Heavy metals in sediments of the rhine and elbe estuaries: Mobilization or mixing effect?

On their way from the Rhine estuary into the North Sea and Dutch Wadden Sea, Rhine sediments “lose” large portions of their original heavy metal concentrations. Until now these losses were explained by a mobilization process, solubilization — the decomposition products of organic matter form soluble organometallic complexes with the metals of the sediment. Our investigations of the sediments of the Elbe clearly indicate that a mixing process, whereby highly polluted Elbe sediments mix with relatively non-polluted North Sea sediments, rather than solubilization, is the cause of the dilution of heavy metals in the sediments of the Elbe estuary. Because of the similarity of the Elbe data with those from the Rhine River, we propose that a mixing process is also effective in the Rhine estuary and adjacent North Sea areas. The mechanism by which heavy metals are “diluted” is important to the marine ecosystem. In the mixing process proposed in this paper, the heavy metals fixed to the suspected material are trapped in bottom sediments of the marine environment, whereas solubilization would increase the concentration of heavy metals in the sea water and thus they would be more available for uptake by aquatic organisms.     

Geochemistry of Miocene lacustrine sediments from the Sokolov Coal Basin (Czech Republic)

Sediments of the upper part of the Sokolov Formation of the Sokolov Brown Coal Basin consist mostly of brown lacustrine clays and claystones enriched in organic matter (2–18% TOC). The lower portion of the stratigraphic profile is formed mostly by kaolinite–illite clays and claystones, while the montmorillonite content increases in the upper portion. The change in the lithology of sediments is caused by the gradual erosion of the weathering crust in the source areas of the clastic material. Inversion of the weathering profile during erosion is manifested geochemically in a decrease in the Al₂O₃/Na₂O ratio and an increase in the SiO₂/Al₂O₃, Na₂O/K₂O and K₂O/TiO₂ ratios from the base to the top of the studied part of the Sokolov Formation. The amounts of trace elements (La, Ce, Nb, Zr, Cr, V, Sn) also decrease in the same direction. On the other hand, the amounts of Rb and Sr increase. The organic matter of the upper part of the Sokolov Formation consists primarily of Types I and II kerogen. Only near the base of the studied part of the formation, i.e., in the coal stringer, kerogen of Type III prevails. The extremely low degree of thermal maturity permits determination of the source of the organic matter and characterization of its accumulation environment. The organic material in the sediments is predominantly of algae origin. Relatively high amount of pentacyclic triterpanes of the hopane series indicates either the occurrence of cyanobacteria as primary producers or bacterial reworking during sedimentation and diagenesis. Organic matter accumulated under the conditions of a fresh-water lake or lake with slightly elevated salinity, in a dysoxic aqueous environment. The alternation of organic carbon-rich layers with layers low in organic matter is explained in terms of changes in the degree of dysoxia of the aqueous environment and a variation in the intensity of oxidation and mineralization of the organic material.     

Contrasting the geochemistry of oxic sediments across ecosystems: a synthesis

The geochemistry of oxic sediments was contrasted across a range of Canadian aquatic ecosystems; 7 freshwater lakes, (3 circumneutral and 4 acidic), 15 peatlands (5 mineral-rich, 5 moderately-poor and 5 mineral-poor), 9 wetlands (3 oligosaline, 3 mesosaline and 3 euryhaline), an estuary (deposited and suspended sediments) and an intertidal region. Sediments were characterized by a simultaneous extraction that separated sediments into easily reducible (ER) metal (oxyhydroxides of Mn and easily reducible amorphous oxyhydroxides of Fe) and reducible (R) metal (more crystalline forms of oxyhydroxides of Fe), organic matter, and, the concentrations and partitioning of Zn, Cu and Cd associated with these 3 sediment components. Ecosystems were distinct with respect to ER Fe and organic matter [canonical variate analysis (CVA)] with 53% of among system variation in geochemistry attributed to these 2 components. Sediments of peatlands and wetlands contained greater amounts of organic matter whereas sediments of lakes, intertidal and estuarine deposited and suspended sediments were characterized by greater amounts of ER Fe. A further 21% of among system variation could be ascribed to organically bound Fe that was greater in acidic lakes and mineral-rich peatlands as compared to other systems. Concentration and partitioning of Cd within sediments was regionally dependent with 41% of among system variation (CVA) attributed to differences in ER Cd and R Cd. Cadmium from peatlands and lakes located in Ontario was recovered from all 3 sediment components whereas sediment from wetlands, the estuary and the intertidal regions of British Columbia (BC) contained no organically bound Cd with amounts recovered occurring mostly as ER Cd. Lakes and peatlands located in Ontario contained 3–5-fold total Cd as compared to ecosystems located in BC. A further 21% of among ecosystem variation was attributed to Zn partitioning. Zinc in peatland and wetland sediments occurred as R Zn as compared to lake and estuarine deposited sediments where Zn was recovered both as ER and R Zn. Total Zn was also 3–5-fold greater in sediments of systems in Ontario as compared to those sampled in BC. Concentration and partitioning of Cu was similar across all systems with Cu recovered from the organic component of sediment. The geochemistry of surficial oxic sediments with respect to ER Mn, R Fe and organic matter and the geochemical associations among these sediment components is ecosystem and region dependent. For assessing impacts of metals on sediment dwelling biota the geochemical characteristics of the system under study should first be defined.     

沿海表层沉积物中重金属的有效结合态

以浙江沿海表层沉积物为研究对象,系统地研究了重金属有效结合态与沉积环境、矿物组成和人为排放等环境因素之间的相互关系.结果表明:沿海表层沉积物中重金属的积累数量,呈现出潮汐河口沉积物>沿海沉积物>强潮汐河口沉积物的趋势,这反映了不同沉积类型对重金属富集作用的差异;重金属的有效结合态,总体上以铁锰氧化物结合态>碳酸盐结合态>硫化物及有机结合态>可交换态的顺序存在,但是不同的重金属或同种重金属在不同的采点,主要有效结合态的比例存在明显的差异,这不仅与重金属的地球化学性质、沉积环境和沉积物中的粘土矿物组成有关,更受到重金属污染物的人为排放量的影响.     

东海陆架泥质区沉积有机质的物源分析

色谱和色谱／质谱分析表明，济州鸟西南泥质区正构烷烃、姥鲛烷、植烷、藿烷和甾烷等生物标志物的特征与现代长江口、老黄河口和新黄河口的河流沉积物均区别很大，该泥质区的沉积有机质主要来源于海洋低等生物（如细菌和藻类等）以及陆源高等植物的输入，表现为不同来源和成熟度的生物标志物的混合，同时该泥质区沉积有机质与矿物碎屑沉积物来源不尽相同。长江口泥质区正构烷烃高相对分子质量部分与长江口沉积物相似，正构烷烃和藿烷所反映的有机质成熟度高于现代长江和老黄河口沉积物，甾烷的成熟度与长江相仿而明显高于老黄河口沉积物。长江口泥质区的沉积有机质主要来源于长江输入的陆源高等植物碎片和海洋源的低等生物。东海陆架近岸与远端泥质区沉积有机质的物源很不相同。     

Spatial trends in the geochemical composition of sediments in the Panuco River discharge area, Gulf of Mexico.

Major and trace elements, organic matter, carbonates, loss of ignition, grain size, gravel, sand, silt, clay, and qualitative mineralogical composition were determined on surficial marine sediments sampled during the stormy (February), dry (May), and rainy (September) seasons in the coastal area adjacent to Panuco River discharges into the Gulf of Mexico. The sediments supplied by the river move in a north-east direction, and are deposited in the north-east extreme of the studied area. Terrigenous sediments show a strong association of Al₂O₃ with Fe₂O₃, Na₂O, K₂O, P₂O₅, Rb, Cu, Zn, organic matter, clay, and grain size (Mz). Mineralogical analysis shows that they are formed by quartz, kaolinite, montmorillonite, illite-montmorillonite and biotite. The highest metal concentration of Cu (25 mg/kg), Zn (155 mg/kg), Pb (50 mg/kg) and organic matter (1.26%) was observed in the sampling points located very close to the river mouth. A statistical analysis was done with the information contained in the variables. Five significant factors explain 77% of the total variance: factor 1 is due to sediments from a terrigenous source, factor 2 corresponds to sediments from a biogenous source, factor 3 is associated to sediments with heavy minerals, factor 4 is due to Co concentration, and factor 5 is due to Ni concentration. The sediments supplied from the river had a short-term local impact on the sediment distribution, as observed by the carbonate and heavy mineral concentration of the sediments.     

Microelectrode Study of Oxygen Uptake and Organic Matter Decomposition in The Sediments of Xiamen Western Bay

Sediment cores were sampled from Xiamen Western Bay at five sites during the summer and winter of 2006 and Hg–Au microelectrodes were used to make on board measurements of the concentration gradients of dissolved oxygen, Mn²⁺, and Fe²⁺ within the sediments. The O₂ concentrations decreased sharply from about 200 μmol L⁻¹ in the bottom seawater to zero within a depth of a few millimeters into the sediment. Dissolved Mn²⁺ was detected below the oxic zones with peak concentrations up to 600 μmol L⁻¹, whereas dissolved Fe²⁺ had peak concentrations up to 1,000 μmol L⁻¹ in deeper layers. The elemental contents of organic carbon and nitrogen within the sediments were analyzed and their C/N ratios were in the range of 9.0 to 10.1, indicative of heavy terrestrial origin. Sediments from two sites near municipal wastewater discharge outlets had higher organic contents than those from the other sites. These high organic contents corresponded to shallow O₂ penetration depths, high dissolved Mn²⁺ and Fe²⁺ concentrations, and negative redox potentials within the sediments. This indicated that the high organic matter content had promoted microbial respiration within the sediments. Overall, the organic content did not show any appreciable decrease with increasing sediment depths, so a quadratic polynomial function was used to fit the curve of O₂ profiles within the sediments. Based on the O₂ profiles, O₂ fluxes across the seawater and sediment interface were estimated to be in the range 6.07 to 14.9 mmol m⁻² day⁻¹, and organic carbon consumption rates within the surface sediments were estimated to be in the range 3.3 to 20.8 mgC cm⁻³ a⁻¹. The case demonstrated that biogeochemistry within the sediments of the bay was very sensitive to human activities such as sewage discharge.     

Spatial and Temporal Variability of Sediment Organic Matter Recycling in Two Temperate Eutrophicated Estuaries

This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon (δ ¹³C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m^?2 day^?1 in the Elorn estuary and 10 mmol m^?2 day^?1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O₂ fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO _x ^? (>200 μM) and the large NH₄ ⁺ increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ ¹³C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ ¹³C values in the Aulne watershed. A high increase of δ ¹³C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.     

Heavy metal distribution in surface sediments of the Tirumalairajan river estuary and the surrounding coastal area, east coast of India

Surface sediments collected at the Tirumalairajan river estuary and their surrounding coastal areas were analyzed for the bulk metal concentration. The sediments were collected from post- and premonsoon seasons. Dominances of heavy metals are in the following order: Fe > Mn > Zn > Pb > Cu in both seasons from estuary and coastal area. The results reveal that Fe, Mn, Cu, Pb, and Zn demonstrated an increased pattern from the estuary when compared to the coastal area. The heavy metal pattern of the sediments of the Tirumalairajan river estuary and its surrounding coastal area offered strong evidence that the coastal area was a major source of heavy metals to the estuarine region. For various metals, the contamination factor and geoaccumulation index (I _geo) have been calculated to assess the degree of pollution in sediments. The contamination factor and geoaccumulation index show that Zn, Pb, and Cu unpolluted to moderately pollute the sediments in estuarine part. This study shows the major sources of metal contamination in catchment and anthropogenic ones, such as agriculture runoff, discharge of industrial wastewater, and municipal sewage through the estuary and adjoining coastal area.     

Grain size and geochemistry of surface sediments in northwestern continental shelf of the South China Sea

Eighty-six surface sediments collected from the northwestern continental shelf of the South China Sea (SCS) were analyzed for grain size distribution, calcium carbonate, organic carbon, and major and trace element compositions to investigate sediment provenance and factors controlling their geochemical composition. Sediments from the eastern continental shelf of Hainan Island have higher sand and lower clay content, while the samples from the nearshore Hainan Island have higher contents of gravel and clay. Calcium carbonate contents in samples show a positive correlation with water depth in northwestern shelf of SCS, suggesting that it is related to biological factors. However, the nearshore sediments have higher contents of organic carbon compared to those of the outer shelf, possibly suggesting that the terrigenous organic matter usually deposited in nearshore environments such as bays and estuaries. Compared with the upper continental crust, the samples have relatively lower contents of SiO₂ and Al₂O₃, higher than those of the Pearl and Red river sediments. The low contents of K₂O and Na₂O in sediments from the northwestern continental shelf are consistent with intense chemical weathering in the river basin due to the seasonally hot and humid climate regime. The sediments mainly consist of three components, including the gravel fraction composed of calcareous debris, the sand fraction composed of quartz, and the silt and clay fractions mainly composed of clay minerals. The content of each component depends on grain size, sediment source, biogenesis, and hydrodynamic conditions, which finally controls the chemical composition of the sediments. The distributions of Co/Al₂O₃, Cr/Al₂O₃, and Zr/Sc ratios for sediments in the northwestern continental shelf suggest that source rocks are mainly composed of felsic rocks rather than mafic rocks. There is a distinct difference in sediment source between eastern and western shelf sediments; the eastern shelf sediments are characterized by high Zr/Sc ratios mainly derived from the Pearl River, while the western shelf sediments have relatively low values of Zr/Sc indicating a main contribution possibly sourced from the Red River Basin. Terrigenous materials from Hainan Island usually influence the geochemistry of sediments deposited in the nearshore area.     

Spatial and temporal variations in terrestrially-derived organic matter from sediments of the Delaware estuary

Terrestrially-derived organic matter in sediments of the Delaware Estuary originates from riverine transport of soils and fresh litter, sewage and industrial wastes, and marsh export of organic matter. The quantity, composition, and spatial distribution of terrigenous organic matter in sediments was determined by elemental (C and N), lignin, and stable carbon isotope analyses. Sediments in the upper Delaware Estuary had low organic carbon content and high lignin content. In contrast, sediments in the lower Delaware Estuary had high organic carbon content and low lignin content. There was a slight decrease in the proportion of syringyl and cinnamyl phenols relative to vanillyl phenols between the upper estuary and lower estuary. Differences in lignin and stable carbon isotope compositions between sediments of the Delaware Estuary and sediments of the Broadkill River estuary (an adjoining salt-marsh estuary) supported previous observations that marshes do not export substantial quantities of organic matter to estuaries. Additional results suggested that lignin-rich sediments were concentrated in the upper estuary, most likely in the zone of high turbidity. Furthermore, algal material diluted lignin-rich sediments, particularly in the lower estuary. The weaker algal signal in bottom sediments compared to that in suspended particulate matter suggested algal material was decomposed either in the water column or at the sediment-water interface. Physical sorting of sediments prior to deposition was also indicated by observations of compositional differences between the upper and lower estuary bottom sediments. Finally, seasonal variations in primary productivity strongly influenced the relative abundance of terrestrial organic matter. In fall, however, the proportion of lignin was greatest because of a combination of greater inputs of terrestrially-derived organic matter, lower river discharge, and a decrease in algal biomass.     

Determination of the origin of suspended matter and sediments in the Elbe estuary using natural tracers

The clay mineral composition, the concentrations of carbonates, the proportions of carbon and oxygen isotopes in carbonates and organic matter, as well as the concentrations of different nonanthropogenic metals were used to determine the origin of different grain size fractions of sediments and suspended matter in the Elbe estuary. Analysis of the smectite/kaolinite proportion revealed that solid material ≤2 μm from the North Sea is transported up the river, about 40 km beyond the most upstream position of the salt wedge. In the 2–20 μm fraction, the¹⁶O/¹⁸O ratio in carbonates and the kaolinite/chlorite proportion demonstrate a transport of North Sea material between 40 and 20 km upstream of the marine water limit. The transport behaviour of the 20–63 μm grain size fraction could be determined by the hafnium concentration, representative for the heavy mineral zircon. In this case, the transport distance beyond the salt wedge was up to 20 km. No information was available on the origin of the fine organic matter, whereas the coarser fractions were derived primarily from debris of salt marsh vegetation. The results demonstrate that in the Elbe estuary mixing between marine and fluvial solid material occurs upstream of the salt wedge and is significantly responsible for the observed decrease in the concentration of various pollutants in sediments and suspended matter along the estuary. The cause of the upstream particle transport is probably a scour lag mechanism based on asymmetries of the flood- and ebb-tide current distribution, especially their differing maximum velocities.     

Effects of grain size distribution on mineralogical and chemical compositions: a case study from size‐fractional sediments of the Huanghe (Yellow River) and Changjiang (Yangtze River)

The influence of hydrodynamics on the chemical composition of sediments is based on the uneven distribution of element abundances in different size fractions. In this study, 72 size‐fractional sediments from the Huanghe (Yellow River) and Changjiang (Yangtze River) riverbeds were measured with XRD, SEM, ICP‐AES and ICP‐MS. The analysis results show that the mineral and chemical characteristics change with grain size in the Huanghe and Changjiang sediments. According to the principal components analysis, three independent geochemical factors were found. The first factor elements, Zr, Hf, Th, U, Y, La and TiO₂ are influenced by the existence of heavy minerals. The second factor elements, Al₂O₃, alkalis, alkaline earth (excluding Ca and Sr) and most of the transitional metals are dominated by clay minerals. The third factor group includes Ca and Sr, which were controlled by calcium‐bearing mineral contents and chemical weathering intensities. The various grain size distributions greatly affect the mineralogical and chemical compositions of bulk sediments. Compared to other size fractions, the 5–6PHI size fractions of the Huanghe and Changjiang sediments have special mineralogical and chemical compositions, and intermediate volume percentages. Weight or volume percentage of each size fraction may be more suitable than mean grain‐size of the bulk sediment to elucidate the grain size effects. Chemical Index of Alteration (CIA) values increase steeply with decreasing grain size, while Weathering Index of Parker (WIP) values are relatively stable. Because of the big influence of the abundance of clay minerals on CIA values, it is questionable to use CIA as a proxy of weathering intensity. Considering the clay mineral effects, stability in values and heterogeneous material properties, WIP has the potential to indicate the chemical weathering intensity of sediments. Copyright © 2014 John Wiley & Sons, Ltd.     

Concentration distribution and assessment of heavy metals in sediments of mud area from inner continental shelf of the East China Sea

Heavy metals (Cr, Cu, Zn, Cd, Pb, Hg, and As), grain-size, pH, Eh, and total organic material (TOM and TN) of 59 surficial sediments of mud area from the inner continental shelf of the East China Sea have been analyzed. The relations of the heavy metals to sediment composition, pH, reduction/oxidation conditions and total organic materials were evaluated with multivariate statistics analysis, and the hydrodynamic conditions such as coastal current and Taiwan warm current are the other important controlling factors to the distribution of heavy metals. Sediment enrichment factors and potential ecological hazard index ( E_\textRI E_{\text{RI}} ) were used to assess the heavy metals accumulation; the results indicate that moderate contamination of most heavy metals is prevalent, and the contamination level in the estuary is rather high, which is mainly from anthropogenic source. Compared with other areas in China, the contaminant level of the study area is moderate.     

I–P<Subscript>2</Subscript>O<Subscript>5</Subscript> diagrams as an indicator of depositional environment in marine sediments: preliminary findings (Sri Lanka)

The concentrations of Br and I in marine sediments have been used to categorize the sedimentary environments of different coastal regions of the world with respect to organic matter contents. The present study uses the concentrations of Br, I and P₂O₅ of different marine settings as a new proxy to interpret the depositional environments. A total of 150 coastal lagoon sediment samples (suspended sediments, surface sediments and sediment cores) were analyzed for Br, I and P₂O₅ concentrations by X-ray fluorescence spectrometry. They were compared with the Br, I and P₂O₅ concentrations of the 2004 Indian Ocean tsunami sediments. Sediments from various sources are separately clustered in I–Br plot and a trivial negative correlation is found for the whole plot. A similar correlation pattern exists in the I–P₂O₅ diagram. This correlation is explained by the distribution of marine plants (higher and lower) in different sedimentary environments of the coastal profile. Therefore, the concentration of I and its relation to P₂O₅ can be used as a tool to identify sediment depositional environments in marine settings.     

Retention of fly ash-derived copper in sediments of the Pandu River near Kanpur,India

A coal-based thermal power plant is situated on the bank of the Pandu River, which is a tributary to the Ganges near Kanpur. River sediments downstream from the ash pond outfall are contaminated by fly ash. In order to establish the role of soils and sediments in retaining fly ash-derived heavy metals, copper was investigated as a model metal. A maximum concentration of 70 ppm Cu could be leached from the fly ash, confirming that it is a major source of this metal. Soil samples and river sediments were examined for Cu adsorption in the natural state as well as after treatment with H₂O₂, EDTA, and H₂O₂ followed by EDTA. The organic fraction of the samples was determined, and it had a major control on removal of Cu from a solution with 10^–4 M initial concentration. Further characterization of organic matter indicated that with reference to natural samples, the humic acid fraction had a copper enrichment factor in the range 9.1–15.1. The factor for fulvic acids, in contrast, was between 3.5 and 5.5. This leads to the conclusion that river deposits rich in humic acids would withstand relatively high metal loads. Only when the metal input exceeds the maximum retention potential, would the metal be fractionated into the aqueous phase and act as a potential biocide.     

Organic carbon burial rates,and carbon and sulfur relationships in coastal sediments of the southern Baltic Sea

Organic C burial rates and C–S relationships were investigated in the Holocene sediment sequences of 3 shallow polymictic coastal lagoons in the southern Baltic Sea to better understand the biogeochemical cycling of C and S in these environmental systems. The results show that these lagoons may have a considerable influence on the environmental status of the southern Baltic Sea area in having the potential to act as a temporary sink or source for heavy metals. High organic C accumulation rates (C_org-AR) can be observed in the sediments due to a high organic matter supply from land and a high productivity of the water bodies as a result of eutrophication. However, organic C burial does not increase as a result of increasing sediment accumulation rates (SAR). Even when high sedimentation rates do occur, there appears to be a thorough recycling and resuspension of the sediment enhancing the biological decay of organic matter before burial or the removal of organic matter from the system by transport. That is why high SAR in the coastal lagoons do not enhance pyrite formation, and thereby permanent fixing of heavy metals in the sediments, to the extent that could be expected from their magnitude. Initially there is a high potential for a temporary binding of heavy metals, but the latter are likely to be subject to mobilization and redistribution within the sediments and the water column. The patterns of burial of organic and mineral matter are different from those observed in the present-day Baltic Proper, implying possible important links in deposition between the central and coastal areas of the Baltic Sea and implications for C cycling in the ecosystem of the Baltic Sea.     

Heavy metal mobility assessment in sediments from the Odiel River (Iberian Pyritic Belt) using sequential extraction

The Tessier sequential extraction scheme (SES) was applied to sediments from the Odiel river catchment (Iberian Pyritic Belt, SW of Spain), one of the most acid rivers on Earth, to assess the chemical association (exchangeable, carbonatic, bound to manganese and iron oxides, bound to organic matter and residual mineral) of heavy metals (Zn, Cd, Pb, Cu, Cr, Mn, Ni, Fe, and Hg). Sediments are very heterogeneous in their textural characteristics, showing different grain size. Twenty-seven samples were studied from from areas along the Odiel River, from the source to the mouth, with special interest in the Odiel Marshes Natural Park due to its ecological significance. Samples were classified as sandy (especially at the river mouth with low iron oxide and organic matter content) and clay-silty (in the middle of the river catchment with high iron oxide content). The numerous sandy samples with low pH values explain the low levels of metals upstream, although potential metals contributions arise from mining and ore. However, the presence of sulfate in the mining area and carbonate at the mouth may explain the high presence of lead and iron in these sandy zones. Some percentage of mobile Ni, Cu, and Zn were detected in the mining area, but the elevated relative percentage of exchangeable Cd in the estuary is even more remarkable. The percentage of Zn bound to carbonate is considerable in the catchment but especially in the estuary. However, Cu is only detected in the carbonate phase downstream, in spite of the low concentration of carbonate, which represents a drawback in the application of the Tessier SES to these types of samples. Finally, relatively high percentages of residual, non-mobile, Hg and Pb were observed, in the estuarine and mining areas, respectively. Sand, lime, and clay fractions of representative samples from Areas I, II, and III were used in a metal speciation study. Mainly, the elements analyzed had accumulated in the non-residual fractions. In the mining area of the Pyrite Belt, the elements analyzed are mainly bound to Fe–Mn oxides (Fe + Mn + Cu + Cr + Pb + Mn ± Zn) and the organic matter/sulfide fraction (Ni + Zn + Hg ± Cd), independent of sediment grain size. In conclusion, we show that the results of the study of chemical speciation in sediments from acid rivers are independent of the sediment grain size considered.     

Heavy metals in sediments—problems concerning determination of the anthropogenic influence. Study in the Krka River estuary,eastern Adriatic coast,Yugoslavia

Factors that govern heavy metal concentration in sediments were examined by a combined analytical, geochemical, and geological approach. The constrains encountered in the determination of the anthropogenic influence are exposed. The region examined was the Krka River estuary located in the typical karst region of the eastern Adriatic, Yugoslavia.Sedimentological research revealed that: the Krka River (main water supplier) is almost free of suspended terrigenous material; the main supplier of suspended terrigenous matter of flysch origin is a small torrent-type Gudua Creek, and that this fine grained terrigenous material is sedimented mostly in the central enlarged part of the estuary, the Prokljan Lake.Three different groups of heavy metals were identified in recent sediments. Increased concentrations of nickel and zinc were found in estuarine sediments due to strongnatural enrichment in source rocks. Manganese and chromium were found to benaturally enriched and depleted in surface layer respectively, due to the different postdepositional geochemical behavior. Lead and copper concentrations were found to be increased in surface sediments in the central part of the estuary, apparently from anthropogenic source.     

Geochemistry of C25 and C30 biogenic alkenes in sediments of the narragansett bay estuary

The distributions of a series of structurally related C₂₅ and C₃₀ biogenic alkenes in sediments of the Narragansett Bay estuary have been determined. The suite of alkenes detected differs both quantitatively and qualitatively from those previously reported in other estuanne and coastal regions. Four C₂₅ mono- and dienes and one C₃₀ diene comprise 73–91% of the total alkenes in all surface (upper 2.5–5 cm) sediments analyzed. However, significant geographic variations exist in the relative abundance of these five compounds throughout the estuary. A comparison of alkene concentrations with δ¹³C of the bulk sedimentary organic matter has shown that the geographic variations of some alkenes reflect the distribution of marine organic matter, suggesting a marine source for these compounds. The distributions of other alkenes are not similarly correlated. In particular, concentrations of the C₃₀ diene are relatively constant and exhibit no dependence on the origin of organic matter in these sediments. This distribution implies an in situ production of this alkene throughout the estuary. Analysis of several sediment cores reveals that alkene concentrations are generally highest at the surface and decrease to low, constant values within the upper 25 cm. An exception is the subsurface concentration of one C₂₅ diene, which exhibits an increase at the same depth in two separate upper bay cores.