青岛近海秋末冬初悬浮颗粒物中部分金属元素的组成与影响因素研究

2008年11月末在青岛近海和胶州湾11个站点采集表层和底层海水中的悬浮颗粒物(SPM)样品,经消解后用等离子体发射光谱法测定了Al、Ca、Fe、Mg、Mn、Ti和Ba、Co、Cr、Cu、Ni、Pb、Sr、V、Zn共15个金属元素以及P的含量,结合SPM和元素含量聚类分析的结果探讨了秋末冬初青岛近海SPM的来源以及金属元素组成的影响因素.SPM含量范围在1.7～16.1mg/L之间,平均为7.9 mg/L;SPM来源以陆源风化产物为主,生物生产有较小的贡献.SPM中Ti、Fe、Mn、Mg、Al、V、Co、Sr和Ni的含量相对恒定,且主要受陆源输入的控制;Ca和P除受陆源影响外,生物生产亦有附加贡献.离陆地相对较远的区域表层海水SPM中Pb、Zn和Ba、Cr、Cu的含量较高,特别是Pb和Zn的富集因子较大,可能受到了潜在的污染影响.Ti的恒定性以及与SPM的良好相关性代表着在青岛近海可用Ti作为颗粒物陆源指示元素,且优于Al.     

Major- and trace-element composition of suspended matter in the north-east gulf of Alaska: Relationships with major sources

Seasonal variations of the distributions and chemical compositions of suspended particulate matter in the north-east Gulf of Alaska were studied during 1975–1976. Selected samples were analyzed for total suspended matter by gravimetry; particulate C and N by dry combustion gas chromatography; and particulate Al, Si, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu and Zn by thin-film X-ray secondary emission spectrometry. The results showed that suspended material from the Copper River and the coastal streams which drain the Bering, Guyot, and Malaspina glaciers was carried westward along the coast and deposited in nearshore environments. However, near Kayak Island, significant quantities of suspended material of terrestrial origin were deflected to the south-west, past the edge of the outer shelf, by an anticyclonic gyre.The distribution patterns of the major and trace elements in the particulate matter and their elemental ratios with aluminum indicated that: K, Ti, Mn and Fe were primarily associated with aluminosilicate material and C and N with organic material in all samples; and Si, Ca, Cr, Ni, Cu and Zn were primarily associated with aluminosilicate material in near-shore surface and near-bottom samples and with organic material in offshore surface samples. Only C, N, Ca, Cú and Zn showed significant seasonal variations which appeared to be related to biological production of organic matter.     

东海陆架晚第四纪沉积物化学成分及物源示踪

东海陆架EA1孔和EA5孔沉积物化学成分变化范围较大。与东海陆架表层沉积物相比，钻孔沉积物的Si,Al,Mg,Mn,Ti,P,Ba,Zr,Co,Ni,Cu,Zn,Cr明显偏高，而Fe,Na,Ca,Sr,Li,U明显偏低，与全球大陆地壳化学组成相比，钻孔沉积物的Si,Li,Rb,Ba,Th,Zr,Hf,Cu,Zn,Pb偏高，而Al,Na,Ca,Mg,Fe,Mn,Ti,P,Sr,U,Co,Ni,V,Cr偏低，钻孔沉积物的化学成分在垂向上具有明显变化，主要受岩性和沉积环境的控制，钻孔沉积物中元素的富集因子（EF）均小于10，接近于1，表明钻孔沉积物主要来自大陆地壳，一些元素因分异或外来物质加入而富集，一些元素则因分异带出而亏损，钻孔沉积物源区的DF值判别表明，钻孔沉积物与现代黄河，长江沉积物均有亲缘关系，可能是在末次冰期最盛期，由于气候带南移，干旱区域扩大，在古长江搬运沉积物中类似现今黄河沉积物的干旱组分明显增加，从而导致了地球化学示踪结果的长江与黄河双重性，或者说古气候的变化导致了古长江搬运物质成分的变化。     

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.     

南海铁锰结核(壳)的元素地球化学研究

本文利用南海11个铁锰结核(壳)样品的化学分析资料,研究了铁锰结核(壳)中Fe,Mn,Cu,Co,Ni,Pb,Zn,Cr,K,Na,Ca,Mg,Si,P,Al,Ti,Sr,Ba及∑REE的元素地球化学特征。结果表明:(1)铁锰结核(壳)以高Fe,∑REE,低Mn,Cu,Co,Ni等元素为主要特征;(2)铁锰结核(壳)中Fe,Mn间无明显相关,而Fe与∑REE,∑Ce,∑Y呈弱的正相关,Mn与∑REE,∑Ce,∑Y呈明显的正相关,结壳中Fe,Mn与Si,Al,Cu Co Ni呈负相关;(3)结核(壳)中Mn/Fe与Cu/Ni,Ce/La呈负相关,Mn/Fe主要受Mn控制;(4)结核(壳)中Fe,∑REE等元素主要来自南海陆源中酸性岩类的风化、淋滤和沉积。     

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。     

Factors influencing particulate matter geochemistry in the St. Lawrence estuary turbidity maximum

635 samples of suspended particulate matter (SPM), collected in the St. Lawrence river and estuary during periods of high and low river flow from a series of individual and anchor stations on a transect traversing the turbidity maximum zone, as well as two sediment box cores, were analyzed for Al, Si, Ca, Mg, Fe and Mn.An abrupt change in elemental composition occurs when traversing the front at the landward edge of the turbidity maximum. As the SPM concentration increases across the front from 20–200 mg l^?1, the Ca/Al and Mg/Al ratios of the SPM increase and the Si/Al, Fe/Al and Mn/Al ratios decrease. The almost 50% decrease of the Mn/Al ratio is not related to changes in salinity. Within the turbidity maximum the tidal-averaged Si/Al, Ca/Al, Mg/Al and Fe/Al ratios of the SPM do not differ significantly from the landward to the seaward end of the turbidity zone, but on one tidal station the ratios of Si, Ca and Fe to Al are significantly lower at high river flow than at low flow. The Mn/Al ratio is insensitive to the extreme variations of either salinity (0.6–30‰) or SPM concentrations (10–480 mg l^?1) within the turbidity zone. A tendency for higher Mn/Al ratios to be associated with near-bottom SPM, observed in the center of the turbidity zone during the low river flow period, is well developed in the lower reaches of the zone.Diagenetic mobilization within the rare fine-grained bottom sediments of the turbidity maximum is responsible for changes in Mn and Fe content of particulate matter, and early settling of coarse-grained components and size sorting within the zone are responsible for other compositional changes. Local sources, desorption and precipitation are apparently of secondary importance. The depletion of both Mn and Fe in the SPM and sediment of the upper estuary implies a net seaward escape of diagenetically mobilized metal.     

Methodology of X-ray fluorescence analysis of suspended matter in estuarine waters

Twenty-seven samples of suspended sediments collected on Millipore filters from the St. Lawrence estuary were directly analysed for Si, Al, Ca, Mg, Na, K, Fe, Ti, Mn, Ni, Co, Cu, Cr and Zn by X-ray fluorescence using standards prepared from suspended matter collected by continuous flow centrifugation. Calibration curves prepared from the analysis of these standards could be directly used in calculating the weight percent of elements for the unknown samples, if the weight of the total suspended matter on the filters did not exceed 25 mg.     

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.     

The geochemistry of deepwater particulate matter over the hydrothermal field at 9°d50′ N (the East Pacific Rise)

The results of geochemical studies of particulate matter in the water mass over the hydrothermal field at 9°50′ N on the East Pacific Rise are presented. The particulate matter was tested in background waters, in the buoyant plume, and in the near-bottom waters. The contents of Si, Al, P, C_org, Fe, Mn, Cu, Zn, Ni, Co, As, Cr, Cd, Pb, Ag, and Hg were determined. No definite correlations were found between the ele-ments in the background waters. Many of the chemical elements correlated with Fe and associated with its oxyhydroxides in the buoyant plume. In the near-bottom waters, microelements are associated with Fe, Zn, and Cu (probably, to their sulfides formed under fluid mixing with seawater). The matter precipitated in a sed-imentation trap was similar to the near-bottom particulate matter in the elemental composition.     

Selective removal of trace elements from the Baltic by suspended matter

Suspended matter was collected at 30 stations in the Baltic and Kattegatt, at the thermocline and at the bottom, and analysed for Na, Ca, Mg, Si, Ti, Al, Fe, Mn, Ba, Sr, Ni and V. The composition of the suspended matter varies considerably, but can be described as a mixture of: (1) 12–25% terrigenous detritus with much Si, Al, Ti and Fe; (2) 75–88% biological matter with much Ni, V and Ba; and (3) some Mn-oxyhydroxide.The annual efflux of water from the Baltic is about 460 km³, with a suspended load in the Baltic straits of ～1.2–3.6 mg ash material l^?1 These values imply that much Si, Ti, Al, Fe, Sr, Ni and V and particularly much Ba and Mn are lost from the Baltic in the suspended load.The average suspended matter is richer in Mn(5×), Ba(2.5×), Sr(4×) and V(1.8×) than permanently depositing Baltic sediments. These constituents are relatively enriched in pelagic deposits, i.e. it is likely that much Mn, Ba and V in deep-sea sediments derive from the continents via suspended transport. This conclusion is supported by the similarity between suspended matter and average Atlantic pelagic sediment.     

中太平洋北部锰结核的主要元素化学

本文测定了中太平洋北部锰结核的主要化学元素的含量。研究表明,元素的含量分布与组成锰结核的主要矿物有关;与共生元素及渗入锰结核中的粘土矿物和其他碎屑矿物有关。文中还指出了锰结核中富Mn贫Ca,沉积物中富Ca贫Ti,而沉积物对Ca的富集又与海洋生物相关。同时说明,Mg在锰结核与沉积物之间的交换比例约为1∶1。锰结核区的海水深度、pH和Eh值的大小对锰结核的形成产生重要影响。     

Composition of the inorganic fraction of the particulate organic matter in seawater

Na, K, Mg, Ca, Fe, and Mn have been measured in both naturally occurring particulate matter and artificially created aggregates taken from water from the Nova Scotian coastal region and from the North Atlantic Ocean. The order of concentration of these elements is the same in both the aggregates and the natural particulate matter as it is in seawater. There is an inverse relationship between depth of the water and the amount of inorganic matter in artificially created aggregates, while a direct relationship is found with the naturally occurring particles. This direct relationship may reflect the utilization of organic material in the surface waters. Iron and manganese are enriched in both kinds of particles.     

顺序提取法探讨沉积物中主量元素在不同相态的分配特征

在Tessier以及欧共体标准局BCR等前人顺序提取方法的基础上,采用一套改进的顺序提取法对海洋沉积物以及一些水系沉积物标准物质的主量元素进行逐步提取。利用ICP—AES、ICP—MS方法分析了各提取液中Ti、A1、Na、Mg、K、Ca、P、Fe、Mn的含量以及它们在不同相态的分配特征,同时,进一步探讨了酸去除沉积物中非陆源组分的效果,结果显示,最后经盐酸淋滤后的样品,沉积物中的生物、自生组分已经被溶解,而残留下来的剩余物质基本上可代表海洋沉积物的陆源碎屑组分。     

青藏高原东北部黄土沉积化学风化程度及古环境

通过对青藏高原东北部西宁盆地大墩岭剖面24种常微量元素的测定及数据的处理分析，研究了该地区黄土沉积的化学风化程度及某些地球化学特征。相对上部陆壳(UCC)元素平均值，大墩岭剖面显著富集Ca、Mg、Ti、V、Cr、Ni、Y、Zr等，而亏损Si、Al、K、Na、Sr、Nb等；相对于中国黄土(CL)元素平均值，大墩岭剖面明显富含Fe、Ca、Mg、K、Ti、Cr、Mn、Cu、Rb、Sr、Nb、Ba和P，而Si、Na、Co、Ni、Pb则表现为亏损；在UCC标准化图与CL标准化图中，大墩岭黄土与古土壤变化趋势基本一致。大墩岭剖面尚处于脱Ca、Na的大陆风化初期阶段。与其他地区的风尘沉积相似，大墩岭黄土沉积很可能也起源于上部陆壳，但不排除物源存在一定差别。风尘堆积时该区的气候环境比黄土高原要干冷，这与青藏高原第四纪以来的强烈隆升有直接关系。     

晚第四纪南海北部陆坡沉积物常量元素比值对气候变冷事件的指示意义

南海北部陆坡柱状沉积物的常量元素统计分析表明, 沉积物中的Ti、Al、Fe、K、Mn、Mg代表了陆源元素组合;而消除粒度效应的陆源元素比值Al/Ti、Fe/Ti和K/Ti等的变化曲线与浮游有孔虫氧同位素曲线对比表明, 在气候变冷事件(Heinrich事件、Younger Dryas事件、PME斜室普林虫低值等事件)期间, 陆源常量元素比值明显降低。这一对应特征, 一方面体现了气候变冷事件的发生对陆源区化学风化强度的制约, 另一方面也说明与指示长时间尺度气候相似, 陆源元素比值对短时间尺度的气候变化也具有明显的指示作用。     

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.     

Particle transport from the West African shelves of Liberia and Sierra Leone to the deep sea: A chemical approach

The chemical and mineralogical composition of suspended particle suites has been used to assess off-shelf transport on the West African shelves of Liberia and Sierra Leone. Using the ratios of Si/Al, Fe/Al, Mg/Al and Mn/Al as tracers, it was possible to detect shelf-derived materials in slope waters. In the majority of cases, these inputs could not have been detected using particle mass or light scattering measurements and could only be measured by using the chemical signatures of the particulate matter. At the time of sampling, the suspensate which had been moved seaward over the slope was detected adjacent to submarine canyons and highly turbid areas on the outer shelf. The chemical and mineralogical composition of the suspensates, and sediments in the adjacent eastern Atlantic basin are similar to those found in the water column seaward of the West African continental shelves and yet distinct from the Sahelian dust which is considered the major source of sedimentary material for the tropical and semi-tropical areas of the deep eastern basin. These findings suggest that materials from this shelf area could be a more important input to the deep sea than was previously realised.     

Summer distribution and geochemical composition of suspended-particulate matter in the east china sea

The distribution and geochemical composition of suspended-particulate matter (SPM) in the East China Sea (ECS) were investigated during the summer period of high continental runoff to elucidate SPM sources, distribution and cross-shelf transport. The spatial variability of SPM distribution (0.3–6.5 mg l⁻¹) and geochemical composition (POC, Al, Si, Fe, Mn, Ca, Mg and K) in the ECS was pronounced during summer when the continental fluxes of freshwater and terrestrial materials were highest during the year. Under the influences of Changjiang runoff, Kuroshio intrusion, surface production and bottom resuspension, the distribution generally showed strong gradients decreasing seaward for both biogenic and lithogenic materials. Particulate organic carbon was enriched in surface water (mean ∼18%) due to the influence of biological productivity, and was diluted by resuspended and/or laterally-transported materials in bottom water (mean 9.4%). The abundance of lithogenic elements (Al, Si, Fe, Mn) increased toward the bottom, and the distribution correlations were highly significant. Particulate CaCO₃ distribution provided evidence that the SPM of the bottom water in the northern part of the study area was likely mixed with sediments originally derived from Huanghe. A distinct benthic nepheloid layer (BNL) was present in all seaward transects of the ECS shelf. Sediment resuspension may be caused by tidal fluctuation and other forcing and be regarded as the principal agent in the formation of BNL. This BNL was likely responsible for the transport of biogenic and lithogenic particles across or along the ECS shelf. Total inventories of SPM, POC and PN are 46, 2.8 and 0.4 Tg, respectively, measured over the total area of 0.45 × 10⁶ km² of the ECS shelf. Their mean residence times are about 27, 13 and 11 days, respectively. The inventory of SPM in the water column was higher in the northernmost and southernmost transects and lower in the middle transects, reflecting the influences of terrestrial inputs from Changjiang and/or resuspended materials from Huanghe deposits in the north and perhaps from Minjiang and/or Taiwan’s rivers in the south. The distribution and transport patterns of SPM and geochemical elements strongly indicate that continental sources and cross-shelf transport modulate ECS particulate matter in summer.     

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.