Element geochemistry of Holocene sediment and paleoenvironmental change in the Changjiang Estuary

Analyses of 41 elements reveal that Holocene sediments In the Changjiang Estuary bear regular elemental compositions in different sedimentary environments, and Holocene sediments came mainly from the Changjiang River based on compositions of REEs and most trace elements. Some heavy metals are more enriched in the surface sediment than in the deltaic sediments, reflecting human impact. Elemental compositions of the river channel sediment are related to the influence of proximal sediments. Sedimentary environments exert some influences on elemental compositions. Some chemical indices can be used to record chemical weathering undergone by the Changjiang sediment and environmental change.     

A simple solution to expanding available reference materials for Laser Ablation Inductively Coupled Plasma Mass Spectrometry analysis: Applications to sedimentary materials

Analytical data on sediments are of great importance in understanding and documenting environmental issues. For laboratories interested in in-situ chemical analysis of sediments by LA-ICP-MS, a major issue is the lack of appropriate matrix matched sediment reference materials. Those available were largely designed for partial extractions which generally do not reflect the total elemental compositions. In this work we provide a comprehensive study on chemical compositions of seven currently available sediment reference materials (Lake sediments: LKSD-1, LKSD-2, LKSD-3, Stream sediments: STSD-2, STSD-3, and Marine sediments: PACS-2, MESS-3) as determined by Solution Nebulization Inductively Coupled Plasma Mass Spectrometry (SN-ICP-MS) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) after digestion in a mixture of concentrated HNO₃ and HF acids. We also report a simple method to prepare these sediment reference materials and more generally appropriate sediment cores for LA-ICP-MS analysis using epoxy resin. This sample preparation method maintains sediment integrity for high spatial resolution analysis which is required for tracing changes in environmental conditions over short time periods. This work also demonstrates the application of fs-LA-ICP-MS as a tool for direct, rapid and high spatial resolution analysis of sediments.     

Analysis of major and trace elements by INAA to predict the thousands year old sediment deposition environment in the Meghna river delta

Major, trace and rare earth elements have been measured in sediments of different layers to determine the controls of constituent minerals on the distribution of elements and sediment deposition environment in the Meghna river delta. The geochemical composition of sediments was enriched in SiO₂, Ca, Mg and Ba and depleted in Al, Fe, Ti, Mn, and Sr relative to PAAS (Post-Archaen Average Shale) value. The X-ray diffraction and elemental analyses demonstrate the dominant presence of quartz, micas, feldspar, chlorite, amphibole and clay minerals in sediments. The very low contents of trace elements suggest that the oxic condition was more prevalent during sediment deposition of Pleistocene-Holocene period and reflect the massive chemical weathering by biogeochemical reactions. The enrichment of light rare earth elements and La/Yb ratio reflect the intense silicate weathering of crustal materials and the high sediment depositional rate in the Meghna river delta.     

Distribution of trace elements in the marine sediments along the South China Sea,Malaysia

In order to complete having data base of elemental assessment of the east coast of Peninsular Malaysia marine sediments along the South China Sea coasts, trace elements are analyzed and their distribution in marine sediments is undertaken. The present study is done parallel with pervious study on elemental assessment of heavy metals, rare earth elements and actinides in the marine sediments of the east coast of Peninsular Malaysia. Thirty surface sediment samples were collected in this area, including regions of Kelantan, Terengganu, Pahang, Rompin and Johor Baharu. Multielemental analysis was carried out by instrumental neutron activation analysis and inductively coupled plasma atomic emission spectroscopy. In both cases methodology validation was performed by certified reference material analyses. For the surface elemental distributions the enrichment factor values, average I _geo and mC _d values indicate that the trace elements of the surface sediments are uncontaminated in all sampling stations that are consistent with previous studies results of heavy metals, rare earth elements and actinides.     

Considerations about the226Ra gross alpha counting determination

Chemical elemental compositions of some silicate, magnetic and glass spherules were investigated with INAA. The elements determined include Os, Ir, Ni, Co, Fe, Cr, Au, La, Ce, Sm, Eu, Yb, Lu and Sc etc. The elemental correlation, as well as their enrichment (or depletion) factors relative to Cl chondrite were examined. The high concentrations of the refractory siderophile elements contained in these spherules support the proposal that they originate from extraterrestrial substances. Some useful chemical criteria for identifying the sources of silicate, magnetic and glass spherules are put forward.     

Heavy-metal distribution in river waters and sediments around a "firefly village", Shikoku, Japan: application of multivariate analysis.

River water and sediment samples were collected at the same site in a vicinity of an abandoned mine, and the concentrations of major elements and heavy metals were determined. The chemical correlations were observed by principal component analysis (PCA), and the samples were classified by cluster analysis (CA) based on the PCA scores. The PCA results presented a macroscopic viewpoint of covariance structure, i.e., the chemical elements could be classified into three groups: 1) major elements and heavy metals in the river water, 2) Cd, Fe and Mn in the sediments, and 3) Cu and Zn in the sediments. The CA results implied a similarity of chemical compositions in most parts of the study area, except the ranges close to the abandoned copper mine. At the mixing location of mining water with natural river water, major elements and cadmium showed simple physical mixing (conservative mixing). Other heavy metals (Cu, Fe, Mn and Zn) showed the massive precipitation at the mixing event. The PCA structure was mainly interpreted in terms of the mixing process between mining water and diluted natural river water.     

Cluster analysis of the elemental composition of five austrian peats

The elemental composition of peat depends on the plant residues from which the peat was formed. The concentrations of 45 elements were determined for five peat samples by plasma emission spectrometry. Literature data on the composition of three bogs was added. The elemental abundances of six rock or soil categories, the elemental compositions of several peat-forming plants, and the results of the elemental analyses of bog samples, were examined by the SIMCA method. A clear difference was found between fens and raised bogs. Factor analysis of the elemental compositions shows that the concentrations of most of the elements reflect their natural abundance in the surrounding region. Some concentrations are influenced by anthropogenic pollution, e.g. lead, and by plant metabolism. The cluster analysis together with the training sets shows the degree of the deposition of mineral material from adjacent rivers and the type of plant growth which formed the peat.     

Characterization of sediment reference materials by x-ray photoelectron spectroscopy

The chemical composition of surface layers of three sediment reference materials, Pond Sediment (Japan NIES CRM No. 2), River Sediment (US NBS SRM 1645) and Estuarine Sediment (US NBS SRM 1646), has been studied comparatively by X-ray photoelectron spectroscopy (XPS). The composition of River Sediment as determined by XPS is peculiar in that the concentration of Cr is much higher but that of Si is much lower than that expected from the bulk composition of the sample. This can be attributed to the structure of the sediment particles, which consist of silica-rich cores covered by surface layers rich in Cr(III). Organic substances are predominant in the surface layers of all three materials, as indicated by the C 1s and N 1s lines. The elemental composition of the surface layers can be reasonably related to the origin of the sediments. The bonding states of some elements in the sediment samples, deduced from the photoelectron binding energies, are briefly discussed.     

Trace elements distribution in the Amazon floodplain soils

Neutron activation analysis was performed on aluvial soil samples from several sites on the floodplains of the Amazon River and its major tributaries for trace elements determination. The spatial and temporal variations of chemical composition of floodland sediments in the Amazon basin are discussed. No significant difference was found in trace elemental distribution in the floodland soils along the Amazon main channel, even after the source material has been progressively diluted with that from lowland draining tributaires. It was also seen that the average chemical composition of floodplain soils compares well with that of the suspended sediments.     

Amazon estuary — assessment of trace elements in seabed sediments

The interactive processes operating on the continental shelf adjacent to the river mouth control the amount and the characteristics of the Amazon discharge reaching the Atlantic Ocean. In this study, the distribution of trace elemental concentrations, with emphasis to the rare-earth elements, in sediment cores collected at several stations from the Amazon continental shelf during the falling water period was investigated by instrumental neutron activation analysis. Cores from the terrigenous and blue water zones have relatively uniform REE concentrations throughout the profile. Cerium anomalies for samples of the upper section of the eight stations are consistently positive and of high values (normally >2). Similar variation in the elemental concentration ratios between the seabed sediments and Amazon River suspended sediments was seen for stations located in the biogenic and blue water zones, with an enrichment for Ce, Sm, Fe, Th, and Sc and a depletion for the La, Eu, Tb, Yb, Co, Cr, Cs, Hf, Ta, and Zn. The shale-normalized REE patterns from shelf sediments are enriched in LREE relative to HREE, with enrichment factors varying from 1.5 for stations near the river mouth (terrigenous zone) to 1.9 for stations located far in the blue water zone. Published data for the Amazon River suspended sediment agree remarkably well with this observation of LREE-enrichment.     

Energy dispersive X-ray fluorescence and neutron activation analysis of surficial sediments of the Sea of Marmara and the Black Sea around Istanbul

Surficial sediment samples, collected from 27 sampling sites of the Sea of Marmara and the Black Sea nearby Istanbul area in 1996 and 1999 years, were analyzed quantitatively for some heavy metals and some other elements by using radioisotope excited energy dispersive X-ray fluorescence (EDXRF). The U and Th concentrations of the samples were determined by instrumental neutron activation (INAA). The results were compared with those from other contaminated and uncontaminated sedimentary materials. It is found that some elemental concentrations of the Sea of Marmara and the Black Sea sediments are comparable with those in most other sea sediments in the vicinity of densely populated regions.     

Concentrations of some elements in the coastal sea sediments: Bays with marinas

Summary Surface sediments and sediment cores from two bays in the Adriatic sea (Punat Bay and Soline Bay, Croatia) have been analyzed for a number of elements, in particular: Ti, V, Mn, Fe, Cu, Zn, As and Pb, by using XRF. Maps of elemental distribution in surface sediments show increased concentrations for some elements present in antifouling paints (Cu, Zn, Pb) near the service areas in the villages or marinas. Core profiles for these elements were used to evaluate the environmental impact of newly constructed marinas. Source partition indicates the influence of other sources located in near by villages. The critical factor in these considerations was shown to be water exchange with the open sea.     

二碘荧光素、荧光素稀土配合物的合成及性质的研究

本文报导了一种合成二碘荧光素、荧光素稀土配合物的新方法,得到了定组成的固体配合物,并对它们的一系列性质进行了研究。通过化学分析、元素分析确定了它们的组成。     

Effects of freeze-drying on partitioning patterns of major elements and trace metals in lake sediments

The effect of freeze-drying on elemental partitioning pattern in four lake sediments was evaluated using the sequential extraction method developed under the auspices of Community Bureau of Reference (BCR) of the Commission of European Communities. Redox-sensitive elements like iron, manganese, phosphorus, and sulfur were analyzed simultaneously with several trace metals. This allows a qualitative determination of which trace metal-scavenging phases commonly found in freshwater sediments that are most susceptible to freeze-drying.The comparison of a surface layer and a deeper more reduced layer collected from four sediment cores ranging from sub-oxic to anoxic condition indicate the changes in partitioning pattern due to freeze-drying. Two of the lakes exhibiting clearly reduced environments are most affected by freeze-drying in terms of change in partitioning patterns. However, this effect is element specific and varies with sediment depth along the redox gradient. Elements commonly associated with a sulfide phase (S, Fe, Cu, Zn, and Pb) and extracted in BCR step 3 are the most affected elements, but at the same time also dependent on the organic matter content in the sediment. Si and Al that are often considered as conservative elements show a shift from step 3 to step 2, and it is interpreted as a release of Si and Al from organic matter and the subsequent formation of oxides during freeze-drying. Calcium and manganese, elements that are often associated with a carbonate phase, do not seem to be severely affected by this kind of treatment. Carbonate-associated iron (operationally defined), however does show a clear tendency to oxidize during the freeze-drying process. In fact, the shift in iron (carbonate to oxide fraction) corresponds to 3-4% (w/w) of the total sediment in some cases. Surprisingly, a significant fraction of iron originally extracted in step 1 (as “carbonate”) seems to be immobilized during freeze-drying.These results clearly show that freeze-drying does not preserve the speciation pattern of major elements, trace metals, phosphorus, and sulfur in anoxic lake sediment core sections during storage prior to BCR sequential extraction procedures.     

Neutron activation analysis on sediments from Victoria Land,Antarctica: multi-elemental characterization of potential atmospheric dust sources

The elemental composition of 40 samples of mineral sediments collected in Victoria Land, Antarctica, in correspondence of ice-free sites, is presented. Concentration of 36 elements was determined by instrumental neutron activation analysis, INAA. The selection of 6 standard reference materials and the development of a specific analytical procedure allowed to reduce measurements uncertainties and to verify the reproducibility of the results. The decision to analyze sediment samples from Victoria Land ice-free areas is related to recent investigations regarding mineral dust content in the TALos Dome ICE core (159°11′E; 72°49′S, East Antarctica, Victoria Land), in which a coarse local fraction of dust was recognized. The characterization of Antarctic potential source areas of atmospheric mineral dust is the first step to identify the active sources of dust for the Talos Dome area and to reconstruct the atmospheric pathways followed by air masses in this region during different climatic periods. Principal components analysis was used to identify elements and samples correlations; attention was paid specially to rare earth elements (REE) and incompatible/compatible elements (ICE) in respect to iron, which proved to be the most discriminating elemental groups. The analysis of REE and ICE concentration profiles supported evidences of chemical weathering in ice-free areas of Victoria Land, whereas cold and dry climate conditions of the Talos Dome area and in general of East Antarctica.     

Determination of elemental selenium and pyrite-selenium in sediments

A method is described for the selective determination of concentrations of elemental selenium and pyrite-selenium in sediments. A 1 M sodium sulfite solution is used to solubilize elemental selenium and a Cr(II) solution releases selenium in pyrite. The accuracy of the methods was evaluated by using various selenium compounds. The detection limits for the elemental and pyrite-selenium procedures are 0.001 and 0.025 μg Se per gram of sediment, respectively. The relative standard deviationis < 10% for elemental selenium and < 16% for pyrite-selenium. These and other procedures were used for selenium speciation in marine and freshwater sediments.     

Microwave digestion of bottom sediments from Lake Baikal for the inductively coupled plasma mass-spectrometric determination of their elemental composition

A microwave digestion procedure with the use of specially designed autoclaves and a domestic microwave oven is proposed for the mass-spectrometric determination of the elemental composition of bottom sediments. The throughput of sample preparation in routine analysis was considerably increased because of the elimination of a purification step. Reaction mixture compositions and microwave digestion conditions were chosen to reach complete decomposition (within the limits of error of semiquantitative ICP MS analysis) of Baikal bottom sediments with respect to the majority of elements. It was found that the procedure is unsuitable for the determination of Sn, Zr, Nb, Hf, As, and Sb. The approximate concentrations of elements in a BIL-1 certified reference material of Baikal bottom sediments were found: Tl, 0.52 ± 0.16 ppm; Bi, 0.33 ± 0.10 ppm; I, 14.3 ± 4.3 ppm; Cd, 0.31 ± 0.09 ppm; and Pb, 0.24 ± 0.07 ppm.     

Underwater sediment analyses by laser induced breakdown spectroscopy and calibration procedure for fluctuating plasma parameters

Laser Induced Breakdown Spectroscopy (LIBS) was applied on sediments directly under water. The aim of the research was to develop a method for measuring the sediment elemental composition, including minor elements, which could be implemented in-situ. The plasma was generated by a double-pulse, Q-Switched Nd:YAG laser operated at 1064 nm. For signal detection, both ICCD and non-gated, compact detectors were used. The major difficulties in underwater sediment analyses are related to the natural and laser induced surface roughness, and to the sample softness. The latter is responsible for the formation of particle clouds above the surface, which scatter both the laser and plasma radiation, and often results in breakdown formation above the analyzed surface. In such cases, a broad sonoluminescence emission from water, formed during the gas bubble collapse was sometimes registered. Under optimized experimental conditions, even by using a non-gated detector and single shot acquisition, it was possible to detect several minor sediment constituents, such as titanium, barium, manganese and others. A crude estimation of the Limit of Detection (LODs) for these elements was performed by underwater measurements on certified soils/sediments. Due to strong shot-to-shot fluctuations in the plasma temperature, well correlated calibration curves, aimed for quantitative analyses, could only be obtained after applying an appropriate data processing procedure. The latter selects automatically only the spectra characterized by similar plasma parameters, which are related to their continuum spectral distribution. Application of such a procedure improves the measurement accuracy also in other surroundings and on samples different from the ones analyzed here.     

Chemical characterization and recent sedimentation rates in sediment cores from Rio Grande reservoir,SP, Brazil

The Rio Grande reservoir lies southeast of the Metropolitan Area of São Paulo. In order to evaluate if the sediments contain a historical registration of anthropogenic activity, four sediment cores were sampled from the reservoir. In these cores the Hg concentration was determined by the CV AAS technique, major and trace elements by instrumental neutron activation analysis and the sedimentation rates by the ²¹⁰Pb method. The results obtained for Hg are much higher than expected, showing an anthropogenic contribution. As a general trend, the elemental concentration decreases with depth, indicating recent contamination.     

Sediment Assessment of the Pchelina Reservoir,Bulgaria

The temporal dynamics of anthropogenic impacts on the Pchelina Reservoir is assessed based on chemical element analysis of three sediment cores at a depth of about 100–130 cm below the surface water. The ¹³⁷Cs activity is measured to identify the layers corresponding to the 1986 Chernobyl accident. The obtained dating of sediment cores gives an average sedimentation rate of 0.44 cm/year in the Pchelina Reservoir. The elements’ depth profiles (Ti, Mn, Fe, Zn, Cr, Ni, Cu, Mo, Sn, Sb, Pb, Co, Cd, Ce, Tl, Bi, Gd, La, Th and U_nat) outline the Struma River as the main anthropogenic source for Pchelina Reservoir sediments. The principal component analysis reveals two groups of chemical elements connected with the anthropogenic impacts. The first group of chemical elements (Mn, Fe, Cr, Ni, Cu, Mo, Sn, Sb and Co) has increasing time trends in the Struma sediment core and no trend or decreasing ones at the Pchelina sampling core. The behavior of these elements is determined by the change of the profile of the industry in the Pernik town during the 1990s. The second group of elements (Zn, Pb, Cd, Bi and U_nat) has increasing time trends in Struma and Pchelina sediment cores. The increased concentrations of these elements during the whole investigated period have led to moderate enrichments for Pb and U_nat, and significant enrichments for Zn and Cd at the Pchelina sampling site. The moderately contaminated, according to the geoaccumulation indexes, Pchelina Reservoir surface sediment samples have low ecotoxicity.