Metal concentrations in sediment and Nereis diversicolor in two Moroccan lagoons: Khnifiss and Oualidia

Metal concentrations were measured monthly during an annual cycle (December 2004 to January 2006) in the tissues of Nereis diversicolor ragworms and sediment from two Moroccan Atlantic coastal lagoons: Oualidia in the north, situated in a highly industrialised urban area and Khnifiss in the south, far from anthropogenic influences. Relatively high levels of Zn, Ag and Cd were found in the sediment of Oualidia lagoon, while Ni concentrations were shown to be high at Khnifiss. The significant metal levels at Oualidia are a result of industrial and urban discharges, coupled with discharges from adjacent phosphate ore processing plants. Trace metal concentrations in worms vary according to season; they are usually high in winter and spring, in relation to the animal's reproductive cycle. Comparing the two lagoons, trace metal levels appear to be higher in worms from Khnifiss lagoon, suggesting a higher bioavailability of these elements in a relatively pristine area.     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.     

Distribution of Trace Metals in the Surface Sediments of Two Pristine Subalpine Lakes in Taiwan

Sediment cores were collected from two remote subalpine lakes: the rather shallow (1.5 m) Little Ghost Lake at 2040 m elevation and the deeper, Great Ghost Lake (40 m) at 2150 m elevation. Different early diagenesis of metals were observed. the seasonally anoxic hypolimnion drives the annual iron redox cycle and causes the remobilization of metals in the mobile fractions of sediments in the Great Ghost Lake. These result in the redistribution of metals in the mobile fractions of sediment and poor correlation between metal concentrations. in the Little Ghost Lake, the shallow water column is always oxic with less change of metals in the mobile fractions of sediments. As a result, most metals have strong positive correlations with each other.

The distributions of metal/Al ratios, total metal contents and acid-leached metal concentrations in the near-surface sediments of these two lakes suggest that the anthropogenic inputs from the atmospheric fallouts in recent decades are one of the major factors affecting the distributions of metals such as cadmium, lead and, to a lessor extent, zinc. the Pb-206/Pb-207 ratios confirm the anthropogenic lead input in these surface sediments.     

Importance of background values in assessing the impact of heavy metals in river ecosystems: case study of Tisza River,Serbia

The main objective of this paper is to evaluate how a choice of different background values may affect assessing the anthropogenic heavy metal pollution in sediments from Tisza River (Serbia). The second objective of this paper is to underline significance of using geochemical background values when establishing quality criteria for sediment. Enrichment factor (EF), geoaccumulation index (I _geo), pollution load index (PLI), and potential ecological risk index (PERI) were calculated using different background values. Three geochemical (average metal concentrations in continental crust, average metal concentrations in shale, and average metal concentrations in non-contaminated core sediment samples) and two statistical methods (delineation method and principal component analyses) were used for calculating background values. It can be concluded that obtained information of pollution status can be more dependent on the use of background values than the index/factor chosen. The best option to assess the potential river sediment contamination is to compare obtained concentrations of analyzed elements with concentrations of mineralogically and texturally comparable, uncontaminated core sediment samples. Geochemical background values should be taken into account when establishing quality criteria for soils, sediments, and waters. Due to complexity of the local lithology, it is recommended that environmental monitoring and assessment include selection of an appropriate background values to gain understanding of the geochemistry and potential source of pollution in a given environment.     

The relationship between epilithic periphyton (biofilm) bound metals and metals bound to sediments in freshwater systems

Surficial sediments and epilithic periphyton (biofilm) were sampled from six sites on the River Churnet and five sites on the River Manifold in Staffordshire and analysed for cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn). The sites demonstrated a wide range of sediment trace metal concentrations determined by inductively coupled plasma optical emission spectrometry (ICP-OES) and atomic absorbtion spectroscopy (AAS). Biofilm was removed from the substrate using physical abrasion and 0.005 M ethylenediaminoethanetetra-acetic acid (EDTA) extractant. The European Standards, Measurements and Testing Programmes (BCR) operationally defined geochemical speciation scheme was used to determine the exchangeable, acid soluble fraction of the sediments. Significant positive correlations were determined between the EDTA extractable biofilm and the exchangeable sediment fraction for Cd, Cu and Zn but not for Pb. Natural epilithic periphyton may be a potential metal biomonitor particularly of Cu, Cd and Zn in aquatic systems and provide supporting information in relation to potential sediment toxicity.     

Seasonal and spatial variations of acid-volatile sulphide and simultaneously extracted metals in the Yangtze River Estuary

Surface sediments were collected from the Yangtze River Estuary (YRE) in May 2012, August 2012, November 2012 and February 2013 to analyse the seasonal and spatial distributions of acid-volatile sulphide (AVS), simultaneously extracted metals (SEM) and the sediment toxicity. An optimised method was used for the AVS and SEM analysis and the results showed that the seasonal variations of AVS were positively correlated with changes in water temperature and the position of higher AVS was relatively fixed. The average of SEM was gradually increased from May 2012 to February 2013 and there were abnormally high values of SEM_Cu and SEM_Ni in the YRE. Concentrations of the five SEM components were in the following order: Cd?相似文献   

Accumulation and metal fluxes in the central Venice Lagoon during the last century

Samples from 18 short sediment cores were analyzed for major and trace metals (Al, Fe, Ca, K, Mg, Mn, Si, Ti, Pb, Zn, Cu, Ni, and Cr), ²¹⁰Pb, ¹³⁷Cs, total organic carbon, grain size, and mineralogical composition to find the record of major environmental changes, either natural or anthropogenic, and to establish their chronologies. Some sediments are characterized by nearly constant composition over time, but others clearly show signs of an increasing marine influence, as an increase of the carbonate contents, after the opening of the Malamocco-Marghera Canal in 1969. These changes sometimes obscure the real pattern of pollutants and tracers, which is revealed by normalization against Al. Zn is the most important contaminant, with concentration factors up to 9.3 times the background level, and the most contaminated sediments are those within a few kilometers from the industrial district of Porto Marghera. ²¹⁰Pb activity-depth profiles were used to calculate apparent accumulation rates that provide a basis for the assessment of metal fluxes. The sediments of several sites show a significant increase in anthropogenic metal contamination starting from the second decade of last century, with maximum inputs from 1930 to 1970. The decrease of heavy metal concentrations observed in surficial sediments of some sampling sites could be related to a recent reduction of pollutant inputs.     

Distribution of Trace Metals in the Surface Sediments of Two Pristine Subalpine Lakes in Taiwan

Sediment cores were collected from two remote subalpine lakes: the rather shallow (1.5 m) Little Ghost Lake at 2040 m elevation and the deeper, Great Ghost Lake (40 m) at 2150 m elevation. Different early diagenesis of metals were observed. the seasonally anoxic hypolimnion drives the annual iron redox cycle and causes the remobilization of metals in the mobile fractions of sediments in the Great Ghost Lake. These result in the redistribution of metals in the mobile fractions of sediment and poor correlation between metal concentrations. in the Little Ghost Lake, the shallow water column is always oxic with less change of metals in the mobile fractions of sediments. As a result, most metals have strong positive correlations with each other.

The distributions of metal/Al ratios, total metal contents and acid-leached metal concentrations in the near-surface sediments of these two lakes suggest that the anthropogenic inputs from the atmospheric fallouts in recent decades are one of the major factors affecting the distributions of metals such as cadmium, lead and, to a lessor extent, zinc. the Pb-206/Pb-207 ratios confirm the anthropogenic lead input in these surface sediments.     

Sediment and porewater geochemistry in a metal contaminated estuary,Dulas Bay,Anglesey

Remobilisation of contaminant metals from sediments can occur by chemical, biological or physical changes. This in turn can lead to contaminant fluxes to the porewaters and ultimately the water column. The aim of the research presented here is to document post-depositional controls on metal mobility and fluxes in a heavily metal-contaminated estuary. This will allow for an improved understanding of the impact of contaminated sediments on water quality from both a short-term and long-term perspective. Dulas Bay is situated on the east coast of Anglesey, North Wales, and receives polluted waters from Parys Mountain. Metals within Dulas Bay sediments show surface enrichment and variations in mineralogical form. Diagenesis clearly plays a role in post-depositional behaviour of the metals, forming sulphides and potentially carbonates. The presence of a dominant exchangeable/carbonate fraction, and elevated porewater metals, in this sulphidic system is significant and could indicate the presence of freshwater diagenesis, or, reflect the high levels of metals in the sediment.     

Heavy metal speciation,leaching and toxicity status of a tropical rain-fed river Damodar,India

Speciations of metals were assessed in a tropical rain-fed river, flowing through the highly economically important part of the India. The pattern of distribution of heavy metals (Cd, Co, Cr, Cu, Mn, Ni, Pb and Zn) were evaluated in water and sediment along with mineralogical characterization, changes with different water quality parameters and their respective health hazard to the local population along the Damodar River basin during pre-monsoon and post-monsoon seasons. The outcome of the speciation analysis using MINTEQ indicated that free metal ions, carbonate, chloride and sulfate ions were predominantly in anionic inorganic fractions, while in cationic inorganic fractions metal loads were negligible. Metals loads were higher in sediment phase than in the aqueous phase. The estimated values of I_geo in river sediment during both the seasons showed that most of the metals were found in the I_geo class 0–1 which represents unpolluted to moderately polluted sediment status. The result of partition coefficient indicated the strong retention capability of Cr, Pb, Co and Mn, while Cd, Zn, Cu and Ni have resilient mobility capacity. The mineralogical analysis of sediment samples indicated that in Damodar River, quartz, kaolinite and calcite minerals were dominantly present. The hazard index values of Cd, Co and Cr were >?1 in river water, which suggested potential health risk for the children. A combination of pragmatic, computational and statistical relationship between ionic species and fractions of metals represented a strong persuasion for identifying the alikeness among the different sites of the river.     

Metal distribution in marine sediments of the Mar Piccolo in Taranto (Ionic Sea,southern Italy)

The spatial distribution of selected metals (Fe, Ni, Mn, Zn, Cu, Pb, Hg and Cd) and their partition in the different chemical forms (speciation) were determined in benthic sediments from Mar Piccolo, Taranto (Ionic Sea, southern Italy). The aim of this study was to assess the degree of sediment contamination and bioavailability of metals, very important for Italian mussel culture, in a semi-enclosed marine ecosystem. In sediments, grain size distribution, total organic carbon (TOC), and humic (HA) and fulvic (FA) acids contents were also determined. The compounds TOC, HA and FA, in fact, have a great influence on metal complexation. High concentrations of copper, lead, zinc and mercury were found, especially in sediments of the first inlet of Mar Piccolo. Statistical analysis of results shows significant correlation among Cu, Pb and Zn concentrations and the influence of organic matter on the sediment distribution of Cu, Pb and Zn. Metal speciation analysis, carried out with sequential extraction method, shows that Fe and Ni are present in sediments mainly as sulphides. Mn and Pb are present principally in an ion-exchangeable form or bound to carbonate and Cu is associated to organic matter. Metal pollution index (MPI), calculated as a weighed mean of the metal contamination factors in each station, shows that with regard to Cu, Ni, Pb and Zn, some stations investigated are unpolluted (MPI <1), whereas in other areas, pollution level is not very high. On the contrary, for mercury, the pollution level in the first inlet of the basin is very high.     

A Petrographic Investigation of two Sequential Extraction Techniques Applied to Anaerobic Canal Bed Mud

The application of sequential extraction procedures to determine metal speciation in sediments is fraught with uncertainty regarding what is actually dissolving or re-precipitating at each stage. In order to choose an appropriate scheme for the investigation of contaminated anaerobic mud two different sequential extraction procedures (Kersten and Förstner, 1986; Quevauviller, 1998) were investigated using a Cryogenic SEM (CryoSEM) technique coupled with energy dispersive X-ray analysis (EDXA). This enabled assessment of the degree of reagent selectivity and any re-precipitation associated with the respective methods. Analysis of the non-leached sediment revealed the most abundant authigenic minerals in order of decreasing abundance to be Fe²⁺-phosphate vivianite (Fe₃(PO₄)₂·8H₂O), mixed Fe, Zn, Cu sulphides, pyrite and calcite. After each stage of the sequential extraction the sediment residue was examined using CryoSEM. After extraction of the exchangeable fraction no obvious evidence of mineral dissolution was observed. Calcite was not completely dissolved during the carbonate extraction stage of either procedure. Vivianite began to dissolve in the carbonate extraction stage of both procedures and was completely dissolved by oxide extraction stage of both procedures. The sediment leached by acidified ammonium oxalate, contained abundant Fe oxalate crystals, suggesting that a large proportion of the Fe released from the vivianite has been re-precipitated. The Fe oxalate was then dissolved with the subsequent sulphide fraction. The technique used to extract the sulphide and organic fraction is the same in both schemes and no sulphide or metal rich organic matter was found in either residue.     

Remobilization of selected metal ions from Nile sediment (Egypt) according to sequential extraction and metal–EDTA complex

River sediments are basic components of our environment, providing nutrients for living organisms and serving as sinks for deleterious chemical species. The metal contents may be remobilized and released back into waters with changes in environmental conditions, thus affecting living organisms and human activities. This paper aims to determine the effect of a synthetic anthropogenic chelating agent (EDTA) as industrial discharges on the remobilization of several metals (Cu, Zn, Cd, and Pb) in River Nile sediments (at Aswan and Mansoura cities) under different concentrations and pH values, and to investigate the influence of metal–EDTA complexes on this remobilization. For these purposes, sequential extraction and experiments on the effect of pH and metal EDTA complex were carried out on the two representative sediment samples south and north of the River Nile in Egypt. The results of sequential extraction show that most of metal contents present in the residual form (Cu, 11.36–72.34%; Pb, 29.64–66.67%; and Zn, 43.76–50.09% at Aswan and Mansoura, respectively). Non-residual fractions which may be available for the remobilization by EDTA represented anthropogenic (industrial, agriculture, and domestic discharges) and lithiopogenic (metals bound to Fe and Mn oxides) sources. A clear increase was detected for Cu and Zn remobilization from the increase in EDTA concentrations, in contrast, Cd independent of the EDTA concentration and slight influence on Pb content. The remobilization of metals as a function of pH exhibited. The metals were greatly remobilized under the complexing action of EDTA, showing that some of these elements were adsorbed on the sediments. The remobilization rate of metals was dependent upon the added metal–EDTA complex (with the exchange rate being in the order Ca–EDTA>Zn–EDTA>Cd–EDTA>Cu–EDTA>Pb–EDTA), due to the stability constant of the metal–EDTA complex. The results of these experiments showed that heavy metals are greatly remobilized under the complexing action of EDTA when it is present in excess, so all precautions should be taken to prevent any wastewater containing EDTA or any chelating agents discharging directly or indirectly via the River Nile stream because most EDTA remains in the aquatic phase. The ability of this portion to remobilize metals from sediments should be taken into account.     

Metal contamination of riverine sediments below the Avoca mines, south east Ireland

The River Avoca is severely polluted by discharges of acid mine drainage (AMD) from the abandoned sulphur and copper mines at Avoca. The riverine sediments were studied during a low flow period to establish the degree of contamination and to identify the major processes affecting sediment metal concentrations. pH plays a major role in the regulation of zinc adsorption and desorption in sediments, showing a significant correlation (p&0.001). The zinc concentration in the sediment falls below background levels after the input of AMD. However, the metal precipitated when the pH increased downstream of a fertiliser factory (pH8.0), some 7 km below the mine. In contrast Cu and Fe significantly increased (p0.001) both in the sediment (0--30 mm depth) and the surface ochre immediately below the mixing zone. Copper removal appears to be primarily by co-precipitation. Higher sediment enrichment factors for all metals were obtained in the surface sediment layer (ochre) deposited on larger stones and in floc material collected in sediment traps, compared with the subsurface sediment. Cadmium was not recorded in any of the sediment collected at the detection limit used (0.01 g g-1). Metal deposition in the sediments was found to be spacially variable, so sub-sampling is required, although replicates show little variation. Results indicate that short term variation in metal inputs is identified by sampling the surface layer only, whereas sampling of the subsurface layer (<63 m fraction) is more suitable for identifying long-term trends in sediment quality. The implication of sediment analysis in assessing environmental impact is discussed.     

The application of solid-phase micro-extraction (SPME) to the analysis of polycyclic aromatic hydrocarbons (PAHs)

There are many established extraction techniques regularly used in the isolation and analysis of PAHs and similar organic compounds from various phases. These include Soxhlet or ultrasonic extractions from solids, and liquid-liquid or solid-phase extraction from aqueous samples. However, these methods have some inherent disadvantages; most require large volumes of organic solvents, they can be time consuming and many involve multi-step processes that always present the risk of the loss of some analytes (Zhang et al., 1994). Solid-phase micro-extraction (SPME) is a relatively new technique that has been used with much success in the analysis of a variety of compounds including PAHs. Experiments are being carried out to determine the optimum range of conditions for the extraction of a range of PAHs. Parameters under investigation include temperature, equilibration time, salinity and compound concentration. Presented here are some preliminary experiments into the applicability of SPME for PAH analysis. Further work will investigate the reproducibility of the technique, limits of detection and matrix effects. When an optimised method has been developed the technique will be used in investigations into PAH profiles in sediment cores.     

Speciation of particulate trace metals in sediments of Anarbe reservoir∗

Total concentration and chemical forms of heavy metals in samples of sediment from a drinking water reservoir have been analysed. The result of total metal contest shows Fe and Mn concentration increase along the reservoir, from 4.4% in Fe and 0.07% in Mn in the end part to 6.4% Fe and 0.22% Mn at the dam. However, a decrease in organic matter along the reservoir is observed. In order to test the accuracy of the digestion methods used, a standard reference material was also analysed.

Trace metal concentrations, with exception of Cadmium, Pb and Mn, found in fraction 5 are higher than those observed in the others extractions, Fe, Ni, Zn, Cr and Cu content in non‐residual fraction is found mainly in moderately reducible fraction, but the percentage of this fraction in each metal is very different.     

Trends in sediment metal concentrations in the River Avoca, South-East Ireland

Variation in sediment metal concentrations in the River Avoca, which is severely polluted by acid mine drainage (AMD) discharged from the abandoned sulphur and copper mines in Avoca, is reported. A survey of surface and subsurface sediments was repeated after seven years during exceptionally low flow conditions in 2001. The present study found that the reference (up-stream) site used in the original 1994 study was itself impacted by AMD, showing sediment metal enrichment by AMD to be greater than originally thought. The new reference site contained elevated Pb (570 µg g^–1) in the subsurface sediment due to abandoned Pb-Zn mines 25 km further upstream. Concentrations of Cu (43 µg g^–1), Zn (349 µg g^–1) and Fe (4.0%) were normal for uncontaminated rivers. All the downstream sites showed sediment metal enrichment arising from the AMD (Cu and Zn p < 0.001; Fe p < 0.01). Subsurface concentrations of metals immediately below the mixing zone were Cu 904 µg g–1 (sd 335), Zn 723 µg g–1 (sd 93), Fe 6.3% (sd 1.5) and Pb 463 µg g^–1 (sd 279). Monthly variation in metal concentrations at sites was not significantly different (p > 0.05). Although surface sediment metal concentrations were more variable, they followed similar trends to subsurface sediment. There were no significant differences in the subsurface sediment concentrations for either Cu or Zn over the period 1994 and 2001 immediately below the mines, although at the lowest site Zn had decreased by 35% over the period (p < 0.01). However there was a significant (p < 0.01) decrease over the period in the Fe concentration at all the impacted sites. This corresponds to a reduction in Fe concentration in the AMD and indicates that some remediation has occurred in the river since 1994.     

Historical record of anthropogenic polycyclic aromatic hydrocarbons in a lake sediment from the southern Tibetan Plateau

High-altitude lake sediments can be used as natural archives to reconstruct the history of pollutants. In this work, the temporal distribution of polycyclic aromatic hydrocarbons (PAHs) was determined in a sediment core collected from the southern Tibetan Plateau (TP), which was dated by using the ²¹⁰Pb dating method and validated with the ¹³⁷Cs fallout peak. The concentrations of the anthropogenic PAHs (Σ₈PAH) in the sediment core ranged from 0.83 to 12 ng/g dw, and the fluxes of the Σ₈PAH were in the range of 2.1–27 g/cm²/year. The temporal variations in the concentration and input flux of anthropogenic PAHs were low with little variability before the 1950s, and then gradually increased from the 1950s to the 1980s, and an accelerated increase was observed after the early 1980s. The content of total organic carbon played an insignificant role in affecting the time trends of PAHs in the sediment core. Diagnostic concentration fractions of PAH components indicate PAHs in the lake sediment of the southern TP which are mainly from biomass burning and/or from long-range atmospheric transport.     

Trace metals in fish,sediment and water from the south west coast of the Arabian sea,Pakistan

Concentrations of ten metals (As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn and Hg) in the edible muscle of Arius maculatus captured from eight different near‐shore and off‐shore sites off the south west coast of the Arabian Sea, Pakistan, were determined by atomic absorption spectrophotometry. Relevant water and sediment samples from the sites were also analysed for the metals. Zinc showed the highest metal concentration (6.763 μg/g, wet weight) in the muscle of the fish, while Mn and Hg showed lowest level (0.019 μg/g, wet weight). Of all the metals investigated, largest scatter (measured as σ) was observed for Zn (σ = 2.058 /μg/g) in fish muscle, for Fe and Mn in sediment (σ = 27481 and 44.50 μg/g) and for As in water (σ = 0.270 μg/L). The metal distribution data pertaining to water, fish and sediment were examined on the basis of simple metal correlations. The statistical study revealed that Ni, Cr, Pb and Cu had significant positive correlations (r > 0.830 at ρ = 0.01). The finding substantiated a trace metal concentration gradient in the area, thereby indicating that the local marine environment is contaminated by anthropogenic sources.     

Trace metal distribution in different chemical fractions of marine sediments along the eastern Aegean shelf

The major objective of this study was to carry out sequential chemical extraction for the partitioning of particulate trace metals in sediment samples, collected along the eastern Aegean shelf during cruises July‐August 1994, in the framework of a National Marine Measurement and Monitoring Programme for the Aegean Sea.

Five metals, Cd, Pb, Cu, Zn and Cr were examined in each of sediment samples. Three chemical fractions of the sediments were separated and concentrations of the trace metals were determined by AAS techniques. The three different leaches used were hydroxylamine hydrochloride‐acetic acid, hydrogen peroxide and nitric‐perchloric acids.

Metals were concentrated mainly in the fraction extracted by nitric‐perchloric acids. Lead in the first fraction were found in the sediments of Northern part of Aegean, where the concentration of organic material was high.

The total concentrations of Cd, Cu, Zn, Cr were higher in Izmir Bay than the other sampling points. The distribution of Pb concentrations was the highest in Edremit Bay and Izmir Bay.