Geochemical distribution,bioavailability and potential toxicity of some trace metals in a complex micro-tidal estuary,Southwest India

The spatial and temporal variations of some trace metals in the surface sediments of Cochin Estuary were analyzed along with their geochemical associations to identify the possible sources, bioavailability and the health risks posed by them. The dominance of kaolinite and suggested that clay minerals distribution is influenced by sediment sorting. Total metal analysis revealed enrichment for Cd, Pb and Zn due to anthropogenic activities. The speciation analysis established that notwithstanding the large availability, carbonate as well as organic and sulfides bound fractions showed negligible associations with most of the metals. Hydrous Fe–Mn oxides appeared to play a major role in controlling the fate and transport of these metals in the sediments of Cochin Estuary. Lower contribution of the residual fractions for Cd (21%–26%), Pb (<60%) and Zn (24%–42%) indicated an obvious increase of other geochemical fractions. Risk assessment analysis revealed that regardless of total concentration, none of the analyzed metals were at safe levels in the estuary as appreciable percentages were found to be associated with mobile geochemical forms. The speciation study conspicuously established that the metals originating from non-geogenic sources are largely associated with the labile fractions and hence are more detrimental to the aquatic biota.     

Trace Metal Distribution and Enrichment in Benthic, Estuarine Sediments: Southport Broadwater, Australia

The distribution and enrichment of selected trace metals (Cd, Cr, Cu, Ni, Pb, Sn, Zn) in benthic sediments of the Southport Broadwater, a semi-enclosed coastal body of water adjacent to the Gold Coast city, south-eastern Queensland, Australia, was studied with the objective of assessing the extent and degree of sediment contamination. Sediment samples from the 0–10 cm and 10–20 cm depth intervals of 32 sites within the Southport Broadwater and surrounding residential canals were analysed for particle size distribution, pH, organic C and ‘near-total’ major (Al, Ca, Fe, Mn) and trace (Cd, Cr, Cu, Ni, Pb, Sn, Zn) metal contents. Sediment contamination for each trace metal was assessed by (1) comparison with Australian sediment quality guidelines, (2) calculation of the index of geoaccumulation based on regional background values, and (3) geochemical normalisation against Al (i.e. the abundance of alumino-silicate clay minerals). Based on this approach, the results indicate that submerged sediments in the study area are not presently enriched with Cd, Cr or Ni, with the spatial distribution of these metals being very well explained by the abundance of alumino-silicate clay minerals. However, several sites were strongly enriched with Cu, Pb, Sn and Zn, arising from sources related to either urban runoff or vessel maintenance activities. The study indicates that several varying approaches are needed for a satisfactory assessment of contaminant enrichment in estuarine sediments.     

Historical trends of trace metals in a sediment core from a contaminated tidal salt marsh in San Francisco Bay

Sedimentation of metals preserves historical records of contaminant input from local and regional sources, and measurement of metals in sediment cores can provide information for reconstruction of historical changes in regional water and sediment quality. Sediment core was collected from Stege Marsh located in central San Francisco Bay (California, USA) to investigate the historical input of trace metals. Aluminum-normalized enrichment factors indicate that inputs from anthropogenic sources were predominant over natural input for Ag, Cu, Pb, and Zn. Among these, lead was the most anthropogenically impacted metal with enrichment factors ranging from 32 to 108. Depth profiles and coefficients of variation show that As, Cd, and Se were also influenced by anthropogenic input. The levels of these anthropogenically impacted metals decline gradually towards the surface due to regulation of the use of leaded gasoline, municipal and industrial wastewater discharge control, and closure of point sources on the upland of Stege Marsh. Although trace metal contamination is expected to be continuously declining, the rates of decline have slowed down. For lead, it is estimated to take 44, 82, and 153 years to decrease to probable effects level (112 μg/g), the San Francisco Bay ambient surface sediment level (43.2 μg/g), and the local baseline levels (5 μg/g), respectively. Some metals in surface sediments (0–6 cm) are still higher than sediment quality guidelines such as the probable effects level. To further facilitate the recovery of sediment quality, more efficient management plans need to be developed and implemented to control trace metals from non-point sources such as stormwater runoff.     

人为活动对城市湖泊沉积物重金属污染的影响——以武汉墨水湖为例

人类活动使得大量的重金属向水环境中排放,导致了城市湖泊严重的重金属污染.为了研究中国的工业化、城市化发展对城市水体重金属污染的影响,以武汉墨水湖为例,测定了沉积物中几种常见痕量重金属Zn、Pb、Ni、Cu、Cr的含量和富集系数,并运用主成分分析对重金属的污染来源进行了初步探讨.结果表明,墨水湖表层沉积物重金属污染程度较重,主要受人为输入的影响;5种重金属在全湖区域上具有比较高的富集系数,尤以排污口为甚,排污口是重金属富集的主要区域.主成分分析表明,Pb可能主要来自于暴雨径流面源,而Cr可能主要来自于工矿企业的点源排放,其他3种金属则有着大小相当的点、面源输入贡献。以上结果表明,城市化和工业化进程已经给城市湖泊带来了很高的重金属污染负荷.     

Geographical and seasonal variation of trace metal bioavailabilities in the Gulf of Gdansk,Baltic Sea using mussels (<Emphasis Type="Italic">Mytilus trossulus</Emphasis>) and barnacles (<Emphasis Type="Italic">Balanus improvisus</Emphasis>) as biomonitors

The barnacle Balanus improvisus and the mussel Mytilus trossulus have been used as biomonitors of the trace metals Cu, Zn, Cd, Fe, Pb, Mn and Ni at five sublittoral sites in the Gulf of Gdansk (Baltic Sea) between February 2000 and September 2001. The study has established a benchmark against which future biomonitoring programmes will be able to establish changes in local metal pollution, particularly if metal loadings in the river Vistula (draining into the Gulf) alter in the future. The study highlighted differences in trace metal bioavailabilities to both barnacles and mussels, geographically and over time. Accumulated metal concentrations of Cu, Zn, Fe, Pb and Ni, but not Cd or Mn, were correlated in the barnacles and mussels, suggesting that the bioavailabilities of the former metals to the two biomonitors were similar. The barnacles showed greater discriminatory power than the mussels as trace metal biomonitors. Concentrations of trace metals in surficial sediments (<63 m) did not correlate significantly with accumulated metal concentrations in either barnacles or mussels, indicating that sediment metal concentrations are not necessarily good proxy measures of ambient trace metal bioavailabilities to the local coastal filter feeders.Communicated by J.P. Thorpe, Port Erin     

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.     

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.     

Seasonal variation and partition of trace metals (Fe, Zn, Cu, Mn, Cr, Cd and Pb) in surface sediments: relationship with physico-chemical variables of water from the Calabar River, South Eastern Nigeria

The seasonal variation and partition of trace metals (Fe, Cu, Zn, Mn, Cd, Cr and Pb) in the surface sediments of the Calabar River are reported. Chemical partition of the metals in the sediments reveals that 2–30% of the total metal load was contributed by the non-detrital (acid-soluble) fraction, while fine-grained host minerals/compounds are the main carriers of the detrital (acid-insoluble) fraction (70–98%). Using multivariate statistical analysis, the seasonal fluctuations in the distribution of some of the metals show significant influence by physio-chemical changes (dissolved oxygen, pH, salinity and conductivity) in the water column. Fe–Mn oxide grain coatings and sulphide materials have been identified as scavengers of some of the non-detrital and detrital trace metals in the sediments. On the basis of index of geoaccumulation (I-geo) and comparison with previous studies, the Calabar River surface sediments have been classified as unpolluted.     

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.     

Heavy Metals in the Bed and Suspended Sediments of Anyang River, Korea: Implications for Water Quality

The objective of this study is to compare Anyang River bed sediments with water chemical composition and to assess the anthropogenic chemical inputs into the river system. Eight sampling locations were chosen along the river channel. Bed and suspended river sediments and water samples were collected, and analyzed for their chemical and physical composition. Data revealed that trace element concentrations in the river water were generally below world average, except for As, Mn, Ni and Cr. Among the three phases: water, bed and suspended sediment, more than 99% of the trace elements was associated with the bed sediment. Concentrations of trace elements in the sediment were a function a particle size distribution and organic content. The calculated degrees of enrichment based on the least influenced sample (ASD 1) indicated the river sediments were enriched with respect to background. The enrichment factors for Pb, Zn and As were relatively lower than for Cr, Co, Ni and Zn. The difference in the enrichment seems to reflect the human activities influence in the basin, and specially for Cd. Speciation of the elements in the five different chemical forms in the sediment by sequential extraction indicated that the reducible fraction was predominant for Fe, Zinc and Cu showed an irregular variation among the different fractions; whereas, Cd and Pb were more regular. Zinc and Cu highly existed mostly in exchangeable forms. Acid soluble and reducible forms were also important for most metals. The speciation implies that the metals associated with the sediment are subject to release into water bodies as goechemical variables (pH and Eh) change. Currently, the introduced metals are deposited near the source area and are mostly associated with the sediment, implying that the river bed sediment acts mainly as a sink, rather than a pool. The accumulated and enriched toxic trace elements can pose a potential pollution of river water.     

Heavy metal contamination in river water and sediments of the Swarnamukhi River Basin,India: risk assessment and environmental implications

The concentration of heavy metals was analyzed each of 20 river water, suspended sediments and bed sediments along the stretch of Swarnamukhi River Basin. River water is not contaminated with heavy metals except Fe and Mn. Contamination factor in sediments shows considerable to very high degree contamination with Cr, Cu, Pb and Zn. The sources of these metals could be residential wastes, sewer outfall, fertilizers, pesticides (M-45 + carbondine) and traffic activities apart from natural weathering of granitic rocks present in the basin area. Principal component analyses indicate the interaction between metals in different media. The comparison of metals (Cu, Pb and Zn) in bed sediments of Swarnamukhi River with the Indian and world averages indicates that the values obtained in the basin are above the Indian averages and far below to the world averages. Average shale values and sediment quality guidelines point toward the enrichment and contamination of Cu, Cr, Pb and Zn to several fold leading to eco-toxicological risks in basin.     

城市湖泊表层沉积物中的重金属污染现状及其风险评价——以武汉墨水湖为例

水体沉积物中的重金属会对生态系统构成直接和间接的威胁.为了研究工业化、城市化过程中城市湖泊沉积物重金属污染现状及其暴露风险，以武汉市墨水湖为研究对象，测定了5种重金属Zn、Cu、Ni、Pb及Cr在表层沉积物中的含量，分析了其污染程度、分布特征，并对其稳定度进行了分析.结果表明，墨水湖表层沉积物重金属污染程度较重，在所有采样点5种重金属含量均高于最低效应阈值（LEL），多数采样点甚至超过了严重效应阈值（SEL）.该湖泊沉积物中重金属分布具有比较明显的空间差异性：排污口区>湖中心水域>城区岸边带>林田岸边带；其稳定程度依次为：Zn < Cu < Ni < Pb < Cr，其中Zn交换态及碳酸盐结合态比例超过50%，稳定程度极低.而Pb、Cr稳定程度较高，其交换态及碳酸盐结合态比例小于10%.像墨水湖这样受纳高污染负荷市政污水、暴雨径流的城市湖泊，其潜在的重金属生物活性，必须引起足够的重视.     

城市湖泊表层沉积物中的重金属污染现状及其稳定度分析——以武汉墨水湖为例

水体沉积物中的重金属会对生态系统构成直接和间接的威胁.为了研究工业化、城市化过程中城市湖泊沉积物重金属污染程度,以武汉市墨水湖为研究对象,测定了5种重金属Zn、Cu、Ni、Pb及Cr在表层沉积物中的含量,分析了其污染程度、分布特征,并对其稳定度进行了分析.结果表明,墨水湖表层沉积物重金属污染程度较重,在所有采样点5种重金属含量均高于最低效应阈值(LEL),多数采样点甚至超过了严重效应阈值(SEL);该湖泊沉积物中重金属分布具有比较明显的空间差异性:排污口区>湖中心水域>城区岸边带>林田岸边带;其稳定程度依次为:Zn相似文献   

Levels of heavy metals in blue whiting caught from the eastern Black Sea area of Turkey

This paper presents data on the concentrations of 5 metals, copper (Cu), cadmium (Cd), iron (Fe), zinc (Zn) and lead (Pb) in Blue Whiting sampled from the Eastern Black Sea coast of Turkey. The highest metal concentrations of Cu, Cd, Fe, Zn and Pb were recorded in Blue Whiting with the values of 2.71, 0.601, 14.137, 15.322 and 1.078 μg g^‐1 dry weight, respectively. On average the metal concentrations in Blue Whiting followed the order of Zn > Fe > Cu > Pb > Cd. Temporal differences of concentrations of these metals were significant (p < 0.05). Spatial fluctuations of Cu, Cd, Fe, Zn and Pb concentrations in Blue Whiting were also significant (p < 0.01). It was found that the concentrations of Cu, Cd, Fe, Zn and Pb in the muscle in Blue Whiting were below the limit of Public Health Regulation in Turkey.     

Speciation of heavy metals in Albanian coastal sediments

This article presents results on heavy metal (Fe, Mn, Cr, Ni, Cu, Cd, Pb and Zn) speciation in the coastal sediments of Albania. Sediment samples were collected within the framework of the activities of the Interreg Italia–Albania Project, carried out in the Southern Adriatic Sea in 2000–01. This study shows that Albanian coastal sediments are highly influenced by river input, as the decreasing concentrations from coast to offshore confirm. Pb represents an exception of the general trend; meteoric inputs are prevalent for this metal. Ni, Cr, Fe, Zn and Cu correlate significantly and positively in the entire area, indicating a common origin for these metals in the analyzed sediments. All metals result mostly associated to the most refractory phases, which constitute up to 80% of the total concentration. Nevertheless a recent input of Cr, Ni, Cu and Mn can be observed, as the result of mining and industrial activities, in some selected areas, such as the Drin Bay and Durres. Their high concentration in the bioavailable phase can determine toxic effect upon biota.     

A century-long trend of metal pollution in the Sheyang River,on the coast of Jiangsu (China), reconstructed from sedimentary record

In order to reveal the historical context of metal element accumulation under the economic boom during the last decades in eastern China, concentrations of nine metal elements, radionuclides (²¹⁰Pb), Pb isotope ratios (²⁰⁷Pb/²⁰⁶Pb) and sedimentary characteristics were investigated in two sediment cores collected from the Sheyang River. The sediments have recorded the heavy metal deposition and thus allow establishing a connection between the temporal evolution of the heavy metal pollution and historical changes in industrial and urban discharges. Enrichment factors (EFs) were calculated to estimate the level of contamination in these sediments. A significant anthropogenic enrichment of Cu, Ni, Pb, Cr and Zn was highlighted, which were identified from anthropogenic discharges from cities and industrial sources, according to a cluster analysis. According to the annual variation in GDP growth rate, industrial growth rate, ratio of ²⁰⁷Pb/²⁰⁶Pb and EFs, it was obvious that sedimentary accumulation of metals has a close relationship with anthropogenic activities. In the pre-industrial period, natural inputs prevailed with lower EF and constant ²⁰⁷Pb/²⁰⁶Pb ratios around 0.82. However, during 1980–1995, the rapid industrial development caused a gradual increase in EFs and ²⁰⁷Pb/²⁰⁶Pb (>0.83). Our results disinterred the evolution of anthropogenic metal inputs in the last century into the Sheyang 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.     

Sedimentary records of anthropogenic contribution to heavy metal content in Oum Er Bia estuary (Morocco)

Levels of heavy metals (Cd, Hg, Cr, Cu, Fe, Mn, Ni, Pb and Zn), organic carbon content and textural characteristics in the superficial and cored sediments of Oum Er Bia estuary have been studied. The anthropogenic fluxes of heavy metals were determined in two sediment cores collected in the estuary, facing urban sewages. A dated estuarine core from the inter-tidal area was assessed using ²¹⁰Pb and ¹³⁷Cs data. These data indicate that the mean sedimentation rates are 0.38–68 cm year^?1. The analytical results and the radio-dating of sediment cores show extremely high concentrations of Zn, Pb and Cu in the sediments that can be ascribed mostly to the discharge of the liquid effluent from the sewage since the late 1960s, decreasing towards the present day. The pollution intensity of the estuary is determined by the enrichment factors, which show that the Oum Er Bia estuary is moderately polluted to polluted.     

A comparison of metals in sediments and water in the River Nahr-Ibrahim,Lebanon: 1996 and 1999

Rivers whose basins are underlain by carbonate rocks exhibit high pH, lower desorption of metals and possess high buffering capacity against acidic inputs to the river. The catchment of River Nahr-Ibrahim, Lebanon, is largely underlain by limestone. Compared to neighbouring countries, Lebanon is relatively fortunate since precipitation is high. However, recently a warming in temperature and a drop in precipitation has occurred, thus causing low water levels in rivers. The objective of this study is to investigate the variation of the total metal content (Fe, Mn, Zn, Cu, Pb and Cd) in bed sediments and water of River Nahr-Ibrahim between 1996 and 1999 (two years); and relate these variations to the effect of changes in human activities and/or due to the variations of precipitation rate, temperature and pH of water. Bed load sediments and stream water were collected simultaneously from five sampling sites. Water pH and temperature were determined in situ. Sediment samples were dried at room temperature and sieved; the sediment size <75 m size was retained. Water was analysed for major constituents and trace metals. Metals were extracted from sediments with aqua regia. Metal concentration in water and sediments were determined using ICP-MS technique. Data revealed a drop in metal concentrations (Zn, Cu, Pb, Cd) in sediments at quarry site after its closure. The decrease in precipitation rate, lowering the level of water and the dilution of industrial discharges and decrease in water pH led most probably to the desorption of metals from sediments into the water.     

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.