土壤重金属化学形态的生物可利用性评价

重金属化学形态是近年来土壤化学、植物营养和环境科学研究领域的一个热点和难点,利用重金属的化学形态分布和含量变化来评价重金属的生物可利用性,有利于全面研究重金属的危害性和治理重金属污染土壤。结果表明,水溶态和交换态的重金属易被生物吸收利用,而残留态重金属一般不被生物利用,其它形态如碳酸盐结合态、铁锰氧化物结合态和有机物结合态的生物可利用性主要取决于外界环境的变化。     

Geochemical fractions and phytoavailability of Zinc in a contaminated calcareous soil affected by biotic and abiotic amendments

Many studies have conducted to determine the best management practice to reduce the mobility and phytoavailability of the trace metals in contaminated soils. In this study, geochemical speciation and phytoavailability of Zn for sunflower were studied after application of nanoparticles (SiO₂ and zeolite, with an application rate of 200 mg kg^?1) and bacteria [Bacillus safensis FO-036b(T) and Pseudomonas fluorescens p.f.169] to a calcareous heavily contaminated soil. Results showed that the biotic and abiotic treatments significantly reduced the Zn concentration in the aboveground to non-toxicity levels compared to the control treatment, and the nanoparticle treatments were more effective than the bacteria and control treatments. The concentration of CaCl₂-extractable Zn in the treated soils was significantly lower than those of the control treatment. The results of sequential extraction showed that the maximum portion of total Zn belonged to the fraction associated with iron and manganese oxides. On the contrary, the minimum percent belonged to the exchangeable and water-soluble Zn (F₁). From the environmental point of view, the fraction associated with iron and manganese oxides is less bioavailable than the F₁ and carbonated fractions. On the basis of plant growth promotion, simultaneous application of the biotic and abiotic treatments significantly increased the aboveground dry biomass yield and also significantly reduced the CaCl₂-extractable form, uptake by aboveground and translocation factor of Zn compared to the control treatment. Therefore, it might be suggested as an efficient strategy to promote the plant growth and reduce the mobile and available forms of toxic metals in calcareous heavily contaminated soils.     

Heavy metals availability (Fe, Mn, Zn, Cu and Cr) in Aden Gulf sediments under aerobic and anaerobic conditions

The present study aims to analyse the chemical speciation of heavy metals in relation to aerobic and anaerobic conditions. Two sediment samples (from the Gulf of Aden, Yemen) were incubated under flooded conditions. In particular, the chemical forms of Fe, Mn, Zn, Cu and Cr under the experimental conditions were studied using a sequential chemical extraction method. The pH and Eh of the suspension were measured as critical parameters controlling the fate of the metals in the environment. The results showed that the metals concentration in the different forms varied with time incubation and affected by the variation of redox potential and pH value. Also, the changes in both redox potential (Eh) and pH values had evident effects on heavy metals transformation. It is obvious that the highest redox potential affected the amount of iron and manganese in the oxides form. When the redox potential decreased to-133 and-170 mV, it caused a significant transformation of the Fe-Mn oxide form to the water-soluble and exchangeable fractions. Under anaerobic conditions, the relative percentage of all five metals including the summation of four fractions (the water-soluble and exchangeable, carbonate, oxides and organic fractions) constituted 45-60% of the total amount of iron, 33-50% for manganese, 33-63% for Zn, 63-74% for Cu and 19-43% for Cr. Both zinc and copper among water-soluble and exchangeable fraction were high at the end of incubation period, this accompanied by a significant decrease in the content of the organically bound fraction. In general, the reducing conditions were more favorable for metal bound to water soluble and exchangeable fraction.     

Effect of acid rain on the fractionation of heavy metals and major elements in contaminated soils

Acid rain is a serious environmental problem worldwide. In the present study, we investigated the effect of acid rain (1:1 equivalent basis H₂SO₄:HNO₃) at pH values of 2.0, 4.0 and 7.0 on the fractionation of heavy metals (Cd, Cu, Fe, Mn, Ni, Pb and Zn) and major elements (K, Na, Ca, and Mg) in contaminated calcareous soils over a 2084 h period. Heavy metals and major elements in soil samples were fractionated before and after 2084 h kinetic release using a sequential extraction procedure. Before kinetic studies the predominant fractions of K, Na, Ca, Mg, Cd and Ni were mainly associated with carbonate fraction (CARB), whereas Fe, Mn and Zn were associated with the Fe–Mn oxide fraction (Fe–Mn oxide). The highest percentage of Pb and Cu were found in the exchangeable (EXC) and organic matter (OM) fractions, respectively. After kinetic study using different simulated acid rain solutions, the major fractions of heavy metals (expect of Cu) and Na was the same as before release. Upon the application of different acid rain solutions, K and Mg were found dominantly in Fe–Mn oxide fraction, whereas Ca was in the EXC fraction. The results provide valuable information regarding metal mobility and indicated that speciation of metals (Cu and Zn) and major elements in contaminated calcareous soils can be affected by acid rain.     

Speciation of Heavy Metals in Floodplain and Flood Sediments: a Reconnaissance Survey of the Aire Valley, West Yorkshire, Great Britain

A five-step sequential extraction technique was used to determine the chemical association of heavy metals (Pb, Zn, Cu and Cd), with major sedimentary phases (exchangeable, surface oxide and carbonate, Fe and Mn oxides, organic and residual metal ions), in samples from floodplain and recent flood sediments of the River Aire, West Yorkshire. Analysis indicates that metals Pb and Zn are primarily associated with the Fe and Mn oxides, Cu with the organic fraction and Cd with exchangeable and surface oxide and carbonate metal ions. Knowledge of the chemical speciation of heavy metals in river sediment, despite the procedure's inherent limitations, facilitates an understanding of their bioavailability, storage and remobilisation in floodplain and river channel environments.     

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。     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Seasonal Variations and Chemical Forms of Heavy Metals in Soils and Dusts from the Satellite Cities of Seoul, Korea

This research investigated heavy metal pollution of soils and dusts in two representative satellite cities of Seoul, Korea and studied the seasonal variations in metal concentrations through the rainy season and the chemical forms of metals using a sequential extraction analysis. The metal dispersion pattern was illustrated to match with urban structure. Soil and dust samples were collected from the cities of Uijeongbu and Koyang, which are the northern and northwestern satellite cities of Seoul (the capital), before and after rainy season. Concentrations of Cu, Pb and Zn were higher than those of the world averages for soils, and their levels decreased after rain, particularly in highly contaminated samples. Relatively high pH values were found in roadside soils, but no seasonal variation was found after the rainy season. The three metals (Cu, Pb and Zn) in soils and dusts were associated with various chemical fractions of soils and dusts as distinguished by the sequential extraction scheme, and a strong similarity of metal association between soils and dusts was found, which indicates that airborne dust may be a principle source of soil contamination. Copper is uniformly distributed, and Pb is largely associated with the reducible phase. There is an appreciable proportion of total Zn in the exchangeable/water-acid soluble fraction. After the rainy season, the most soluble fractions in soils and dusts were leached away. In terms of mobility and bioavailability of metals in soils and dusts, the order Zn >> Cu > Pb is suggested. Geographical variations of total metals corresponded well with urbanised areas of cities, especially the industrial complex and major motorways.     

An Investigation Into the Mechanism by Which Synthetic Zeolites Reduce Labile Metal Concentrations in Soils

The addition of synthetic zeolites and similar materials to metal contaminated soils has been shown to reduce soil phytotoxicity and to improve the quality of plant growth on such amended soils. To gain an understanding of the mechanism by which the phytotoxicity of contaminated soils is reduced when treated with synthetic zeolites, sequential extraction procedures and soil solution techniques have been used to identify changes associated with metal speciation in amended soils. Sequential extraction data and changes in soil solution composition are presented for three different contaminated soils, amended with three synthetic zeolites (P, 4A and Y) at concentrations of 0.5%, 1% and 5% w/w, or lime at 1%. The soils were collected from the site of a metal refinery, an old lead zinc mine spoil tip and from a field which had been treated with sewage sludge. After incubation of the zeolite treated soils for between one and three months, results showed a reduction in the metal content of the ammonium acetate fraction between 42% and 70%, depending on soil, zeolite and rate of addition, compared with the unamended soils. In addition, soil solution experiments indicated that synthetic zeolite amendments were more efficient at reducing metal content than comparable lime treatment. The mechanism by which synthetic zeolites reduce metal bioavailability in contaminated soils is discussed and compared to other amendments.     

烟气脱硫石膏对滩涂围垦土壤重金属解吸及残留形态的影响

滩涂围垦土壤是重金属等难降解污染物的主要最终归宿场所之一,其重金属的解吸将影响重金属的迁移性、生物有效性和潜在毒性,研究重金属的解吸对土壤污染评价、修复及环境容量预测至关重要.研究了烟气脱硫石膏对广州市南沙滩涂围垦土壤重金属的解吸效果,并分析了烟气脱硫石膏对重金属形态的影响.在离心管中称取20.0 g过0.25mm筛土样,加入20 mL水和不同量的烟气脱硫石膏,在室温下于恒温振荡器振荡,风干研碎后用原子吸收分光光度法测定重金属全量,并用Tessier连续提取法研究了处理前后重金属形态变化.研究结果表明,随着脱硫石膏施用量的增加,经过振荡离心后的滩涂围垦土壤中重金属质量分数先急剧下降,之后变化趋于平缓.与原土相比各重金属最大解吸率分别为:Cd 30.38%,Cu17.73%,Ni 15.00%,Zn 14.19%,Pb 9.46%,Cr 8.89%.比较处理前后重金属的形态变化,发现各重金属的可交换态解吸率均达50%以上,并且重金属碳酸盐结合态质量分数也有减少.说明烟气脱硫石膏能降低土壤对重金属的吸附,经振荡离心后能降低土壤中重金属的毒性和生物可利用性.     

Seasonal Variations of Trace Metal Chemical Forms in Bed Sediments of a Karstic River in Lebanon: Implications for Self-purification

Although Lebanon has abundant water, its rivers are polluted and aquifer water mismanaged. Effective river water usage requires an understanding of the geochemistry of polluting metals in catchments. Climate is “Mediterranean”: wet winters and dry summers. Active sediment flushing is restricted to winter high discharge episodes. Except in winter, water column pollutants are removed by precipitation or sorption to the surface of static bed sediments. Hence (1) does winter flushing of contaminated sediment and replacement by clean sediment favour self purification? (2) does the distribution of metals between extractable fractions change seasonally and thereby affect metal bioavailability ? Results on the distribution of metals are reported for Fe, Pb, Zn, Cu and Cd in bed sediments from Nahr Ibrahim (a karstic river) for summer and winter. A Tessier-like sequential extraction scheme was applied to samples (< 75 μm) for five locations along a 13 km stretch to the sea. Water pH was above 8.2 at all locations implying a very low solubility for Fe. Sediment was derived from catchment soils and limestone. Total sediment Fe increased in winter at all sites following deposition of eroded soil from upstream. Cadmium, Cu and Pb derived from polluting sources; the sources of Zn were more complex. Dilution by clean sediment explained winter reductions in total Cd, Cu and Pb; Zn changes were less consistent. Iron occurred mostly (> 77 sum of fractions) in the residual fraction compared with 6– 31 for pollutants; residual Cu and Zn showed a small increase in winter whereas Cd and Pb did not change. All readily exchangeable metals decreased in winter and the carbonate bound forms predominated in both seasons. Nahr Ibrahim has a high capacity for self purification and metal resolubilisation from sediment will be limited by the solubility of carbonate forms.     

Effects of eggshell addition on calcium-deficient acid soils contaminated with heavy metals

The eggshell was used to remediate the contaminated soil by heavy metals. The eggshell addition decreased the available state of the heavy metals. The available calcium in the soil increased due to eggshell addition. The efficiency was investigated in different moisture conditions. In this study, effects of water conditions (flooded, wet, or dry) and eggshell dosages (0, 0.1, 1.0, and 10.0 g/kg soil, respectively) on pH variation, content of unavailable state of heavy metals, form of heavy metals, and available nutritious element calcium (Ca) in acid soils contaminated with heavy metals were investigated, respectively. The soil samples were continuously cultivated indoors and analyzed by toxicity characteristic leaching procedure and community bureau of reference (BCR) sequential extraction procedure. The results showed that the addition of eggshell could effectively improve the pH of acid soil and increase it to neutral level. Moreover, the contents of unavailable state of heavy metals Cu, Zn, and Cd increased significantly. Furthermore, when the soil was cultivated under the flooded condition with 1.0 g/kg eggshell, the unavailable state of Cu, Zn, and Cd increased the most, and these heavy metals were transformed into residual state. On the other hand, the amount of available state of Ca increased to 432.19 from 73.34 mg/kg with the addition of 1.0 g/kg eggshell, which indicated that the addition of eggshell dramatically improved the available state of Ca. Therefore, eggshell could ameliorate the soil environment as it led to the decrease of available heavy metals and improvement of fertilization effectively. In a word, this study indicates that the addition of eggshell would be a new potential method for remediation of acid field soils contaminated with heavy metals.     

Bioavailability of trace metals in brownfield soils in an urban area in the UK

Thirty-two brownfield sites from the city of Wolverhampton were selected from those with a former industrial use, wasteland or areas adjacent to industrial processes. Samples (<2 mm powdered soil fraction) were analysed, using inductively coupled plasma–atomic emission spectrometry (ICP–AES) for 20 elements. Loss on ignition and pH were also determined. A five-step chemical sequential extraction technique was carried out. Single leach extraction with 0.12 M hydrochloric acid of Pb, Cu and Zn in soil was determined as a first approximation of the bioavailability in the human stomach. Some of the sites were found to have high concentrations of the potentially toxic elements Pb, Zn, Cu and Ni. The partitioning of metals showed a high variability, however a number of trends were determined. The majority of Zn was partitioned into the least chemically stable phases (steps 1, 2 and 3). The majority of Cu was associated with the organic phase (step 4) and the majority of Ni was fractionated into the residue phase (step 5). The majority of Pb was associated with the residue fraction (step 5) followed by Fe–Mn oxide fraction (step 3). The variability reflects the heterogeneous and complex nature of metal speciation in urban soils with varied historic histories. There was a strong inverse linear relationship between the metals Ni, Zn and Pb in the readily exchangeable phase (step 1) and soil pH, significant at P < 0.01 level. There was a significant increase (P < 0.05) in the partitioning of Cu, Ni and Zn into step 4 (the organic phase) in soils with a higher organic carbon content (estimated by loss on ignition). Copper was highly partitioned into step 4 as it has a strong association with organics in soil but this phase was not important for the partitioning of Ni or Zn. The fractionation of Ni, Cu and Zn increased significantly in step 3 when the total metal concentration increases (P < 0.01). The Fe–Mn oxide fraction becomes more important in soils elevated in these metals, possibly due to the scavenging of metals by oxides. Cu and Pb extracted by HCl was statistically similar to the sum of the metals in steps 1 to 4 (P < 0.01) and HCl available Zn was statistically similar to the sum of Zn in steps 1 to 3 (P < 0.01). Step 4 (the organic phase) was not an important phase for Zn, so it was concluded that any Cu, Zn and Pb present in soil in a nonresidue phase would be potentially available for uptake into the human system once soil has been ingested.     

Geochemical speciation of trace metals in sediments of the northern Nile Delta Lake by sequential extraction technique

ABSTRACT

The present study was performed to investigate surface sediment samples from Lake Edku of the Nile Delta Lagoons, Egypt. The Lake is important for fishing in the region. The importance of research is to understand the mobility and bioavailability of each studied metal. The study was carried out on 10 sampling sites during 2017. The sediments were subjected to the technique of sequential extraction to examine the chemical forms of some trace metals (Fe, Mn, Zn, Cu, Pb and Ni). Five stage extractions were done as the following order: soluble and exchangeable, carbonate, iron and manganese oxides, organic matter fraction and residual fraction. Attained results from the five fractions showed variations in the concentrations of metal contents of different sites under study. The overall metal concentrations (%) in the initial four extractable fractions (exchangeable, carbonate, oxides and organic matter fractions) were assessed to configure the mobility of each studied metal. The risk assessment code (RAC) represents the summation of exchangeable and carbonate fractions, it was between low and medium risk for aquatic environment. The range percentage of RAC for the metals was in the following order: 1.8–13, 4–23.5, 15–26, 5.7–19.5, 9–25 and 4.8–18.2 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. Approximately 30% of the total copper was associated to the organic fraction, which may represent a high mobility of copper in these sediments. The highest mobility of metals in the sediments could be confirmed by its bioavailability factor (BF), which was within the ranges of 0.32–0.61, 0.36–0.59, 0.64–0.83, 0.36–0.72, 0.37–0.62 and 0.52–0.78 for Fe, Mn, Zn, Cu, Pb and Ni, respectively. The BF exhibited the following order: Zn > Ni > Cu > Pb ≈ Mn?>?Fe. The high levels of BF for the studied metals may represent the potentiality for toxic metals to be easily released into the aquatic environment.     

石灰性土壤环境中缺锌机理的探讨

作者认为石灰性土壤中锌活性较低的原因,是由于碳酸盐导致土壤pH上升,在较高pH条件下氧化铁对锌的强烈固定,造成了大量专性吸附状态的氧化铁结合态锌及部份碳酸盐结合态锌,使交换态的有效锌含量很低,同时还证明:自然的石灰性土壤中,松结有机态锌与碳酸盐结合态是活性锌的直接给源,外源加入的锌仅为松结右机态锌。此外,石灰性土壤中各主要土壤的化学组份对外源锌的固定量高伛顺序为:氧化铁>有机质>粘土矿物>碳酸盐>氧化锰:对土壤中原有锌的固定作用大小依次为:粘土矿物>氧化铁>有机质>氧化锰>碳酸盐。     

Selective recovery of Cu, Zn, and Ni from acid mine drainage

In Korea, the heavy metal pollution from about 1,000 abandoned mines has been a serious environmental issue. Especially, the surface waters, groundwaters, and soils around mines have been contaminated by heavy metals originating from acid mine drainage (AMD) and mine tailings. So far, AMD was considered as a waste stream to be treated to prevent environmental pollutions; however, the stream contains mainly Fe and Al and valuable metals such as Ni, Zn, and Cu. In this study, Visual MINTEQ simulation was carried out to investigate the speciation of heavy metals as functions of pH and neutralizing agents. Based on the simulation, selective pH values were determined to form hydroxide or carbonate precipitates of Cu, Zn, and Ni. Experiments based on the simulation results show that the recovery yield of Zn and Cu were 91 and 94 %, respectively, in a binary mixture of Cu and Zn, while 95 % of Cu and 94 % of Ni were recovered in a binary mixture of Cu and Ni. However, the recovery yield and purity of Zn and Ni were very low because of similar characteristics of Zn and Ni. Therefore, the mixture of Cu and Zn or Cu and Ni could be recovered by selective precipitation via pH adjustment; however, it is impossible to recover selectively Zn and Ni in the mixture of them.     

Speciation of heavy metals in sediments from the Scheldt estuary,Belgium

A simple three-step sequential extraction procedure was applied to study the speciation of heavy metals in sediment from Scheldt estuary, and their relationship to sediment grain size and organic matter content. The sedimentary metal content was fractionated into carbonate and exchangeable, metals bound to organic matter and residual fractions. Sedimentary total metal content was also determined using an industrial microwave (ETHOS 900) HF/HNO₃ extraction method. The extracts were analysed for metals using inductively coupled plasma atomic emission spectrometry. The bioavailable fraction (exchangeable and metals bound to organic matter) comprised less than the other forms. Residue metals were the dominant form of metals in almost all studied sites. The average total metal content for the studied sites decreased in the order Fe>Cr>Cu>Co>Zn>Pb>Cd. Based on average values for the studied sites, the highest bioavailable metals in sediments were Cd (38%) from Westkapelle, Zn (17%) from Yerseke, Co (12%) from Domburg, Cr (9%) from Vlissingen, Fe and Pb each (2%) from Yerseke, and Cu (1%) from Domburg. Metal recovery was good, with<10% difference between the total metal recovered through the extractant steps and the total metal determined using HF/HNO₃ extract.     

Comparative study of the fate and mobility of metals discharged in mining and urban effluents using sequential extractions on suspended solids

The fate, bioavailability and environmental impacts of metals discharged in municipal and mining wastewater discharge will depend to a large extent on chemical speciation and distribution. Previous studies on metal bioaccumulation have shown that total metal concentrations are not a good predictor of bioavailability in the dispersion plumes of municipal effluents. The objective of this study was to determine the solid phase speciation of metals in surface waters receiving urban and mining effluents in order to assess their fate and relative mobility in the receiving environment. Suspended particulate matter was sampled using sediment traps at several sites downstream of effluent outfall plumes as well as at reference upstream sites. Particulate metal in operationally defined fractions—exchangeable/carbonates, reducible, oxidisable and residual—were determined in suspended particulate matter with a series of selective chemical extractions. Metal enrichment in suspended particles was generally observed in both mining and urban effluent discharges. When compared to its receiving environment, the mining effluent appeared to release more particulate metals (Cu, Fe, Zn) in the most reactive fractions (i.e. exchangeable/carbonates + reducible forms, 23–43%), while other released metals, such as Cd and Mn, were predominantly in the least reactive forms (i.e., oxidisable + residual, 73–97%). In contrast, the reactivity of all particulate metals, with the exception of Mn, from the urban effluent was much higher, with up to 65, 42, 30 and 43% for Cd, Cu, Fe and Zn, respectively, in the two most reactive fractions. As expected in effluent dispersion plumes, parameters such as the organic carbon, Fe oxide and carbonate contents have specific effects on the partitioning of several trace metals, particularly Cd, Cu and Zn. Our results indicated that the relative distributions of metals among geochemical fractions varied in the effluent receiving waters where organic carbon and Fe oxides appeared as the most important parameters. This could therefore decrease the exposure for aquatic organisms that are exposed to those contaminated sediments as well as the risk to human health.     

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.     

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.