The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

The Influence of Anthropogenic Contamination On Metals Release From Coastal Sediment Suspensions with Aerated Sea Water

The zinc, cadmium, copper and lead release from the uncontaminated and contaminated coastal sediments with aerated sea water was studied. the metals transfer to the dissolved forms was monitored during one-two months by differential pulse anodic voltammetry (DPASV). the sediments with different initial degree of contamination were sampled in the Peter the Great Bay, Sea of Japan around Vladivostok-the biggest city in Russian Far East. Sediment contamination by metals led to increased release to solution of zinc due to sulphide oxidation and cadmium on account of organic matter decomposition. the copper behaviour was complicated by strong binding with organic matter and enhancements of copper release can only be seen in sediment with a low organic matter content. Significant lead transfer to dissolved forms was not observed regardless of sediment contamination. the temperature affected the release of cadmium and copper through enhanced organic matter destruction. the dissolved metal fluxes from the sediment transformation are compared with metal fluxes towards bottom. Such comparisons show that second contamination by dissolved metals of the studied coastal environment may be important for cadmium only.     

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.     

Heavy metal distribution and speciation in the Northern Adriatic Sea

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

HEAVY METAL DISTRIBUTION AND SPECIATION IN THE NORTHERN ADRIATIC SEA

In the present study the concentrations of cobalt, copper, iron, manganese, zinc were analysed and the speciation of copper and zinc performed, with a summer and winter sampling, for two areas in the Northern Adriatic Sea and crossing at the farthest zones of the Po river-sea water interface. Results show that when salinity increases the concentrations of all investigated metals (with the exception of cobalt) present some degree of biogeochemical cycling. Copper is the element whose dissolved phase has the highest importance in metal transport across the salinity gradient. Results of speciation analysis demonstrate that the presence of excess amounts (5-8 fold) of unbound ligands confers a buffering capacity for potential inputs of dissolved metals into the Northern Adriatic Sea. The speciation of both copper and zinc in the dissolved phase was dominated by organic complexation.     

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.     

Sequentielle Schwermetallextraktion aus Staubniederschlägen und Stra\ensedimenten

For the application of our method for the sequential extraction of heavy metals from microsamples presented in part 1 (“Sequentielle Schwermetallextraktion von Mikroproben” — “Sequential Extraction of Heavy Metals from Micro Samples”) an investigation was carried out to evaluate airborne dust fallout and street sediments at two urban sites where different heavy metal immission rates occur due to traffic influence. In the street sediments the total concentrations of zinc, copper and lead was three to fivefold higher in the silt and clay fraction (< 63 μm) than in the particle size fraction (< 1,12 mm), but showed nearly the same mobilisation behaviour. The dust samples showed equal mobilisation behaviour as the street sediments for copper and lead, while zinc was considerably more mobile in the dust samples: In extraction steps I–IV (I: mobile fraction; II: easily deliverable fraction; III: fraction bound to manganese oxides; IV: fraction bound organic to matter) zinc, copper and lead in street sediments, as well as copper and lead in dust samples, were dissolved to 40–70%, whereas about 80% of zinc in the dust samples was already dissolved in extraction step I.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Spatial Variations of Heavy Metals in the East China Sea Continental Shelf Surface Sediments

Surface sediments collected from continental shelf of the East China Sea were analyzed for heavy metals (iron, manganese, copper, zinc, lead, cadmium), carbonate, organic carbon contents, and grain sizes. the range of concentrations observed were iron: 0.3-1.3 wt%, manganese: 2.3-14 μmole/g, copper: 7.1-184 μmole/g, zinc: 0.16-0.77μmiole/g, lead: 15-98 μmole/g, cadmium: 0.17-3.9 μmole/g, carbonate: 3.6-87 wt%, sand: 10-100%, silt: 0-70% and clay: 0-50%.

A zonal distribution pattern of the heavy metals was found in the East China Sea Continental shelf sediments. High concentrations of most heavy metals, organic carbon and fine-grained sediments were observed in the inner shelf zone, especially those near the discharge of the Yangtze River. Concentrations of these heavy metals decreased from the inner shelf to the shelf break region. High concentrations of metals were also found in sediments near Taiwan. Iron concentrations decreased north-east of the central shelf region. High concentrations of cadmium were found in the shelf break region where biogenic carbonate is predominant. This study showed that biogenic carbonate in the East China Sea shelf break region and the terrigenous sediments from the Yangtze River and island of Taiwan were the major sources of heavy metals. Heavy metal concentrations were strongly influenced by the content of the coarse-grained quartz sand present in the sediments.     

Fractionation of Mn, Fe, Zn and Cu in Sediments of Khor Kalabsha, Lake Nasser, Egypt

Khor Kalabsha is the second largest Khor in Lake Nasser, which is a freshwater side-branch of the main lake. Chemical analysis of the samples indicates that calcium carbonate and organic matter content in the surface sediments average 17.8 and 3.07%, respectively. Moreover, manganese, iron, zinc and copper concentrations are lower in Khor Kalabsha than in other lakes of Egypt. It has been found that both oxides and residual forms constitute the major part of the measured elements in the study area, while manganese and iron play an important role in building up clay minerals. It is noted that both zinc and copper fractions are controlled by biological and biochemical processes.     

碳酸盐对铜离子在黄土中吸持及形态影响的实验研究

选用黄土和重金属Cu为研究对象，通过等温吸持实验和Tessier形态提取实验，研究了碳酸盐对铜离子在黄土中吸持及形态的影响。结果表明：黄土去除碳酸盐后，其吸持铜离子的量大幅度降低；碳酸盐结合态、铁锰氧化物结合态和有机质结合态铜含量明显降低，而可交换态铜含量显著增加。     

Sources, spatial variation, and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.     

Trace Metal Studies on the Starfish Asterias rubens L. From the Western Baltic Sea

In 1984, 115 samples of the starfish Asterias rubens L. collected in the south-eastern part of Cadet Trench (Mecklenburg Bay/Western Baltic Sea) were analyzed for their contents of a few major (calcium, magnesium) and trace elements (cadmium, copper, iron, mercury, manganese, nickel, lead, selenium and zinc). Distinct differences were found between starfish from different stations, and these are attributed to the composition of the sediments acting as a substrate for their prey (mussels, snails). Except for cadmium, the concentrations of the elements studied all correlated negatively with the diameter and weight of the starfish.

Parallel analyses of starfish arms and the central discs of the same animals showed that iron, zinc, copper and mercury levels were 16 to 30% higher, and selenium, manganese, magnesium, calcium and lead were 4 to 9% higher in the arms. Cadmium concentrations were 20% higher in the central discs than in the arms.

Stock estimations (about 52,000 tons fresh weight) show that starfish play a significant role in the benthic ecosystem of the western Baltic Sea. They can consume up to 200,000 tons of mussels and clams (Mytilus edulis, Macoma baltica) a year and may therefore represent a notable factor in the trace metal balance of the region.     

Sources,spatial variation,and speciation of heavy metals in sediments of the Tamagawa River in Central Japan

Sediments of the Tamagawa River in central Japan were studied to explain the spatial variation, to identify the sources of heavy metals, and to evaluate the anthropogenic influence on these pollutants in the river. Sediment samples were collected from 20 sites along the river (five upstream, four midstream, and 11 downstream). Heavy metal concentrations, viz. chromium, nickel, copper, zinc, lead, cadmium, and molybdenum, in the samples were measured using inductively coupled plasma-mass spectroscopy. The chemical speciations of heavy metals in the sediments were identified by the widely used five-step Hall method. Lead isotopes were analyzed to identify what portion is contributed by anthropogenic sources. The total heavy metal concentrations were compared with global averages for continental crust (shale) and average values for Japanese river sediments. The mean heavy metal concentrations were higher in downstream sediments than in upstream and midstream samples, and the concentrations in the silt samples were higher than those in the sand samples. Speciation results demonstrate that, for chromium and nickel, the residual fractions were dominant. These findings imply that the influence of anthropogenic chromium and nickel contamination is negligible, while copper, zinc, and lead were mostly extracted in the non-residual fraction (metals in adsorbed/exchangeable/carbonate forms or bound to amorphous Fe oxyhydroxides, crystalline Fe oxides, or organic matter), indicating that these elements have high chemical mobility. The proportion of lead (Pb) isotopes in the downstream silt samples indicates that Pb accumulation is primarily derived from anthropogenic sources.     

Trace Metal Studies on the Starfish Asterias rubens L. From the Western Baltic Sea

In 1984, 115 samples of the starfish Asterias rubens L. collected in the south-eastern part of Cadet Trench (Mecklenburg Bay/Western Baltic Sea) were analyzed for their contents of a few major (calcium, magnesium) and trace elements (cadmium, copper, iron, mercury, manganese, nickel, lead, selenium and zinc). Distinct differences were found between starfish from different stations, and these are attributed to the composition of the sediments acting as a substrate for their prey (mussels, snails). Except for cadmium, the concentrations of the elements studied all correlated negatively with the diameter and weight of the starfish.

Parallel analyses of starfish arms and the central discs of the same animals showed that iron, zinc, copper and mercury levels were 16 to 30% higher, and selenium, manganese, magnesium, calcium and lead were 4 to 9% higher in the arms. Cadmium concentrations were 20% higher in the central discs than in the arms.

Stock estimations (about 52,000 tons fresh weight) show that starfish play a significant role in the benthic ecosystem of the western Baltic Sea. They can consume up to 200,000 tons of mussels and clams (Mytilus edulis, Macoma baltica) a year and may therefore represent a notable factor in the trace metal balance of the region.     

Chemical fractionation of metals in core sediments of Orogodo River,southern Nigeria

Sequential chemical extraction of metals (Cu, Ni, Mn, Fe, Pb, Cr, and Zn) from core sediments of the Orogodo River was carried out with a view of providing information on the phase distribution of these metals with respect to depths and seasons. The results indicate that copper was speciated into organic matter/sulfide, Fe–Mn oxides, and residual forms at 0–5?cm depth while at deeper sections copper was predominantly in the residual form. Nickel was speciated mainly into Fe–Mn oxides and residual forms. The average of lead in various particulate phases of the sediment are 0–100% for residual; 0–8% for carbonate; 0–16.2% for exchangeable; 0–10% for organic matter/sulfide form and 22–56% for Fe–Mn oxides bound metals. Manganese was speciated into exchangeable (10–36%) and Fe–Mn oxides bound (10–48%) at the surface layers of 0–20?cm depths and predominantly in the residual form in deeper sections implying partitioning into trioctahydral clay and/or well-defined crystalline oxides. Iron was predominantly in the Fe–Mn oxides and residual fractions, less than 8% in the organic fraction, and 24.4–37.3% in the exchangeable and carbonates fractions at the surface. The percentage contributions of iron in the exchangeable and carbonate fractions decreased to 3.2% at 55–60?cm depth. The amount of chromium in the exchangeable fraction ranged from 0% to 7% for exchangeable; 0–26.5% for organic matter/sulfide bound; 3.8–17.9% for Fe–Mn oxides; and 46.8–100% for residual fraction. The mobility factors of the metals indicated that these metals were relatively mobile at top sections as compared with deeper sections. The overall picture of metal mobility and availability indicates potential contamination risk by Fe, Zn, Mn, and Pb in the Orogodo River sediment system.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

Geochemical forms of trace metals in mangrove sediments—Red Sea (Egypt)

Seven sediment samples from mangrove sediments of the Red Sea were taken in order to evaluate the possible contamination of the sediments by trace metals (iron (Fe), manganese (Mn), zinc (Zn), copper (Cu), lead (Pb) and cadmium (Cd)). Sequential extraction techniques were performed to study the different geochemical forms of these metals. X-ray diffraction analysis has been performed to correlate the mineralogical composition with the geochemical forms of the studied elements. The results of Fe and Mn contents indicate that they are in large part from lithogenous origin. The elevated concentrations are associated with the residual form ranged from 70 to 93% for Fe and 46 to 70% for Mn. The percentage of Zn, Cu, Cd and Pb in the non-residual form was much greater than that of the residual fractions. This reflects the high mobility and bioavailability of these metals in mangrove sediments of the Red Sea. X-ray diffraction analysis revealed the presence of silicate components including quartz, feldspars and clay minerals in some locality. Non-silicate components recorded in the study area as calcite as well as, Mg-calcite. Quantitatively both components i.e. silicate and carbonate varied according to their source material.     

Metal transport phases in rivers around Jameshedpur†

Transport phases of four metals of geochemical and water quality importance were investigated in rivers around Jamshedpur. The metals iron, manganese, zinc and copper were partitioned into dissolved, adsorbed and or ion exchangeable, solid organic, oxide coating and crystalline phases applying filtration for the dissolved phase and a chemical fractionation scheme for the particulates. Iron and copper were transported mainly in the particulate phases at all sites, while manganese and zinc were found in the dissolved phase up to a hundred percent depending on the pH of water sample and pollution at the site concerned. Except copper more than 75 percent of all other three metals occurred in transport modes thought to be available to aqueous and biotic interactions. Copper was in available phases from 50 to 70 percent. The significance of metal partitioning as a factor in controlling metal availability and toxicity to biota is discussed.     

Assessment of Trace Metals in the Sediments From the Coastal Zone of Alexandria, Egypt

Freshly deposited surface sediments from the Alexandria coastal zone were collected and analysed in 1995 for their trace metal concentrations. Metal concentrations in the sediments vary between sites within a wide range for copper, zinc, iron, lead, chromium and cadmium. the statistical analysis between the metal concentrations and the different constituents (organic carbon, total nitrogen, silt, clay and total iron) showed significant correlations. the enrichment factors for the sediments ranged between 3 and 4-fold for copper, chromium and zinc and reached up to 9-fold for lead and 113-fold for cadmium. the highest index for cadmium and lead may be attributed to the anthropogenic inputs from the surrounding area, where they are highest in lower discharge areas.