Influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments

To investigate the influence of mangrove reforestation on heavy metal accumulation and speciation in intertidal sediments, core sediments from a restored mangrove forest and adjacent mud flat in Yifeng Estuary (southeastern China) were analyzed. The chemical speciation of heavy metals (Pb, Zn, Cu, Cr and Ni) was determined according to a sequential extraction procedure. Special attention was paid to the upper 20 cm of sediment, in which metal accumulation was enhanced and speciation was obviously modified. Mangrove reforestation decreased the concentrations of all metals in the acid-soluble fraction and increased metal concentrations in the oxidizable fraction. Increased Pb, Zn and Cu concentrations and decreased Ni and Cr concentrations were observed in the reducible fraction. These results suggest that mangrove reforestation facilitated the accumulation of heavy metals in the upper sediment layers but decreased their bioavailability and mobility.     

The role of vegetation in the retention of fine sediment and associated metal contaminants in London's rivers

Many urban rivers receive significant inputs of metal‐contaminated sediments from their catchments. Restoration of urban rivers often creates increased slack water areas and in‐channel vegetation growth where these metal‐contaminated sediments may accumulate. Quantifying the accumulation and retention of these sediments by in‐channel vegetation in urban rivers is of importance in terms of the planning and management of urban river restoration schemes and compliance with the Water Framework Directive. This paper investigates sediment properties at four sites across three rivers within Greater London to assess the degree to which contaminated sediments are being retained. Within paired restored and unrestored reaches at each site, four different bed sediment patch types (exposed unvegetated gravel, sand, and silt/clay (termed ‘fine’) sediments, and in‐channel vegetated sediments) were sampled and analysed for a range of metals and sediment characteristics. Many samples were found to exceed Environment Agency guidelines for copper (Cu), lead (Pb) and zinc (Zn) and Dutch Intervention Values for Cu and Zn. At all sites, sediments accumulating around in‐channel vegetation were similar in calibre and composition to exposed unvegetated fine sediments. Both bed sediment types contained high concentrations of pseudo‐total and acetic acid extractable metal concentrations, potentially due to elevated organic matter and silt/clay content, as these are important sorbtion phases for metals. This implies that the changed sediment supply and hydraulic conditions associated with river restoration may lead to enhanced retention of contaminated fine sediments, particularly around emergent plants, frequently leading to the development of submerged and emergent landforms and potential river channel adjustments. High pseudo‐total metal concentrations were also found in gravel bed sediments, probably associated with iron (Fe) and manganese (Mn) oxyhydroxides and discrete anthropogenic metal‐rich particles. These results highlight the importance of understanding the potential effects of urban river restoration upon sediment availability and channel hydraulics and consequent impacts upon sediment contaminant dynamics and storage. Copyright © 2014 John Wiley & Sons, Ltd.     

Laboratory scale study of an industrial phosphate and thermal treatment for polluted dredged sediments

Dredged sediments are being chemically treated with phosphoric acid on an industrial scale.The effectiveness of the treatment was evaluated by performing the chemical reaction in a tubular reactor, followed by convective drying and maturation of the treated sediment at ambient temperature and finally thermal destruction of the organic matter by calcinations(500℃-900℃).The influence of acid concentration and calcination temperature on the specific surface area of the sediment was investigated. The stabilization of the heavy metals was evaluated by leaching tests and sequential extraction procedures.The phosphoric acid treatment is effective in reducing heavy metal mobility,a prerequisite for recycling the sediments in various construction materials.     

Assessment of heavy metal contamination and mineral magnetic characterization of the Asopos River sediments (Central Greece)

The content and distribution of heavy metals in sediments of the intermittent and contaminated Asopos River, located in Central Greece, was assessed by means of total dissolution, dilute acid and sequential extraction procedures. Mineral magnetic properties were used as proxy parameters of transport mechanisms of land-derived material to the sea. The combination of enrichment factors estimated against local background levels and the levels of labile metals revealed that surface sediments are enriched in Cu, Cd, Ni and Cr. The low flow of the system allows particles and organic matter to accumulate in the estuarine shallow “pools” where they undertake a series of redox reactions, authigenic formation, etc. The most fine of these particles, which are metal rich, are transported to relatively long distances off the Asopos River mouth, even under low energy conditions, converting the system to a secondary source of pollution for the adjacent marine environment.     

Unusual grain size effect on trace metals and organic matter in contaminated sediments

Grain size effect on trace metals (cadmium, copper, lead, zinc, and iron) and total organic content distribution in various fractions (<0.063, 0.063–0.105, 0.105–0.250, 0.250–0.500, and 0.500–1.000 mm) of contaminated sediment has been studied. Selective partitioning of the studied contaminants in sediment fractions was observed, with a minimum content in the fine sand fraction of grain size 0.125–0.250 mm. Anomalously high concentrations of trace metals and organic matter content in the medium and coarse sediment fractions (>0.250 mm) was explained by the formation of large agglomerates (clusters) during the generally recommended drying procedures. These large agglomerates, formed from smaller sediment fraction particles enriched by various contaminants kept on their large specific area by adsorption forces, have been observed in photographs of the medium and coarse sediment fractions only. The formed agglomerates consist of small particles cemented either by dissolved organic matter or by sea salts present in the marine sediment. The formation of such agglomerates should be taken into consideration when conducting metal contamination studies on sediments.     

Evaluation of geochemical behavior and heavy metal distribution of sediments：The case study of the Tirumalairajan river estuary,southeast coast of India

The purpose of this study was to assess the chemical partitioning of selected heavy metals(Fe,Mn,Cu,Zn,Pb,Cr,Co and Ni) in 10 surface sediments at Tirumalairajan River Estuary in the southeastern coast of India.A five-step sequential extraction technique was used to assess the environmental status of heavy metals.Most of metals were considered to be immobile due to the high availability in the residual fraction of heavy metals.The sediments of Tirumalairajan River estuary had not been polluted by heavy metals,and they didn’t pose any high ecological risk.The seasonal variations of heavy metals were slightly higher in summer than in monsoon season.Factor analysis was also carned out to understand the associations of metals in different fractions with sand,silt,clay,organic matter,pH,salinity and other metals.The relationship between the Q-mode and R-mode cluster analyses was useful for identifying the pollution levels in both seasons.It was proved that the enrichment of heavy metals was related with geogenic and anthropogenic sources.The information on total metal concentrations in sediments was not sufficient for assessing the metal behavior in the environment,but the sequential extraction technique was more effective in estimating the environmental impact of contaminated sediments.     

Eutrophication and heavy metal pollution in the Flensburg Fjord: A reassessment after 30 years

A study of surface sediment organic matter and heavy metal content (e.g. Cu, Zn, Pb and Sn) was carried out in 2006 to assess changes in eutrophication and pollution in the periodically anoxic Flensburg Fjord since 1972. Low hydrodynamic activity together with sewage discharges and high primary production in the inner fjord promote the enrichment of present day surface sediments in organic matter and metals in contrast to the outer fjord. However, heavy metal contents in the fjord are typical for the western Baltic Sea, although they are higher than in the preindustrial period.Although the anthropogenic nutrient load has substantially decreased since the 1970s, sediments from the inner fjord contain more organic material in 2006 than in 1972 resulting from still high levels of primary production supported by internal nutrient loading. Of the heavy metals measured, a decrease in Pb content since the 1970s is distinct, which is explained by the banning on gasoline lead. Taken together, these results suggest that the amelioration of environmental conditions needs time but is indeed related to reduced anthropogenic inputs.     

Heavy metals in surface sediments from nine estuaries along the coast of Bohai Bay,Northern China

Concentrations of heavy metals in river water and sediment were investigated in nine estuaries along the coast of Bohai Bay, Northern China. Multivariate statistical techniques such as principal component analysis and cluster analysis, in combination with metal concentration analysis and correlation analysis, were used to identify the possible sources of the metals and the pollution pattern in nine estuaries along the coast of Bohai Bay. The environmental risks of metals, evaluated by sediment quality guidelines and background values, revealed Hg contamination in the estuaries. However, levels of Cd in estuarine sediments were low, and they were less than those levels in river sediments, partly due to the high mobility and dilution of river or seawater. Cd did not contribute to sediment deposits in estuaries. High organic matter from effluents from large municipal sewage treatment plants was predominantly responsible for restricting Hg mobility from the river to Bohai Bay.     

Effects of prokaryotic diversity changes on hydrocarbon degradation rates and metal partitioning during bioremediation of contaminated anoxic marine sediments

We investigated changes of prokaryotic diversity during bioremediation experiments carried out on anoxic marine sediments characterized by high hydrocarbon and metal content. Microcosms containing contaminated sediments were amended with lactose and acetate and incubated in anaerobic conditions up to 60 d at 20 or 35 °C. Microcosms displaying higher degradation efficiency of hydrocarbons were characterized by the dominance of Alphaproteobacteria and Methanosarcinales and the lack of gene sequences belonging to known hydrocarbonoclastic bacteria. Multivariate analyses support the hypothesis that Alphaproteobacteria are important for hydrocarbon degradation and highlight a potential synergistic effect of archaea and bacteria in changes of metal partitioning. Overall, these results point out that the identification of changes in the prokaryotic diversity during bioremediation of contaminated marine sediments is not only important for the improvement of bio-treatment performance towards hydrocarbons, but also for a better comprehension of changes occurring in metal partitioning which affect their mobility and toxicity.     

Distribution of dissolved and labile particulate trace metals in the overlying bottom water in the vistula river plume (southern Baltic Sea).

Overlying bottom water samples were collected in the Vistula River plume, southern Baltic Sea, (Poland) and analysed for dissolved and labile particulate (1 M HCl extractable) Cu, Pb, Zn, Mn, Fe and Ni, hydrological parameters being measured simultaneously. Particulate organic matter (POM), chlorophyll a and dissolved oxygen are key factors governing the chemical behaviour of the measured metal fractions. For the dissolved Cu, Pb, Zn, Fe and Ni two maxima, in the shallow and in the deeper part of the river plume, were found. In the shallow zone desorption from seaward fluxing metal-rich riverine particles account for markedly increased metal concentrations, as confirmed also by high particulate metal contents. For Pb, atmospheric inputs were also considered to have contributed to the elevated concentrations of dissolved Pb adjacent to the river mouth. In the deep zone desorption from detrital and/or resuspended particles by aerobic decomposition of organic material may be the main mechanism responsible for enrichment of particle-reactive metals (Cu, Pb, Zn) in the overyling bottom waters. The increased concentrations of dissolved Fe may have been due to reductive dissolution of Fe oxyhydroxides within the deep sediments by which dissolved Ni was released to the water. The distribution of Mn was related to dissolved oxygen concentrations, indicating that Mn is released to the water column under oxygen reduced conditions. However, Mn transfer to the dissolved phase from anoxic sediments in deeper part of the Vistula plume was hardly evidenced suggesting that benthic flux of Mn occurs under more severe reductive regime than is consistent with mobilization of Fe. Behaviour of Mn in a shallower part has been presumably affected by release from porewaters and by oxidization into less soluble species resulting in seasonal removal of this metal (e.g. in April) from the dissolved phase. The particulate fractions represented from about 6% (Ni) and 33% (Mn, Zn, Cu) to 80% (Fe) and 89% (Pb) of the total (labile particulate plus dissolved) concentrations. The affinity of the metals for particulate matter decreased in the following order: Pb > Fe > Zn > or = > Cu > Mn > Ni. Significant relationships between particulate Pb-Zn-Cu reflected the affinity of these metals for organic matter, and the significant relationship between Ni-Fe reflected the adsorption of Ni onto Fe-Mn oxyhydroxides. A comparison of metal concentrations with data from other similar areas revealed that the river plume is somewhat contaminated with Cu, Pb and Zn which is in agreement with previous findings on anthropogenic origin of these metals in the Polish zone of southern Baltic Sea.     

Speciation of heavy metals on suspended sediment under high flow conditions in the River Aire,West Yorkshire,UK

Concentrations of heavy metals (Cd, Cu, Pb and Zn) on suspended sediments during a flood event at Thwaite Mills, River Aire, were analysed using a five step sequential extraction technique to determine their major chemical associations (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions). Total metal concentrations were lowest at higher discharges, resulting from dilution by clean sediment. The major transport fractions are the Fe and Mn oxides, which carry 29% of the total metals. Knowledge of the chemical forms of heavy metals on suspended sediment is essential for estimating their biological availability and physicochemical reactivity. © 1998 John Wiley & Sons, Ltd.     

Textural and geochemical characteristics of off shore sediment of North Bay of Bengal:A statistical approach for marine metal pollution

Metal pollution study on sediments of North Bay of Bengal sediments presented in this paper is based on existing Lithostratigraphy of upstream,mineralogy and geochemical analysis of 42 sediment samples.The statistical analysis identifies the metal pollution as well as its apparent source in the off shore regions.Samples were analyzed for grain size,organic content and heavy metals(Fe,Mn,Cr,Cu,Ni,Pb,Cd,Zn and Co) using the sequential extraction method to evaluate geochemical processes and pollution load.In an effort to surmise anthropogenic input,several approaches including classification by quantitative indexes such as enrichment factor,contamination factor,degree of pollution,pollution load index and geo accumulation index,were attempted.Metal speciation results indicate high%of Cd in exchangeable fraction of Mahanadi transect sediments where as a considerable amount of oxidizable fraction of Cr was detected at Dhamra.Quantitative indexes place North Bay of Bengal under moderately polluted zone due to high level of Cd.Normalization of metals to Fe indicated relatively high enrichment factors for Cd and Cr.Factor analysis identified seven possible types of geochemical associations where sediment pH plays a major role for the heavy metal mobility.The higher Cd concentration in exchangeable fraction as well as the higher EF for Cd and Cr present in sediment may pose a risk of secondary water pollution under slightest disturbance in the geo-chemistry of sediments.Comparison study with available data of near costal zones and upstream stratigraphy revealed that open cast mining,overburden dumping,mineral based industrial effluents were the major source of pollution for catchment area contamination.Bay of Bengal is likely to face a serious threat of metal pollution with the present deposition rates unless rigorous pollution control norms are applied.     

Chemical forms of Pb, Zn and Cu in the sediment profiles of the Pearl River Estuary

The chemical forms of heavy metals (Pb, Zn and Cu) in sediment cores of the Pearl River Estuary were studied using a sequential chemical extraction method. The isotope ratios of 206Pb/207Pb in various chemical fractions were also measured to assess the potential Pb sources. Zinc and Cu were mainly associated with the residual fraction. The Fe-Mn oxide and organic/sulphide fractions were the next important phases for Zn and Cu, respectively. For Pb, different chemical partitioning patterns were found among different sediment cores. Most Pb was associated with the residual fraction in the sediments. In some sediment profiles, the major phase of Pb in the top layers was the Fe-Mn oxide fraction. The proportion of Pb in the Fe-Mn oxide fraction decreased significantly with increasing depth. Among the different depths, the 206Pb/207Pb isotope ratios in the residual fraction remained fairly stable, with a mean value of 1.202, which may represent the natural background value. The 206Pb/207Pb ratios in the exchangeable fraction were the lowest among the five fractions, particularly in top sediments, showing the anthropogenic inputs of heavy metals from recent rapid industrial development in the surrounding region. For the other three non-residual fractions, there was a similar trend of increasing 206Pb/207Pb ratios down the profile. Results from this study are useful in assessing both the chemical changes for heavy metals in marine sediments and the potential of heavy metal release into the water environment of an estuary area.     

Magnetic characteristics of sediment grains concurrently contaminated with TBT and metals near a shipyard in Busan,Korea

Bottom sediments near shipyards are often susceptible to receiving accidental spills of TBT and metals or their degradation products from hull scraping of antifouling system paints applied prior to 2008, when the AFS Convention 2001 was not in force. We investigated TBT and metal contamination of sediments near the shipyards of a small marina located in Busan, Korea and found that they were highly contaminated with TBT, Cu, and Zn. To better understand the environmental impacts and to make an optimal remediation plan, we characterized individual antifouling fragments in terms of metal and TBT contents, magnetic properties, and grain-size. Coarse-sized individual antifouling fragments exhibited simultaneously high levels of TBT, metals and high magnetic susceptibility, and appeared to be a major source of pollution in the sediment. Therefore, magnetic separation in combination with size-separation appears to be a cost-effective remediation method to remove the TBT and metals from contaminated shipyard sediments.     

Chemical forms of heavy metal contaminants in sediments of Miyun reservoir

The chemical forms, spatial distribution and sources of As, Hg, Cd, Pb and Zn in sediments of the Miyun reservoir were studied. The results of sequential extraction demonstrate that most of As, Pb and Zn were bound to the residual fraction, Hg was associated with the sulfide fraction while Cd was associated with the carbonate fraction and the residual fraction. On the vertical profiles the concentrations of the heavy metals in total and each fractions mostly decreased with increasing depths in sediments, suggesting that the heavy metals input from the upstream watershed increases yearly. Summation of the residual fraction, the sulfide fraction and the carbonate fraction accounts for 60.03%―85.60% of the total heavy metal contents in the sediments, which represent the geochemical background values of the elements and relate closely to soil erosion. Results of the main factor analysis show that most sediments of the reservoir come from the upstream soil erosion, the point source pollution and domestic waste. Moreover, the microbial activities taking place on the sediment-water interface are also one of the major factors to cause the increasing content of the organic matter fraction and the iron-manganese oxide fraction. Environmental change of the reservoir water could make the removability of the heavy metals increase, leading to the increase of their concentrations in pore water in sediments, and imperiling water quality of the reservoir.     

Anthropogenic influence on the degradation of an urban lake - The Pampulha reservoir in Belo Horizonte, Minas Gerais, Brazil

The artificial reservoir Lagoa da Pampulha in central Brazil has been increasingly affected by sediment deposition and pollution from urban and industrial sources. This study investigates water chemistry and heavy metal concentrations and their fractionation in the lake sediment using ICP-OES, ICP-MS, and XRD analyses. Fractionation analysis was done by sequential extraction under inert gas as well as after oxidation. The lake exhibits a permanent stratification with an oxygen-free hypolimnion below 2 m depth. Nutrient concentrations are enriched for phosphorous components (SRP, PO₄). In the sediment it was not possible to detect oxygen. Carbon, sulfur, and most of the analyzed heavy metals are enriched in the top sediment layer with a pronounced downward decrease, indicating the presence of an anthropogenic influence. Statistical analysis, including correlations and a Principal Component Analysis (PCA) of depth-related total concentration data, helps to distinguish presumably anthropogenic heavy metals from geogenic components. Some samples with high element concentrations in the sediment also show elevated concentrations in their pore water. Analyses of element distribution between sediment and pore water suggest a strong bonding of heavy metals to the anoxic sediment. The trend towards elevated solubility in the pore water of oxidized samples is clear for most of the analyzed elements. Fractionation analysis reveals characteristic associations of selected elements to specific mineral bonding forms. In addition, it indicates that the behavior of heavy metals in the sediment is strongly influenced by organic substances. These substances provide buffering against oxidation, acidification, and metal release. The high nutrient loading causes reducing conditions in the lake sediment. These conditions trigger the accumulation of sediments rich in S²⁻, which stabilizes the fixation of heavy elements. In the future, care must be taken to reduce the supply of contaminants and to prevent the release of heavy metals from sediments dredged for remediation purposes.     

Bioremediation of petroleum hydrocarbons in anoxic marine sediments: Consequences on the speciation of heavy metals

We investigated the effects of biostimulation and bioagumentation strategies applied to harbor sediments displaying reducing conditions and high concentrations of petroleum hydrocarbons and heavy metals. We compared the microbial efficiency of hydrocarbon removal from sediments maintained for 60 days in anoxic conditions and inoculated with acetate, sulfate-reducing bacterial strains and acetate and sulfate-reducing bacteria. All treatments determined a significant increase in the microbial growth and significant decreases of hydrocarbon contents and of redox potential values. The addition of sulfate-reducing bacterial strains to the sediment was the most efficient treatment for the hydrocarbon removal. In all experiments, significant changes of the heavy metals’ phase repartition were observed. The results reported here suggest that the biodegradation of petroleum hydrocarbons in anoxic marine sediments may be enhanced by stimulating microbial anaerobic metabolism, but care should be applied to monitor the potential changes in the mobility and bioavailability of heavy metals induced by bio-treatments.     

Trace element study in Tisa River and Danube alluvial sediment in Serbia

The contaminated sediment serves as a long-term source of toxic elements,since that mobility and transport in the environment of these elements are strongly influenced to associated solid phase.In this study,the modified Tessier sequential extraction procedure was applied for the fractionation of Cd,As,Hg,Cu,Zn,Cr,Pb,Ni and V in the sediments（Tisa River and canal sediments - Danube alluvial formation）,to obtain an overall classification of trace element pollution in these areas through its spatial distribution.Investigations of this region are important due to the widespread occurrence of metal mining activities throughout the Tisa and Danube drainage basins and possibilities of contamination with toxic elements at studies localities.Five steps of the sequential extraction procedure partitioned elements into CH₃COONH₄ extractable（F1）,NH₂OH·HC carbonate extractable and easily reducible（F₂）, H₂C₂O₄/（NH₄）₂C₂O₄ moderately reducible（F3）,H₂O₂-HNO₃ organic extractable（F4）,and HCl acid soluble residue （F5）.Analyses of the extracts were performed by flame atomic absorption spectrometry.To indicate the degree of risk of toxic elements,risk assessment code and contamination factor have been used.The results of partitioning study indicate that more easily mobilized forms（metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe and Mn oxyhydroxides and Fe and Mn oxides） were predominant for copper,zinc,cadmium and lead,which can be used as indicators for input from anthropogenic source.In contrast,the largest amount of chromium and nickel were associated with the inert fraction,which reduced their solubility and rendered them immobile under natural conditions and indicative of natural origins.Most of remaining portion of metals was bound to ferromanganese oxides fraction.It is concluded that sequential extraction results proved useful to distinguish between anthropogenic and geochemical sources of elements in the sediments.     

Time dependent calibration of a sediment extraction scheme

Sediment extraction methods to quantify metal concentration in aquatic sediments usually present limitations in accuracy and reproducibility because metal concentration in the supernatant is controlled to a large extent by the physico-chemical properties of the sediment that result in a complex interplay between the solid and the solution phase. It is suggested here that standardization of sediment extraction methods using pure mineral phases or reference material is futile and instead the extraction processes should be calibrated using site-specific sediments before their application. For calibration, time dependent release of metals should be observed for each leachate to ascertain the appropriate time for a given extraction step. Although such an approach is tedious and time consuming, using iron extraction as an example, it is shown here that apart from quantitative data such an approach provides additional information on factors that play an intricate role in metal dynamics in the environment. Single step ascorbate, HCl, oxalate and dithionite extractions were used for targeting specific iron phases from saltmarsh sediments and their response was observed over time in order to calibrate the extraction times for each extractant later to be used in a sequential extraction. For surficial sediments, an extraction time of 24 h, 1 h, 2 h and 3 h was ascertained for ascorbate, HCl, oxalate and dithionite extractions, respectively. Fluctuations in iron concentration in the supernatant over time were ubiquitous. The adsorption-desorption behavior is possibly controlled by the sediment organic matter, formation or consumption of active exchange sites during extraction and the crystallinity of iron mineral phase present in the sediments.     

Total and labile metals in surface sediments of the tropical river-estuary system of Marabasco (Pacific coast of Mexico): Influence of an iron mine

Marabasco is a tropical river-estuary system comprising the Marabasco river and the Barra de Navidad Lagoon. The river is impacted by the Pe?a Colorada iron mine, which produces 3.5 million tons of pellets per year. Thirteen surface sediment samples were collected in May 2005 (dry season) in order to establish background levels of Al, Cd, Co, Cu, Fe, Ni, Pb, and Zn in the system and to ascertain the potential mobility of metals in the sediments. Analyses were carried out in the fraction finer than 63 microm, and labile metals extracted according the BCR procedure. Certified reference materials were used for validation of methods. Total concentrations of Cd, Co, Cu, Ni, Pb, and Zn were in the range of 0.05-0.34, 6-95, 0.7-31, 9-26, 2-18, and 53-179 mgkg(-1), respectively; Al and Fe ranges of 24-127, and 26-69 mgg(-1) correspondingly. Cadmium was found to be significantly labile in the sediments (20-100%), followed by Co (0-35%), Ni (3-16%) and Zn (0-25%), whereas the labile fraction for Cu, Fe and Pb was almost negligible (<4%). According with the total metal concentrations, background levels and normalised enrichment factors (NEF) of the metals studied, the impact of the Pe?a Colorada iron mine on the Marabasco system is lower than expected when compared with other similar World systems influenced by mining activities.