is consistent with the data presented in this study as well as many other studies. In this case, the extent of net Al removal in estuaries will be determined by both the amount and nature of the dissolved organic matter present.     

顺序扫描 ICP-AES法测定高纯石墨灰分中14种杂质金属元素的方法研究

本文研究了快速测定石墨灰分中14种杂质元素Al,Ca,Cd,Co,Cr,Cu,Fe,Mg,Mn,Mo,Ni,Ti,V,Zn的分析方法,以满足提纯石墨研究工作对快速了解石墨提纯效果的要求.依据测定样品中各元素的含量情况,实验选择14种元素的分析线.运用ICP-AES谱线轮廓图功能,消除常量元素产生的基体背景干扰.运用干扰系数法进行测定结果校正,并对ICP-AES测定灰分中14种元素的检出线、精密度、准确度进行了测定.结果显示,本方法分析石墨灰分中杂质元素能够满足提纯石墨研究工作的要求.     

Profiles of dissolved and acid-leachable selenium in a sediment core from the lower St. Lawrence estuary

Concentrations of Se in the pore-water and in the solid phase, and the concentrations of other diagenetic constituents (Fe, Mn, phosphate, ammonium and I) in pore-water, were determined in a sediment core from a 350-m deep station in the lower St. Lawrence Estuary. The concentration of dissolved Se in pore-water was 2.1 nmol kg⁻¹ at the surface of the core, increasing to a maximum of 7.6 nmol kg⁻¹ at a depth of 12 cm, and thereafter decreasing gradually with depth. This profile is similar to the profiles of Fe and phosphate, whose concentration maxima occur around 10 cm. The concentration of total sedimentary Se remained almost constant with depth (≈ 0.75 mg kg⁻¹); however, a significant enrichment of oxalate-leachable Se was observed in the top 2 cm. The sedimentary cycling of Se appears to be closely related to that of Fe: adsorption of Se onto Fe oxyhydroxide at or near the sediment-water interface, release of the adsorbed Se by the reduction of Fe oxyhydroxide, and removal by formation of ferroselite (FeSe₂) at depth. The pore-water flux of Se was estimated by two different methods, firstly from the pore-water gradient, and secondly by applying a box model to the oxalate-leachable solid-phase Se data. The methods agree well both giving values for the flux of 0.11 nmol cm⁻² year⁻¹. This agreement suggests that the loss of labile Se in the sediment is balanced by the upward flux of dissolved Se.     

Accumulation of Subcolloidal Fraction Elements of Bottom Sediments in Amur Bay (Sea of Japan)

Oceanology - The mean contents of elements (Fe, Mn, Zn, Pb, Cu, Cr, V, Co, Cd, Ni, As, Sc, Ga, Zr, Hf, Nb, Ta, W, Th, Mo) in the subcolloidal fraction of bottom sediments in the northern part of...     

青海湖裸鲤的无机元素

１９８９年５月及１０月测定青海湖主要经济鱼类青海湖裸鲤Ｇｙｍｎｏｃｙｐｒｉｓ ｐｒｚｅｗａｌｓｋｉｉ ｐｒｚｅｗａｌｓｋｉｉ（Ｋｅｓｓｌｌｅｒ）不同性别，９种组织中的人体及动物必需常量元素６种，微量元素１０种的含量。存在不同组织、性别、季节及年份的差异。雌鱼常量元素总量是骨＞鳞＞鳃＞肝＞肌肉＞肠＞心＞卵巢＞皮；微量元素总量肠＞鳞＞心＞鳃＞骨＞肝＞皮＞卵巢＜肌肉。雄鱼常量元素总量是骨＞鳞＞鳃＞皮＞精     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Spatial distribution and corresponding determining factors of metal concentrations in surface sediments of Beppu Bay, southwest Japan

This study determined the factors contributing to the spatial distribution of 14 metal concentrations in the surface sediments of Beppu Bay on the basis of comparisons of the organic geochemical properties and environmental parameters through principal component analysis (PCA) and redundancy analysis (RDA). The results of PCA and RDA showed that the concentrations of V, Cr, Co, and As were closely related to the distances between the sampling sites and the Oita River. This indicated that these metals originated from the river's drainage area. The Mn, Cu, Mo, and Cd concentrations were related to the water depth. These results indicated that the Mo, Cd, and Cu deposition processes were controlled by oxygen depletion, and that these elements accumulated in the deeper parts of the bay under anoxic conditions.     

Vertical distribution of various elements in sediment cores from the Japan Sea

Deep-sea sediment cores ranging up to 30,000–80,000 yrs in age were taken from a southern region of the Japan Sea and subjected to analyses for 5 major and 11 trace elements by means of instrumental photon activation analysis with 30 MeV bremsstrahlung. These elements were Ca, Fe, Mg, Na, Ti, Ba, Ce, Co, Cr, Mn, Nb, Ni, Rb, Sr, Y and Zr. Additionally, Al was determined spectrophotometrically. Distribution patterns of these elements with depth in the sediment columns were derived. Enrichments of Ca and Sr by biogenous process were observed; these Ca maxima are well correlated with Mn maxima. Below the Holocene—Pleistocene boundary, continuous transportation of poorly degraded continental debris, which was low in metallic constituents, was noted. A distinct enrichment of the top layer of the sediments in Mn was observed. This is the result of post-depositional upward migration of Mn. Fe, Co and Ni were also enriched in the top layers. In the central part of the basin, the oxidized post-glacial zone appears to be a typical pelagic sediment.