Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Interactions Among the Copper Species and Forms in Sea Water/Sediments and Copper Bioaccumulation in Oysters

Earlier papers indicated that the first incident of green discoloration in oysters (Crassostrea gigas) and the mass mortality observed in 1986 along the Taiwan Erhjin Chi coastal area were caused by the higher contents of total copper and copper species (mainly bioavailable and free ion) in sea water. the copper in sea water would be sorbed by suspended matter and transferred to sediments, and the copper in the sediments would also be desorbed to sea water. Processes of copper adsorption and desorption are the major factors influencing the contents of total copper and copper species in sea water and sediments. in this study, the Erhjin Chi sediments were mixed with sea water by a shaker technique. When the mixture was shaken for one hour, analogous to tidal mixing in estuaries, only copper desorption from sediments was observed. If the shaking time is increased for more than 3 hours, the copper released from the sediments was resorbed to the remaining solid phases. the higher the contents of mud (91.71%) and total copper (701 mg kg^-1) in sediments, the higher the copper desorption rate (1.86 ppm hr^-1) and copper adsorption rate (0.50 ppm hr^-1) were observed. in sediments containing lower mud (0.80%) and lower copper (43.5 mg kg^-1), the copper desorption and adsorption rates were 0.83 ppm hr^-1 and 0.22 ppm hr^-1, respectively. the interactions among the total copper and copper species in sea water and sediments, chemical and ecological parameters, and copper bioaccumulation in oysters in the Erhjin Chi estuarine and coastal area are also discussed.     

Metal Concentration in Oyster, Crassostrea Gigas, and Sediment in Ann-Ping Mariculture Ground, Taiwan

This study was to assess the metal contamination in oyster tissue grown in the Ann-ping mariculture ground in Taiwan. the information generated from this work also revealed general metal pollution problem for Taiwan's oyster farmers. Oysters, Crassostrea gigas, and surficial sediments collected from ten locations in Ann-ping mariculture ground in Taiwan for metals concentration (Cu, Zn, Pd, Cd, Fe and Mn) were performed. Analytical results indicated that the yearly averaged oyster copper concentrations (μg g^-1, wet weight) in oyster soft parts from Ann-ping increased from 21.3±4.1 in 1993; 24.1±6.8 in 1994; 36.8±11.9 in 1995 to 43.9±23.1 μg g^-1, wet weight, in the 1996 raising season. the mean oyster copper concentration reached a level of 50 μg g^-1, wet weight, in December 1996. This increasing trend of metal concentration in oyster tissue indicates a potential pollution source which may pose a potential disaster as green oyster incidence, which occurred on the Charting coast in 1986, in Taiwan. Sediment samples in Ann-ping mariculture ground were also collected and examined. the seasonal variation of the copper concentration in surficial sediment from Ann-ping did not show an increasing trend as observed in oyster tissue.     

Interactions Among the Copper Species and Forms in Sea Water/Sediments and Copper Bioaccumulation in Oysters

Abstract

Earlier papers indicated that the first incident of green discoloration in oysters (Crassostrea gigas) and the mass mortality observed in 1986 along the Taiwan Erhjin Chi coastal area were caused by the higher contents of total copper and copper species (mainly bioavailable and free ion) in sea water. the copper in sea water would be sorbed by suspended matter and transferred to sediments, and the copper in the sediments would also be desorbed to sea water. Processes of copper adsorption and desorption are the major factors influencing the contents of total copper and copper species in sea water and sediments. in this study, the Erhjin Chi sediments were mixed with sea water by a shaker technique. When the mixture was shaken for one hour, analogous to tidal mixing in estuaries, only copper desorption from sediments was observed. If the shaking time is increased for more than 3 hours, the copper released from the sediments was resorbed to the remaining solid phases. the higher the contents of mud (91.71%) and total copper (701 mg kg^?1) in sediments, the higher the copper desorption rate (1.86 ppm hr^?1) and copper adsorption rate (0.50 ppm hr^?1) were observed. in sediments containing lower mud (0.80%) and lower copper (43.5 mg kg^?1), the copper desorption and adsorption rates were 0.83 ppm hr^?1 and 0.22 ppm hr^?1, respectively. the interactions among the total copper and copper species in sea water and sediments, chemical and ecological parameters, and copper bioaccumulation in oysters in the Erhjin Chi estuarine and coastal area are also discussed.     

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.     

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.     

Dissolved trace-metal concentrations along the Mediterranean Sea, to the north of the Nile Delta Region, Egypt

This work focuses on four marine sites of the Mediterranean Sea, north of the Nile Delta, Egypt. Surface-water samples were collected seasonally during 2003. The aim of this study is to assess the levels of some dissolved trace metals (Fe, Mn, Zn, Cu, and Pb) in two environmental conditions. The metal concentrations in the coastal zone were in the following ranges: 11.92-30.45 μg l^-1 for Fe, 5.79-17.36 μg l^-1 for Mn, 0.87-7.80 μg l^-1 for Zn, 0.40-1.87 μg l^-1 for Cu, and 1.53-10.31 μg l^-1 for Pb. In the sites with continental water input (mixing zone), the metals were scattered in the following ranges: Fe (19.72-60.33 μg l^-1), Mn (12.63-35.60 μg l^-1), Zn (2.67-22.00), Cu (0.83-8.10 μg l^-1), and Pb (1.72-29.7 μg l^-1). The results for the metal concentrations showed a remarkable decrease in the levels of the different metals going from the estuaries and outlets into the coastal sea water. Generally, the levels of the metals in the two zones are higher than the background levels of the unpolluted area. A comparison of the trace-metal levels in the coastal zone of the Mediterranean Sea north of Nile Delta with the minimal risk concentration (reported by water-quality criteria, WQC) showed a significantly lower content at the coastal area of the Mediterranean sea of Egypt. The study also indicated that the impact of anthropogenic inputs was limited in the distribution of the metals, except that the Pb content was slightly higher in the area of the mixing zone than that reported for WQC. The relationships between the different trace-metal concentrations and the other parameters (salinity, chlorophyll a and suspended particulate matter) were discussed, and the simple regressions between them were evaluated.     

A Comparative Study On the Levels of Trace Metals in Some Mediterranean and Red Sea Fishes

Samples of Mugil cephalus, Liza ramada, Siganus luridus, Siganus rivulatus, Epinephelus alexandrinus, Epinephelus areolatus, Epinephelus fasciatus, Epinephelus chlorostigma, Cephalopholis argus and Cephalopholis sonnerati were collected from the Mediterranean and Red Seas and their muscle and bone analyzed by AAS for some trace metals (Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb). the results showed that these metals accumulate in the bones to a greater extent than in the muscle. the highest accumulated element is cobalt (4.7-20.8 times), while the lowest is lead (1.1-2.5 times). the accumulation is more pronounced in Red Sea species than in Mediterranean species. the elevated levels of lead in Mugil cephalus (2.6-3.0 mg kg^-1) and Epinephelus alexandrinus (3.0-3.9 mg kg^-1) were attributed to the intake in food in the polluted environment of Alexandria coastal water. the relationship between body size and concentration of trace metals using a standard linear regression technique gives a significant positive correlation for cobalt, manganese, iron and lead in the muscle, as well as for lead in the bones of Mugil species from the Red Sea, while the Mediterranean species showed little correlation.

There is a tendency for increased concentrations of the essential metals manganese, iron and copper with increasing trophic level of the fish, while the opposite is true for the toxic metals chromium and lead. Our results indicate that there is no risk from toxic metal concentrations in muscle of fish from the Mediterranean and Red Seas consumed by man even in contaminated areas.     

Reduction of hexavalent chromium with scrap iron in a fixed bed reactor

The reduction of hexavalent chromium by scrap iron was investigated in continuous long-term fixed bed system. The effects of pH, empty bed contact time (EBCT), and initial Cr(VI) concentration on Cr(VI) reduction were studied. The results showed that the pH, EBCT, and initial Cr(VI) concentration significantly affected the reduction capacity of scrap iron. The reduction capacity of scrap iron were 4.56, 1.51, and 0.57 mg Cr(VI)·g^-1 Fe⁰ at pH 3, 5, and 7 (initial Cr(VI) concentration 4 mg·L^-1, EBCT 2 min, and temperature 25°C), 0.51, 1.51, and 2.85 mg Cr(VI)·g^-1 Fe⁰ at EBCTs of 0.5, 2.0, and 6.0 min (initial Cr(VI) concentration 4 mg·L^-1, pH 5, and temperature 25°C), and 2.99, 1.51, and 1.01 mg Cr(VI)·g^-1 Fe⁰ at influent concentrations of 1, 4, and 8 mg·L^-1 (EBCT 2 min, pH 5, and temperature 25°C), respectively. Fe(total) concentration in the column effluent continuously decreased in time, due to a decrease in time of the iron corrosion rate. The fixed bed reactor can be readily used for the treatment of drinking water containing low amounts of Cr(VI) ions, although the hardness and humic acid in water may shorten the lifetime of the reactor, the reduction capacity of scrap iron still achieved 1.98 mg Cr⁶⁺·g^-1 Fe. Scanning electron microscope equipped with energy dispersion spectrometer and X-ray diffraction were conducted to examine the surface species of the scrap iron before and after its use. In addition to iron oxides and hydroxide species, iron-chromium complex was also observed on the reacted scrap iron.     

Phosphorus in Sediments of Lake Edku, Egypt. The Influence of Chemical and Grain Size Parameters

Lake Edku is one of the Nile Delta shallow brackish water coastal lagoons with communications with the southeastern Mediterranean.

Sediment samples were recovered from the top 10 cm of the lake bottom to study principally their total, inorganic and organic phosphorus. Related sediment parameters such as particle size, organic carbon, carbonate and iron contents were also studied in detail.

It is shown that the lake sediments are generally a sand-silt-clay mud enriched with carbonate (11.4-42%), organic carbon (0.9-11.4%) and iron (1.6-5.6%).

The total phosphorus content in these sediments is 503-1329 μg/g, inorganic phosphorus, 468-954 μg/g and organic phosphorus, 35-526 μg/g.     

Speciation of organotin compounds in sediments of semi-closed areas along the Mediterranean coast of Alexandria

Organotin compounds were measured in sediments of four different semi-closed areas of the Mediterranean coast of Alexandria: the Eastern Harbour, Western Harbour, El-Max Bay, and Abu-Qir Bay. Due to the commercial trade activity inside the Western Harbour, in addition to the effect of wastes discharged from El Noubaria canal, it shows the highest concentrations of total tin (6.34 μg g^-1 dry weight), dibutyl tin (1.63 μg g^-1 wet weight), tributyl tin (0.33 μg g^-1 wet weight) and diphenyl tin (1.06 μg g^-1 wet weight) compared with other locations. The concentrations of TBT species showed the highest contents compared with DBT and DPhT compounds in all sampling areas. This trend might be due to the worldwide use of TBT not only as biocides in antifouling paints but also as preserving agents for wood, fungicides in agricultural activities, and heat and UV stabilizers of PVC, which results in a direct release of TBT into the water body, accumulation in aquatic fauna. There is also precipitation into sediments and a decrease in degradation rate into its derivatives. Variations, types, concentrations, and distribution of different organotin compounds are discussed in the areas under investigation. The study reveals a new record of organotin compounds along the Alexandria coast and makes comparisons with other surrounding areas of interest.     

Arsenic species in the well water and sediments of the blackfoot disease area in Taiwan

The blackfoot disease (BFD) observed in southwestern Taiwan is due to drinking high arsenic concentrations in well water. This paper presents some results concerning the distributions of arsenic species in water and sediments collected in the BFD (well, river and coastal) area and the background (lake and ocean) area for comparison. The results show that the concentrations of arsenate (870 ± 26 ug/L) and arsenite (70.2 ± 2.6 ug/ L) in well waters, and the contents of arsenic (1640 ug/g) with high percentage of easily reducible (Fe and Mn oxides, 91.7%) and exchangeable and carbonate (4.6%) phases in well sediments were much higher than those in river, lake and coastal samples. Low arsenic (3.46–31.8 ug/g) with high percentages (73.8–97.3%) of detritus and minerals phase with low percentages (0.4–9.8%) of total carbonate and exchangeable phases were found in the river and coastal samples in the BFD area as well as the lake and ocean samples in background area. It might suggest that the higher concentrations of toxic As(III) in well water and arsenic with higher values of easily reducible, carbonate and exchangeable phases in the well sediments, combined with the higher values of dissolved organic carbon, humic and fulvic acids and aromatic carbon as well as the higher fluorescence indensity in the well water are the key factors to cause the BFD in Taiwan.     

广州城市水体沉积物中重金属形态分布研究

选取广州城市水体中的４ 个污染沉积物样品,采用连续提取法研究沉积物中重金属元素（ Ｐｂ 、 Ｚｎ 、 Ｃｕ 、 Ｎｉ 、 Ｃｒ 、 Ｍｎ） 的形态分布,结果表明：重金属元素主要以残渣态、有机结合态和氧化铁结合态存在,其中 Ｐｂ 、 Ｎｉ、 Ｍｎ 以残渣态和氧化铁结合为主, Ｚｎ 以残渣态和有机结合态为主, Ｃｕ 以有机态和氧化铁结合态为主, Ｃｒ 以氧化铁结合态为主。沉积物中固相组分对重金属的富集能力为：无定型氧化锰＞ ＞ 碳酸盐＞ 氧化铁＞ 有机质,而富集量则是后两者大于前两者。     

UV light induces Ag nanoparticle formation: roles of natural organic matter,iron, and oxygen

Nanoparticles occurring in the environment originate either from engineered, synthetically produced nanoparticles, or from naturally produced nanoparticles. The latter can be formed in natural media by light-induced reduction of metal ions in presence of natural organic matter, such as humic substances occurring widely in waters, soils and sediments. There is actually few knowledge on the effect of sunlight and of the nature of organic matter on nanoparticle formation. Therefore, we studied here the photoreduction of silver(I) ion to silver nanoparticles with and without ferrous ion under oxic and anoxic conditions, using humic and fulvic acids as proxies of natural organic matter. UV light-induced formation of silver nanoparticles was monitored up to 60 min by measuring surface plasmon resonance in air-saturated mixture and nitrogen-saturated mixture of silver(I) ion–organic matter. Results show that the surface plasmon resonance intensity was about 2.5 times higher in the nitrogen-purged solution mixture than the air-saturated solution. This finding suggests the oxygen-containing species had no major role in forming silver nanoparticles. Therefore, photo-driven formation of silver nanoparticles most likely involved photoactivation of silver(I) ion and natural organic matter complexes. We observed also that both iron(II) and iron(III) ions highly modified the surface plasmon resonance spectra of the particles with broader features. Results also reveal that in the presence of humic acid, the intensity of the surface plasmon resonance peak decreased by at least 50 %, while almost no change in the intensity was seen when fulvic acid was used. Overall, our findings demonstrate that the ligand–metal charge transfer process, affected by the nature of organic matter, i.e., humic acid versus fulvic acid, was influenced by redox iron species.     

Accumulation and regulation of heavy metals by the intertidal snail Polinices sordidus

The gastropod Polinices sordidus was collected from an uncontaminated area in Quibray Bay, New South Wales, Australia, in 1990. The snails were exposed for 2 wk to polluted sediments collected from Port Kembla Harbour, Blackwattle Bay, Lake Illawarra, Lake Macquarie in New South Wales, Australia, and the Derwent River in Tasmania, Australia. Metal accumulation and regulation by this species were evaluated. Metal concentrations in snail tissues and total, EDTA and HCl-extractable metals in the sediments were compared. Copper concentrations were extremely varied in snails exposed to the same sediment. This was not the case for other matals tested. No accumulation of copper was found in snails exposed to different sediments. There was no zinc accumulation from sediments containing less then 10 mg Zn/g. P. sordidus could accumulate lead, manganese and iron from some of the sediments. Manganese concentrations in the snail tissues correlated with total, HCl-extractable and, more significantly, EDTA-extractable Mn in the sediments. P. sordidus was not considered to be a good bioindicator of copper and zinc contaimination in sediments; however, this species could be used as an indicator of lead and manganese contamination.     

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.     

Characterization of dissolved organic carbon and Humic substances in the well water of the Blackfoot disease area in Taiwan

Since the early 1960s, many investigators have reported that blackfoot disease, a peripheral vascular disease, observed in southwestern Taiwan is due to drinking the higher arsenic concentration in well water. However, recent studies indicated that the relationship with blackfoot disease is not only with arsenic but also humic substances. This paper presents some results concerning the characterization (such as fluorescence, elemental composition, molecular weight and carbon distribution) of humic substances isolated from the Fuhsing well water of the blackfoot disease area. For comparison, the dissolved organic carbon (DOC) and humic substances in the normal well water from Chiuying and the Nanwan coastal water were also analyzed. In general, in the well water of the blackfoot disease area, extremely high concentrations of DOC (18.5mg/L) and fulvic acid (7.54mg/L) with high fluorescence intensity (59.1, equivalent to 0.0282uM quinine sulfate solution) and high percentages (over 50%) of low molecular weights of less than 1,000 were obtained compared with those of normal waters. C‐13 Nuclear magnetic resonance spectroscopy showed a high content (37.2%) of aromatic carbon. These higher concentrations of DOC and fulvic acid with the higher content of aromatic carbon in well water might be one of the key factors causing the blackfoot disease in Taiwan.     

Metal distribution in sediments from the Adriatic Sea

Total metal concentrations (Cu, Ni, Pb, Zn, Fe, and Mn) and their distribution in different chemical forms (speciation) were determined in sediments from the Adriatic Sea in order to evaluate contamination and mobility of metals. The study was carried out on marine sediments collected in two areas of the Adriatic Sea differently influenced by Po river waters. Metal distribution in the study area depends prevalently on water circulation and on organic matter distribution. Among metal levels, significant correlations between copper and zinc and between lead and nickel were found, suggesting common and specific sources. As regards metal speciation, the distribution of different chemical forms changes with the metal. The prevailing zinc phases, for example mobile forms, and sulphide together are greater than 50% of total metal. Nickel is mainly present in sediments as sulphide, and the preferential association of copper with organic matter is evident. Lead and manganese are preferentially found as mobile forms (more of 30% for lead, 40% or more for manganese).