Elemental characteristics and paleoenvironment reconstruction: a case study of the Triassic lacustrine Zhangjiatan oil shale,southern Ordos Basin,China

Using trace elements to reconstruct paleoenvironment is a current hot topic in geochemistry. Through analytical tests of oil yield, ash yield, calorific value, total sulfur, major elements, trace elements, and X-ray diffraction, the quality, mineral content, occurrence mode of elements, and paleoenvironment of the Zhangjiatan oil shale of the Triassic Yanchang Formation in the southern Ordos Basin were studied. The analyses revealed relatively high oil yield (average 6.63%) and medium quality. The mineral content in the oil shale was mainly clay minerals, quartz, feldspar, and pyrite; an illite–smectite mixed layer comprised the major proportion of clay minerals. Compared with marine oil shale in China, the Zhangjiatan oil shale had higher contents of quartz, feldspar, and clay minerals, and lower calcite content. Silica was mainly in quartz and Fe was associated with organic matter, which is different from marine oil shale. The form of calcium varied. Cluster analyses indicated that Fe, Cu, U, V, Zn, As, Cs, Cd, Mo, Ga, Pb, Co, Ni, Cr, Sc, P, and Mn are associated with organic matter while Ca, Na, Sr, Ba, Si, Zr, K, Al, B, Mg, and Ti are mostly terrigenous. Sr/Cu, Ba/Al, V/(V + Ni), U/Th, AU, and δU of oil shale samples suggest the paleoclimate was warm and humid, paleoproductivity of the lake was relatively high during deposition of the shale—which mainly occurred in fresh water—and the paleo-redox condition was dominated by reducing conditions. Fe/Ti ratios of the oil shale samples suggest clear hydrothermal influence in the eastern portion of the study area and less conspicuous hydrothermal influence in the western portion.     

Geochemistry and Modes of Occurrence of Hazardous Trace Elements in the No. 11 Coal Seam, Antaibao Surface Mine, Shanxi Province

Concentrations of seventeen hazardous trace elements including As, Pb, Hg, Se, Cd, Cr, Co, Mo, Mn, Ni, U, V, Th, Be, Sb, Br and Zn in the No.ll coal seam, Antaibao surface mine, Shanxi Province were determined using Instrumental Neutron Activation Analysis （INAA）, Inductively Coupled Plasma Atomic Emission Spectrometry （ICP-AES）, Cold-Vapor Atomic Absorption Spectrometry （CV-AAS） and Graphite Furnace Atomic Absorption Spectrometry （GF-AAS）. Comparisons with average concentrations of trace elements in Chinese coal show that the concentrations of Hg and Cd in the No. 11 coal seam, Antaibao surface mine are much higher. They may be harmful to the environment in the process of utilization. The variations of the trace elements contents and pyritic suffur in vertical section indicated that： （a） the concentrations of As, Pb, Mn, and pyritic sulfur decrease from roof to floor; （b） the concentrations of Cr, Zn and Mo are higher in roof, floor and lower in coal seam; （c） the concentration of Br, Sb, and Hg are higher in coal seam and lower in roof and floor; （d） the concentrations of Mo, V, Th and AI vary consistently with the ash yield. Cluster analysis of trace elements, pyritic sulfur, ash yield and major elements, such as AI, Fe, P, Ca shows that： （a） pyritic sulfur, Fe, As, Mn, Ni, Be are closely associated and reflect the influence of pyrite; （b） Mo, Se, Pb, Cr, Th, Co, Ca and A! are related to clay mineral, which is the main source of ash; （c） U, Zn, V, Na, P maybe controlled by phosphate or halite; （d） Hg, Br, Sb and Cd may be mainly organic-associated elements which fall outside the three main groups. The concentration distribution characteristics of trace elements in coal seam and the cluster analysis of major and trace elements showed that the contents of trace elements in the No. 11 coal seam, Antaibao surface mine, are mainly controlled by detrital input and migration from roof and floor.     

Geochemical characteristics of the surface layer of bottom sediments from the Deryugin Basin, Sea of Okhotsk

This paper reports data, including new analyses, on the contents of Ni, Co, V, Mo, Fe, Mn, Zn, Ba, Sc, Y, Cd, Rb, Cs, and W in the sediments of the Deryugin Basin. The features of the distribution of chemical elements in the bottom area were identified, and the zones of maximum accumulation of the major and trace elements were allocated. A correlation between the elements was shown.     

Concentration and distribution of trace elements in some coals from Northern China

The concentration, distribution and modes of occurrence of trace elements in thirty coals, four floors and two roofs from Northern China were studied. The samples were collected from the major coalfields of Shanxi Province, Shaanxi Province, Inner Mongolian Autonomous Region, and Ningxia Hui Autonomous Region. The concentrations of seventeen potential hazardous trace elements, including Hg, As, Se, Pb, Cd, Br, Ni, Cr, Co, Mo, Mn, Be, Sb, Th, V, U, Zn, and five major elements P, Na, Fe, Al, and Ca in coals were determined.Compared with average concentration of trace elements in Chinese coal, the coals from Northern China contain a higher concentration of Hg, Se, Cd, Mn, and Zn. They may be harmful to the environment in the process of combustion and utilization. Vertical variations of trace elements in three coal seams indicated the distributions of most elements in coal seam are heterogeneous. Based on statistical analyses, trace elements including Mo, Cr, Se, Th, Pb, Sb, V, Be and major elements including Al, P shows an affinity to ash content. In contrast, Br is generally associated with organic matter. Elements As, Ni, Be, Mo, and Fe appear to be associated with pyrite. The concentrations of trace elements weakly correlate either to coal rank or to maceral compositions.     

Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.     

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.     

Behaviour of the trace elements in a front of metasomatic-metamorphism in the Dalradian of Co. Donegal

The epidioritc and quartzite of the Malin Head district, (Ireland) are considered by Holmes and Reynolds [7] to be metasomatically transformed into skarn-rocks and mica-schist respectively. The trace element contents of these rocks were investigated using semi-quantitative methods in order to study the behaviour of the different trace elements during the metasomatic changes which have taken place. The elements which have been determined are Rb, Ba, Ag and Pb; Sr, Y and La; Li, Cr, Ni, Co, V, Cu, Sc, Sn and Mo; Ga; Zr, Be, Tl, Ge and In. The trace elements follow the major elements for which they can substitute in favourable crystal lattices, the substitution being in accord with Goldschmidts rules. Rb, Ba and probably Pb and Ag follow and substitute for K; Sr and Y for Ca and probably K; Li, Cr, Ni, Co, V, Cu, Sc, Sn and Mo for Mg, Fe² and Fe³; and Ga for Al.     

塔里木盆地寒武系原油微量元素特征及意义

塔里木盆地是中国最大的内陆含油气盆地,有关盆地内主力烃源岩层位时代目前仍存在一定争议。油-油对比能够 发现原油间的亲缘关系,明确不同类型原油地球化学特征,是解决这一问题的有效手段。中深1井及中深1C井发现的中寒 武统阿瓦塔格组、下寒武统肖尔布拉克组原油可以作为重要的端元油类型参与油-油对比。本文通过对比两种寒武系原油 及盆地内多种轻质原油微量元素组成,发现根据多种过渡金属元素比值进行聚类分析可将盆地内轻质原油分为I类和II类, Cr/V,Ni/Mn,Ni/Mo比值是原油分类的良好指标。I类原油较II类原油具有较低的Cr/V比及较高的Ni/Mn与Ni/Mo比,表明 其烃源岩沉积环境相对还原。本次分类结果与前人有机地球化学研究相符,表明无机地球化学指标可作为原油分类的重要 参考,具有较大的应用潜力。     

橄榄石微量元素原位分析的现状及其应用

随着高精度EMPA和LA-ICP-MS分析技术的发展和矿物微量元素测试精度的提高,利用橄榄石中的微量元素示踪地幔部分熔融、地幔交代作用、岩浆早期结晶过程等地质问题成为近年来一个新兴的研究方向。一系列开拓性的研究发现也被陆续的发表,主要涉及橄榄石中Ni、Co、Al、Cr、Zn、Ti、Li、V、Sc、Mn、Ca和P等元素的示踪使用。一些卓有成效的示踪方法为:Ca、Al、Ti、Ni及Mn能够很好的用于区分橄榄石捕掳晶和斑晶;橄榄石-尖晶石地幔演化趋势线(OSMA:olivine-spinel mantle array)图解可以用于表征岩浆源区的亏损程度;玄武岩中橄榄石斑晶的Li同位素及Li含量可以很有效地指示岩浆源区是否存在地壳物质再循环及地幔交代作用;橄榄石斑晶中Ni、Ca、Mn、Cr和Al协变关系图解可以识别岩浆的辉石岩源区;利用橄榄石捕掳晶中Zr和Sc的含量差异特征可将橄榄岩中三种最主要的类型(尖晶石橄榄岩、石榴石橄榄岩以及尖晶石-石榴石橄榄岩)区分开来;一些元素的比值或组合(例如Ni/Co、Fe/Mn、V/Sc、Zr和Sc、Ca和Ti)可以指示源区交代作用、岩浆作用过程及氧化状态;基于橄榄石中Al、Cr及Ca的地质温度计可以为推算地幔热状态提供新方法;基于橄榄石分离结晶Fo-NiO演化线的原始岩浆计算模型可以较好的推算原始岩浆成分;利用橄榄石的环带及微量元素的扩散机制可以判别更多岩石成因信息,如识别交代介质、熔体类型以及地质构造背景等。基于上述最新研究的相关资料和已有成果,本文对橄榄石微量元素的地球化学示踪方法做系统性的归纳整理,并对橄榄石微量元素赋存状况、橄榄石微量元素测试方法、橄榄石微量元素的使用条件及需注意的问题等进行讨论,为读者在做相关研究时提供参考。     

Concentration and distribution of elements in Late Permian coals from western Guizhou Province,China

With the aim of better understanding geochemistry of coal, 71 Late Permian whole-seam coal channel samples from western Guizhou Province, Southwest China were studied and 57 elements in them were determined. The contents of Al, Ca, Co, Cr, Cu, Fe, Ga, Hf, K, Li, Mn, Mo, Nb, Ni, Sn, Ta, Ti, Th, U, V, Zr, and REEs in the Late Permian coals from western Guizhou Province are higher than the arithmetic means for the corresponding elements in the US coals, whereas As, Ba, Br, F, Hg, P, Se, and Tl are lower. Compared to common Chinese coals, the contents of Co, Cr, Cu, Ga, Hf, Li, Mn, Mo, Ni, Sc, Sn, Ti, U, V, Zn, and Zr in western Guizhou coals are higher, and As, F, Hg, Rb, Sb, Tl, and W are lower. Five groups of elements may be classified according to their mode of occurrence in coal: The first two, Group A, Tm–Yb–Lu–Y–Er–Ho–Dy–Tb–Ce–La–Nd–Pr–Gd–Sm, and Group B, As–Sr–K–Rb–Ba–F–Ash–Si–Sn–Ga–Hf–Al–Ta–Zr–Be–Th–Na, have high positive correlation coefficients with ash yield and they show mainly inorganic affinity. Some elements from Group B, such as Ba, Be, Ga, Hf, and Th, are also characterized by significant aluminosilicate affinity. In addition, arsenic also exhibits high sulfide affinity (r_S–Fe>0.5). The elements, which have negative or lower positive correlation coefficients with ash yield (with exceptions of Bi, Cs, Nb, Mn, Se, and Ti), are grouped in other four associations: Group C, Cr–V–Mo–U–Cd–Tl; Group D, Hg–Li–Sc–Ti–Eu–Nb–Cs–W; Group E, Bi–Sb; and Group F, Co–Ni–Cu–Pb–Zn–Mg–Se–Ca–Mn–S–Fe. The correlation coefficients of some elements, including Co, Cr, Cu, Fe, Hg, Li, Mo, Ni, P, S, Sc, U, V, and Zn, with ash yield are below the statistically significant value. Only Cr and Cu are negatively correlated to ash yield (−0.07 and −0.01, respectively), showing intermediate (organic and inorganic) affinity. Manganese and Fe are characterized by carbonate affinity probably due to high content of epigenetic veined ankerite in some coals. Phosphorus has low correlation coefficients with any other elements and is not included in these six associations. There are five possible genetic types of enrichment of elements in coal from western Guizhou Province: source rock, volcanic ash, low-temperature hydrothermal fluid, groundwater, and magmatic hydrothermal inputs.     

Statistical assessment of geochemical pattern in overbank sediments of the river Sava,Croatia

Four overbank profiles from the three terraces of different age were sampled in 10 to 20 cm intervals for the bulk content of major and minor (Ca, Mg, Fe, Ti, Al, Na, K and P) and trace (Mo, Cu, Pb, Zn, Ni, Co, Mn, As, U, Th, Sr, Cd, Sb, V, La, Cr, Ba, W, Zr, Ce, Sn, Y, Nb, Ta, Sc, Li, Rb and Hf) elements in the minus 0.125 mm fraction. Univariate statistics together with analysis of variance discriminated between the lower-lying carbonate (CA) population dominantly composed of carbonates and the overlying silicate (SI) population being dominantly of silicate mineralogy. This stratified pattern resulted from the intensive erosive action of melting glaciers exerted on limestones and dolomites in the alpine region, followed by local inputs mainly of silicate composition. Elements exhibiting the greatest between-population variability are Ca and Mg being enriched in the CA population and Fe, Mn, P, Sr, Al, Na, K, Li, Rb, Y, Zr, Ni, Cr and Ti being enriched in the SI population. Anomalously high Hg, Pb and Ba concentrations (maximum values: 6,500±2,860 ppb, 225±13 ppm and 1,519±91 ppm, respectively) in the lowermost part of the profile S7, which is nearest to the Croatian-Slovenian border, derive from the mineralized Slovenian catchment area. This profile also contains trimodal frequency distributions of Fe, Mn and P whose highest concentrations coincide with increased values of Zn and Cu which are bimodally distributed. Geochemical patterns of majority of elements in all four profiles consistently reflect the average compositions of the upstream drainage basins.     

吉林东部花岗岩区地下水化学成分及其对岩石风化作用的制约

在吉林东部花岗岩区地下水化学成分和化学类型研究的基础上,以Na作为参比元素,确定了花岗岩风化过程中22种主量元素和微量元素的相对活动顺序。花岗岩区地下水的地球化学类型属低矿化度(变化范围为69.51×10-6~386.49×10-6,平均值为199.48×10-6)的HCO3-Ca和HCO3-Na-Ca型。花岗岩风化过程中元素的活动性顺序(RM)从大到小依次为:B、Ca、Mo、Zn、Sr、Na、Mg、Cr、Cu、Ni、K、Co、Li、V、As、Ba、Si、Y、Fe、Ti、Al、Mn。风化产物中的粘土矿物主要为高岭土、蒙脱石,反映出本区花岗岩的风化淋滤程度较弱的特点。     

Taxonomical and Biogeochemical Investigation of Elements in Holocene Mollusk Shells in the South and Southwestern Marmara Basin, Turkey

Concentrations of some heavy metals and trace elements such as Cr,Ga,Ni,Zn,Mo,Cu, Pb,Yb,Y,Nb,Ti,Sr,Ba,Mn,Sc,Co,V,Zr,Fe,Al,W,Se,Bi,Sb,As,Cd in recent mollusk shells and factors affecting their distribution and deposits collected from various depths in the southern and southwestern parts of the Marmara Sea are investigated.The distribution of the elements in the shells is categorized into four groups.Of these,concentrations of 12 elements(As,Bi,Cd,Co,Ga,Mo,Nb, Sb,Se,Sc,W and Yb)are below zero [(0.053-0.79)×10~(-6)];concentrations of seven elements(Cr,Ni, Pb,V,Y,Zr and Cu)are(1.0-6.0)×10~(-6);concentrations of four elements(Ti,Mn,Ba and Zn)are 10- 20×10~(-6);and concentrations of five elements(Si,Al,Fe,Mg and Sr)are(47.44-268.11)×10~(-6).The taxonomic characteristics of the 29 elements were studied separately in mollusk shells such as Chamalea gallina(Linné),Pitar-rudis(Poll),Nassarius reticulatus(Linné),Venerupis senescens (Coocconi),Mytilus galloprovincialis(Lamarck),Mytilaster lineatus(Gemelin in Linné)and Chlamys glabra.It was found that,in mollusk taxonomy,the elements have unique values.In other words, element concentrations in various mollusk shells depend mainly on the taxonomic characteristics of mollusks.In various bionomic environments different element distributions of the same species are attributed to the different geochemical characters of the each environment.Data obtained in this study indicate that the organisms are the most active and deterministic factors of the environment.     

Spatial distribution of metals in urban topsoils of Xuzhou (China): controlling factors and environmental implications

The contamination of soils by metals from various sources is a subject of increasing concern in recent times. Twenty-eight elements (Fe, Ti, Cr, Al, Ga, Pb, Sc, Ba, Li, Cd, Be, Co, Cu, Mn, Ni, V, Zn, Mo, Pt, Pd, Au, As, Sb, Se, Hg, Bi, Ag and Sn) have been analyzed from urban topsoil from the city of Xuzhou. The concentrations of these analyzed elements have been correlated to some soil parameters such as organic matter, pH, cation exchange capacity, carbonate content, and granulometric fractions (clay, silt and sand). Results of the statistical analysis show a large variety and complexity in these relationships. The spatial distributions of these metal concentrations were also constructed using geographical information system. The spatial distribution patterns of the elements analyzed show that traffic and industrial activities are the principal anthropogenic pollutant sources.     

太平洋北部铁锰结核富集区沉积物的元素地球化学特征

本文对太平洋北部铁锰结核富集区沉积物的元素地球化学作了较为详细的研究。因子分析提供的信息表明,元素的分布主要受三个因子控制:（1）粘土及Fe、Mn氧化物水化物胶体的吸附作用;（2）生物化学作用过程有关的自生沉积作用;（3）海底页岩风化及附近海区的火山喷发作用。元素的来源:（1）Fe、Mn、Cu、Co、Ni、Zn、Cr、Cr、Mg、Al、Ti、K共生,主要来自粘土吸附;（2）C_有机、N、Sr、Na及Si、Ca、Sr主要来自生物化学过程沉积;（3）Pb主要来源于岩石碎屑（火山喷发碎屑）。     

残坡积土壤层中铁锰氧化物的吸附特性及其地球化学找矿意义

作者用不同方法研究了粤北某铅锌矿区近矿灰岩风化土壤中铁锰氧化物对微量元素的富集作用。发现铁锰氧化物对Sb、Pb、Cd、Ni等元素具有强烈的吸附作用;对Zn、Cu等21种元素有程度不等的吸附;对Ti、Sr等12种元素不吸附。据此,作者认为在土壤地球化学找矿中,应着重在铁锰结核层和铁锰粘土层取样,或用编提取方法分析铁锰氧化物相的元素含量,强化异常,提高找矿效果。     

Factors affecting the distribution of potentially toxic elements in surface soils around an industrialized area of northwestern Greece

In order to investigate the factors influencing the distribution of 32 potentially toxic elements in the Ptolemais–Kozani basin, northwestern Greece, 38 soil samples were collected and analyzed. Concentrations of Al, Ca, Fe, K, Mg, Mn, Na, P, Ti, Ba, Co, Cr, Cu, La, Li, Ni, Pb, Sc, Sr, V, Y, and Zn were determined by ICP-AES and concentrations of As, Bi, Cd, Cs, Mo, Rb, Sb, Th, Tl, and U by ICP-MS. Bivariate analysis, principal component analysis, and geostatistical analysis were employed to investigate the factors influencing the distribution of the elements determined in the study area. The results indicate that the distribution of the majority of elements determined, especially for Cr, Ni, and associated elements, is greatly influenced by the geology and geomorphology of the study area. Principal component analysis has yielded four factors that explain over 77% of the total variance in the data. These factors are as follows: lithophilic elements that are associated with Al silicates minerals of K (factor I: 29.4%), ultramafic rocks (factor II: 20.5%), elements that are coprecipitated with Fe and Mn oxides (factor III: 18.0%), and anthropogenic activities (factor IV: 9.3%). The anthropogenic activities that influence the distribution of several potentially toxic elements (i.e., Cd, Cu, Pb, Zn) are agricultural practices and the deposition of fly ash in the vicinity of the local power stations.     

Geochemistry of ferromanganese nodule–sediment pairs from Central Indian Ocean Basin

Fourteen ferromanganese nodule–sediment pairs from different sedimentary environments such as siliceous ooze (11), calcareous ooze (two) and red clay (one) from Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements (REE) to understand the possible elemental relationship between them. Nodules from siliceous and calcareous ooze are diagenetic to early diagenetic whereas, nodule from red clay is of hydrogenetic origin. Si, Al and Ba are enriched in the sediments compared to associated nodules; K and Na are almost in the similar range in nodule–sediment pairs and Mn, Fe, Ti, Mg, P, Ni, Cu, Mo, Zn, Co, Pb, Sr, V, Y, Li and REEs are all enriched in nodules compared to associated sediments (siliceous and calcareous). Major portion of Si, Al and K in both nodules and sediments appear to be of terrigenous nature. The elements which are highly enriched in the nodules compared to associated sediments from both siliceous and calcareous ooze are Mo – (307, 273), Ni – (71, 125), Mn – (64, 87), Cu – (43, 80), Co – (23, 75), Pb – (15, 24), Zn – (9, 11) and V – (8, 19) respectively. These high enrichment ratios of elements could be due to effective diagenetic supply of metals from the underlying sediment to the nodule. Enrichment ratios of transition metals and REEs in the nodule to sediment are higher in CIOB compared to Pacific and Atlantic Ocean. Nodule from red clay, exhibit very small enrichment ratio of four with Mn and Ce while, Al, Fe, Ti, Ca, Na, K, Mg, P, Zn, Co, V, Y and REE are all enriched in red clay compared to associated nodule. This is probably due to presence of abundant smectite, fish teeth, micronodules and phillipsite in the red clay. The strong positive correlation (r ? 0.8) of Mn with Ni, Cu, Zn and Mo and a convex pattern of shale-normalized REE pattern with positive Ce-anomaly of siliceous ooze could be due to presence of abundant manganese micronodules. None of the major trace and REE exhibits any type of inter-elemental relationship between nodule and sediment pairs. Therefore, it may not be appropriate to correlate elemental behaviour between these pairs.     

The Distribution and Seasonal Variation of Dissolved Trace Metals in Florida Bay and Adjacent Waters

Florida Bay is a shallow carbonate estuary in South Florida. It receives fresh waters from the Everglades that contribute a number of metals to the Bay. The Bay is the largest estuary in Florida with nearly pristine conditions. In this paper we report the first extensive studies of trace metals in the Bay. The seasonal distributions of trace metals (Sc, V, Cr, Co, Cu, Fe, Pb, Mn, Ni and Al) were determined on surface waters in Florida Bay and adjacent waters. The measurements in the Bay were made from May 2000 to May 2001, and the adjacent waters were sampled in September 2000 and May 2002. Most of the dissolved trace metals exhibited their maximum concentrations in summer, except Al and Pb that did not show any seasonal variability. The seasonal variations of the metals are related to the influx of fresh water from rainfall. The lowest concentrations are found during the dry season in the winter and the highest during the wet season in the summer. Several metals (V, Mn, Al, Sc, Fe, Co, Ni and Cr) exhibited their highest concentrations in the western zone of the Bay. These waters from agricultural areas are influenced by Gulf of Mexico waters, which carry metals coming from Barron, Broad and Shark rivers into the Bay. The Shark River always exhibited high concentrations of V, Mn, Al, Sc, Co and Cr. Other possible influences in the western and north-central zone of the Bay are from Flamingo Center, the creeks of Taylor Slough and the mangrove fringe of the Everglades. High concentrations of Al, Co, Ni, Cr, Cu, Fe, and Pb were detected in the eastern zone. The high values found in the northeast are influenced by Taylor Slough runoff and in the southeast by Key Largo, Tavernier Marina and the drainage from the main highway (US1) on Tavernier Key. The minimum concentrations for most of the metals were found in areas near the Key channels that exchange waters between Florida Bay and the Atlantic Ocean (Gulf Stream). The adjacent waters in the Atlantic side including the Gulf Stream waters showed very low concentrations for all the metals studied except for V. In the Bay correlations of V were found: (1) V with salinity and Al and (2) Sc with Si. Most of the other metals did not show any strong correlations with nutrients or salinity. Florida Bay is thus not a typical estuary due to the unique structure of its mud banks and multiple inputs of metals from the mangrove fringe in the north.     

Environmental quality evaluation of the Vacacaí River, Rio Grande do Sul, Brazil

The water quality of the Vacacaí River was assessed at different sites in the period between winter 2005 and autumn 2006. All samples were analyzed for 52 elements (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th, Li, Be, Mg, Al, Ca, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, In, Cs, Ba, Tl, Pb, Bi, U, Na, K, Hg, B, Mo, Sn, Te, Ti), temperature, pH, ammonia, and alkalinity levels. Water from the Vacacaí River ranged from slightly acidic to alkaline. No difference was observed in the chemical composition at different sites of the Vacacaí River. Levels of Ba, Ca, Sr and Mg increase in the dry seasons and reach their highest concentrations in autumn; Be and U decrease in the dry season and reach their highest concentration in spring. Al, Fe, Cr, Ni, Th, U Mn, Ca and Mg are highly positively related, indicating a common origin. Se and Cu are probably from anthropogenic source, from the rice crops of the margins of the river. Waterborne Al and Fe levels were above the desirable level for drinking water at all sites during all seasons. These results demonstrate the need for constant monitoring of water parameters, which is crucial to ensure water quality for the population of this region.