Geochemistry of surface sediments in the southwestern East/Japan Sea

We analyzed 77 surface sediment samples collected in the southwestern East/Japan Sea from the Korea Strait through the Ulleung Basin and the Korea Plateau for grain size, calcium carbonate, organic carbon, and major (Na, Mg, Al, Fe, K, Ca, and Ti) and trace elements (P, Mn, Sr, Li, Sc, V, Cr, Co, Ni, Zn, Cu, and Pb).The chemical composition of the surface sediments was found to be highly variable spatially. Cluster analysis of surface sediment chemical compositions indicated five major geochemical sedimentary environments: basin, lower slope, coast and upper slope, inner shelf, and outer shelf. Continental-shelf sediments were rich in shell fragments and had relict and coarse-grained characteristics. Recent fine-grained sediments were only distributed in coastal, slope, and basin areas. Concentrations of Al, K, Ca, Ti, Cr, and Sc were highest in the coastal and upper slope areas and decreased with water depth. Elemental ratios using major and trace elements indicated that coastal and upper slope detrital sediments were mixtures of sediments derived from the Changjiang (Yangtze) and Nakdong Rivers. Although the concentrations of organic carbon, P, Mn, V, Co, Ni, Cu, and Pb increased with water depth, their distribution patterns indicated authigenic (V, Cu, and Pb) and diagenetic (Fe, P, Mn, Co, and Ni) origins. The distribution pattern with water depth suggested that the chemical composition of surface sediment was determined by sedimentologic and geochemical processes, such as the supply of detrital and biogenic materials, and authigenic and post-depositional diagenetic processes in sediments.     

Evaluation of elemental enrichments in surface sediments off southwestern Taiwan

Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO₂ versus Fe₂O₃^T suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C–S–Fe relationship owing to authigenic precipitation of Fe–Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.     

The Composition of Phosphatized Bones in Recent Sediments

Mineral and chemical compositions of bone phosphate were studied in two samples from the outer Namibian shelf sediments composed of fish skull fragments and whale ribbon. Fossilization of bones is accompanied by the accumulation of lithogenic components, iron, sulfur, rare earth and other trace elements (Ni, Cu, Co, Cd, Mo, La, Ce, Th, U, and others), whereas the organic and mineral carbon content decreases. The evolution of bone phosphate during fossilization consists in transition from primary hydroxylapatite to a gel-type material, which subsequently becomes globular and crystallizes as fluorcarbonate-apatite crystallites. Additionally, some authigenic minerals, including both relatively widespread minerals (pyrite, uraninite, and coffinite) and rare minerals (graphite and calcium and germanium oxides) are formed in the bones. A considerable proportion of uranium in bones consists of uranium minerals, which also contain rare earth elements.     

Molybdenum isotope composition from Yangtze block continental margin and its indication to organic burial rate

The paper presents the molybdenum isotope data, along with the trace element content, to investigate the geochemical behavior of authigenic Mo during long-term burial in sediments in continental margin settings of the Yangtze block, as well as their indication to the burial of original organic carbon. The burial rate of original organic carbon was estimated on the basis of the amount of sedimentary sulfur (TS content), whilst the carbon loss by aerobic degradation was estimated according to calculated Mn contents. On these points, the original organic carbon flux was calculated, exhibiting a large range of variation (0.17–0.67 mmol/m²/day). The strong correlation between sedimentary Mo isotope values and organic carbon burial rates previously proposed on the basis of the investigations on modern ocean sediments, was also used here to estimate the organic carbon burial rate. The data gained through this model showed that organic carbon burial rates have large variations, ranging from 0.43–2.87 mmol/m²/day. Although the two sets of data gained through different geochemical records in the Yangtze block show a deviation of one order of magnitude, they do display a strong correlation. It is thus tempting to speculate that the Mo isotope signature of sediments may serve as a tracer for the accumulation rate of original organic carbon in the continental margin sediments. __________ Translated from Earth Science—Journal of China University of Geosciences, 2007, 32(6) [译自: 地球科学—中国地质大学学报]     

Arsenic and presumed resistate trace element geochemistry of the Lincolnshire (UK) sedimentary ironstones,as revealed by a regional geochemical survey using soil,water and stream sediment sampling

A regional geochemical survey using soils, stream sediment and stream water sampling revealed multi-element geochemical anomalies, though of low environmental mobility, associated with Mesozoic sedimentary ironstones in Lincolnshire, UK. The most prominent of these anomalies were of As and V in soils and sediments, but elevated levels of elements such as Cr, La, Ce and Th were also observed. These were initially thought to be part of a residual resistate element or heavy-mineral suite, but careful examination suggests that these too may be primarily associated with the process of Fe oxide precipitation during the initial formation of the ironstones.     

Enrichment of trace metals in surface sediments from the northern part of Point Calimere, SE coast of India

This study deals with the geochemical nature of distribution, enrichment of total trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd) in bulk sediments and its association with sediment texture, carbonates and organic carbon. Sixty surface sediment samples were collected during two different seasons in 2002 and 2003 along the coastal regions in three transects from Nagapattinam town, north of Point Calimere in southeast coast of India. The sediments are mostly sandy silt and are dominated by the carbonate content. Organic carbon distribution indicates that they are brought in by the minor river input. Enrichment of trace metals is clearly identified by the domination of Pb, Zn, Cd with high values than the average crustal values and comparison of trace metals from other coastal regions in the southeast coast of India. Statistical analysis clearly indicates that Fe and Mn control the distribution of trace metals and are concentrated in the finer particles and organic carbon fraction. The increase in concentration signifies the need for regular monitoring of the offshore coastal region in southeast coast of India which was recently destroyed by the 2004 December tsunami event, and which is also located near the Sethu Samuthram Ship Canal Project.     

Distribution of trace elements in fracture fillings from the “Mina Fe” uranium deposit (Spain) by sequential leaching: implications for the retention processes

Sequential leaching methods have been used to determine the mineralogical distribution of some trace elements for environmental purposes, such as radiological contamination of soils and sediments, bioavailability studies and natural analogues of deep geological radwaste disposals. In this context, a 7-step-sequential leaching protocol is applied to Fe(III)–U(VI)-rich fracture filling materials from the oxidised zone of the “Mina Fe” U deposit to identify and evaluate the main sinks of natural nuclides and other analogue trace elements, since it is crucial in the performance assessment of a nuclear waste repository.After a careful characterisation of the samples, the analytical data from each leaching step were statistically analysed and then interpreted in light of the mineralogical and geochemical features of the samples. Precise knowledge of the mineralogical distribution of trace elements by sequential leaching methods is quite complex, mainly due to cross-contamination throughout the different steps of the experiments. Thus, the results obtained suggest that U is retained as U-minerals, mainly oxides, closely associated with crystalline Fe-oxyhydroxides. Though Ce and La also form independent compounds, such as Ce oxides and La–Nd phosphates, they are mainly retained by the amorphous Mn-oxyhydroxides. However, the crystalline Mn-oxyhydroxides are the main sink for Ni and crystalline Fe-oxyhydroxides mainly retain P.     

Geogene Versus Anthropogene Origin of Trace Metals in Sediments in Cua Luc Estuary and Ha Long Bay, Vietnam

In the present study, the geochemistry of 49 surficial-bed and 101 core sediment samples is investigated to clarify the origin of trace metals in the Cua Luc Estuary and Ha Long Bay, which is a famous World Natural Heritage Site in Vietnam. Moreover, the potential mobility of trace metals is also assessed and their relationship with reference elements (Al, Fe, and Ca) and organic matter is established in order to make recommendations for sediment management and monitor future pollution. Generally, trace metals display higher concentrations in Ha Long Bay compared to the Cua Luc Estuary. However, this is controlled by the distribution of the fine (clay?+?silt) fraction, and hence the concentrations of Al, Fe, Ca, and organic matter (OM). The comparison of concentrations of trace metals (normalized towards Al) between the surficial sediments and the subsurface core sediments based on ¹³⁷Cs datings indicates that almost all surficial-sediment data fall inside or deviate slightly from the 95 % prediction interval of a background regression line. In addition, as determined by a Community Bureau of Reference three-step extraction, trace metals mainly dominate in the residual fraction (assumed to relate to crystal lattice of primary and secondary minerals), and this fraction does not change much in recent sediment layers. Therefore, trace metals are supposed to be derived from natural bio/geochemical processes and are characterized by a low potential mobility. Consequently, the established linear regression relationships of trace metal vs. Al or multiple regression relationships of trace metal vs. multi-elements (Al, Fe, Ca, and OM) are useful for the prediction of background levels of trace metals in sediments in future pollution monitoring and assessment programs.     

南极普里兹湾表层沉积物微量元素分布特征及其物源指示意义

利用电感耦合等离子体质谱仪测定了中国南极科考21~27航次期间获取的普里兹湾表层沉积物中Cu、Pb、Zn、Cd、Cr、Co、Al、Fe、Mn的含量,分析了普里兹湾微量元素的分布特征,结合沉积物粒度分布、生物硅含量,并利用富集系数和主成分分析的方法,探讨了微量元素的物源指示意义。研究结果表明:普里兹湾沉积物中的微量元素含量与南大洋其他海域具有很好的可比性。Cu、Zn、Cr、Co、Fe、Mn含量在陆坡深海区明显高于冰架边缘区和陆架区;Al、Pb含量在冰架边缘区较高;而Cd含量在陆架区相对较高。人类活动对普里兹湾沉积物中的微量元素没有明显的影响,南极大陆岩石风化产物和海洋生物源性沉降是其主要来源。冰架边缘区及陆架破折处P2-9站位的微量元素主要为岩源性输入。陆架区、陆坡深海区的微量元素Cu、Zn、Cr、Co、Fe、Mn明显受到生源性物质输入的影响。而普里兹湾沉积物中Cd则主要来源于硅藻的吸收利用及硅质软泥的富集。     

Trace element characterisation of Cretaceous Orange Basin hydrocarbon source rocks

Trace elements in the kerogen fraction of hydrocarbon source rock samples from two wells obtained from the Cretaceous units of the Orange Basin, South Africa were determined using X-ray fluorescence spectrometry, in order to determine their distribution and geochemical significances. The concentrations of the elements (As, Ce, Co, Cu, Fe, Mo, Ni, Pb and V) determined ranged from 0.64 to 47,300 ppm for the samples analysed. The total organic carbon (TOC) values indicate that the samples are organic rich but did not show any trend with the distribution of the trace metals except Ce, Mo and Pb. Dendrogram cluster analysis discriminated the samples into three groups on the basis of their level of thermal maturity. Thermal maturity has a significant effect on the distribution of the trace metals. Cobalt/Ni and V/Ni ratios and cross plots of the absolute values of V and Ni indicate that the samples had significant marine organic matter input. The V and Ni contents and V/(V + Ni) ratio indicate that the organic matter of the source rocks had been deposited in reducing conditions. Despite the similarities in the organic matter source input and depositional environment of the organic matter of the samples from the two well, cross plots of Co/Ni versus V/Ni and Mo/Ni versus Co/Ni were able to reveal subtle differences. Cluster analysis of the samples was also able to reveal the subtle thermal maturity differences of the samples.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

海洋沉积物早期成岩作用研究进展

海洋沉积物的早期成岩作用是其沉积和埋藏过程中发生的一系列生物、物理和化学变化,其驱动力为有机质的降解,根据反应自由能大小,参与反应的氧化剂顺序为:O₂>NO3->Mn4+>Fe3+>SO42-。随着埋深增加,形成一系列氧化—还原化学带,并推动着海底沉积物中部分自生矿物的生成及C、N、S、Fe、Mn等元素的地球化学循环和同位素分馏。一系列有机质降解反应会改变原生沉积物中保存的地球化学信息,对古环境和古气候的研究具有重要意义。在早期成岩作用过程中,有机质降解产生的碳酸根离子和钙离子、亚铁离子结合会形成方解石、文石、菱铁矿等碳酸盐矿物。硫酸盐还原产生的还原态硫最终与亚铁离子形成黄铁矿。此外,目前常用于氧化还原环境重建的代用指标有:1）Fe组分;2）C_org/P比值;3）氧化还原敏感微量元素;4）Mo、U同位素。围绕海洋沉积物早期成岩作用中的矿物和元素地球化学行为,评述了早期成岩作用过程中有机质降解反应机制,探讨了反应进程中发生的元素地球化学循环和同位素分馏,以及相伴生的碳酸盐矿物和黄铁矿等自生矿物的形成机理。最后,总结了现有研究的不足,并对未来的研究方向进行了展望。     

Secondary dispersion of trace elements in bottom sediments of the High Dam Lake,South Egypt and North Sudan

Thirty-four chemical elements, pH, total nitrogen, and total organic carbon were determined in 49 bottom sediment samples from the whole High Dam Lake in order to improve our understanding of geochemical characteristics of these sediments and geochemical patterns of trace elements and related feeding sources. The present study revealed that the lake were clearly discriminated into three portions in accordance with the sediment geochemistry and geographic position. Likewise, the analyzed elements in the entire lake sediments were classified into six geochemical association patterns that are indicative of the contributing geogenic and anthropogenic sources. As has been noted here, mineralogy, anthropogenic inputs, pH, and organic matter had significant roles in controlling the behavior, concentration, dispersion, and geochemical patterns of the trace elements in the lake sediments. Consequently, the elevated concentration of Bi, Cd, Co, Cr, Cu, Fe, Ga, Mn, Mo, Ni, Sc, V, Y, and Zn posed moderate contamination level in the sediments. At the same time, the enhancement of Ag, Se, and Te levels caused contamination up to very high levels. Admittedly, the contamination levels were generated by natural and human activities that are coming from the Nile basin countries. Despite progressive deterioration of these sediments, they still have economic applications.     

Heavy metal partitioning in river sediments severely polluted by acid mine drainage in the Iberian Pyrite Belt

This study provides a geochemical partitioning pattern of Fe, Mn and potentially toxic trace elements (As, Cd, Cr, Cu, Ni, Pb, Zn) in sediments historically contaminated with acid mine drainage, as determined by using a 4-step sequential extraction scheme. At the upperstream, the sediments occur as ochreous precipitates consisting of amorphous or poorly crystalline oxy-hydroxides of Fe, and locally jarosite, whereas the estuarine sediments are composed mainly of detrital quartz, illite, kaolinite, feldspars, carbonates and heavy minerals, with minor authigenic phases (gypsum, vivianite, halite, pyrite). The sediments are severely contaminated with As, Cd, Cu, Pb and Zn, especially in the vicinity of the mining pollution sources and some sites of the estuary, where the metal concentrations are several orders of magnitude above background levels. Although a significant proportion of Zn, Cd and Cu is present in a readily soluble form, the majority of heavy metals are bonded to reducible phases, suggesting that Fe oxy-hydroxides have a dominant role in the metal accumulation. In the estuary, the sediments are potentially less reactive than in the riverine environment, because relevant concentrations of heavy metals are immobilised in the crystalline structure of minerals.     

Geographical variations of trace elements in sediments of the major rivers in eastern China

 A total of 26 geographically and hydrologically diverse sediment samples were collected from 12 major rivers in eastern China. The <63-μm fraction of the sediments was analysed for both total concentrations of Cu, Zn, Pb and Cd, and their associations with various geochemical phases. The geographical variations of sediment-bound trace metals can be related to the bedrock types and weathering processes in the corresponding river basins. The rivers in southern China had notably higher concentrations of trace metals in sediments because of abundant non-ferrous mineral deposits and stronger weathering process in the region. A large proportion of trace metals in these sediments was associated with iron and manganese oxides and organic matter. Relative low levels of trace metals were found in river sediments in northern China, and a significant proportion of the metals was bound to organic matter, carbonates, and the residual fraction. The sediments in the Yellow River, originating from special loess, had the lowest concentrations of trace metals. Most of the trace metals were associated with the carbonates and residual phases. Received: 24 March 2000 · Accepted: 11 July 2000     

Assessment of the pseudo total metal content in alluvial sediments from Danube River,Serbia

We used elemental carbon, nitrogen, hydrogen and sulfur as well as ratios of hydrogen and nitrogen with total organic carbon for investigation of source and conditions of organic matter in alluvial Danube sediments. We also determined the pseudo total concentrations of metals presented as a sum of extracted concentration after five sequential extraction steps. The pseudo total metal concentrations were found to be (mg kg⁻¹) for Mn, 666; Fe, 25,852; Mg, 16,193; K, 2,063; Ni, 32.4; Zn, 72.2; Pb, 15.0; Cu, 26.0 and for Cr, 15.9. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were helpful in determining the associations between the pseudo total extracted fractions of metals and with elemental carbon, hydrogen, nitrogen, sulfur, total inorganic and organic carbon. These correlations will help us to identify substrates of trace metals in different oxic/anoxic conditions. The correlation results of the trace metals and Fe, K, Mg and Mn suggest their adsorption, mainly onto Fe and Mn (hydro)oxides and K alumosilicates, whereas correlations of metals with sulfur indicate that they were precipitated as Fe-sulfides.     

Sources,Distribution and Behavior of Major and Trace Elements in a Complex Karst Lake System

Sources and distribution of major and trace elements were investigated in the Plitvice Lakes, a pristine cascade hydrological system of sixteen karst lakes situated in a sparsely populated area of the central Croatia. Water and surface sediment samples from 17 locations, including springs, tributaries and lakes, were analyzed for the content of 22 elements by high-resolution inductively coupled mass spectrometry. Principal component analysis of the collected data set showed that different springs and tributaries displayed distinct multielemental compositions, reflecting primarily the differences in their corresponding geological backgrounds. It was shown that the springs situated in the Upper and Middle Jurassic dolomite bedrock represented the main source of several trace elements, including some toxic metals (Cd, Zn, Ni and Tl), to the Plitvice Lakes system. The concentrations of most of the trace elements (Mn, Fe, Al, Cd, Zn, Cu, Ni, Pb, Co, Cr and Tl) showed decreasing spatial trends in the downstream direction, from sources to the lakes. Such a distribution was interpreted to be a consequence of an efficient removal of the dissolved elements in the lentic parts of the system, mainly by co-precipitation with authigenic calcite and Mn oxides. Nevertheless, most of the elements in the lake sediments were highly correlated with Al, which indicated their prevalent association with terrigenic material. It was shown that the multicascade system of the Plitvice Lakes had an enhanced autopurification efficiency regarding the elimination of most of the trace metals from the aqueous phase.     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998     

Leaching of Trace Elements from Rocks under the Action of Organic Acids

Experiments were carried out on the leaching of trace elements (Li, Rb, Cs, Sr, Ba, V, Mn, Fe, Co, Ni, Cu, Tl, Y, La, Ce, Th, and U) from unmodified ashes of Karymsky volcano (the Kamchatka Peninsula) under the interactions with 0.01 M oxalic, salicylic, tartaric, citric, and acetic acids at various proportions of solid and liquid phases. Based on the data we obtained, it was concluded that the trace elements were mainly mobilized owing to the destruction of crystalline structures of rock-forming minerals, as well as to the reduction of Fe(III) and Mn(IV) oxide–hydroxides into soluble Fe(II) and Mn(II) compounds (in the case of oxalic acid). The formation of organic complexes increased the stability of metals in a solution and provided the attainment of higher concentrations of the dissolved forms compared to the case without organic ligands.     

扬子克拉通古大陆边缘Mo同位素特征及对有机埋藏量的指示意义

通过对扬子克拉通古大陆边缘不同时期沉积岩的Mo同位素进行测定,结合Mo微量元素组成,对古大陆边缘Mo的自生作用规律进行了研究,并根据Mo丰度对原始有机碳堆积速率进行了计算.结果表明,其原始有机碳堆积速率在0.17～0.67mmol/m2/day之间.利用已建立的现代大陆边缘δ98Mo与有机碳埋藏速率模型,对该区不同时期沉积岩的有机碳埋藏速率进行恢复.结果表明,扬子克拉通显生宙不同时期沉积岩的有机碳埋藏速率有较大的变化范围(0.43～2.87mmol/m2/day),并与原始有机碳堆积速率具有明显的相关性,因此,δ98Mo有可能成为评价有效烃源岩的潜在指标.