Assessment of the environmental significance of heavy metal pollution in surficial sediments of the River Po

The magnitude and ecological relevance of metal pollution of the middle Po river deriving from the River Lambro tributary was investigated by applying different (complementary) sediment quality assessment approaches: (1) comparisons of concentrations with regional reference data, and (2) comparisons with consensus-based sediment quality guidelines (SQGs), as well as by investigations of the partitioning patterns of target heavy metals (Cd, Cu, Ni, Pb, Zn). Total metal concentrations in the surficial sediments revealed significant pollution inputs on the whole river stretch investigated, with a distinct peak at the inlet of the River Lambro. Based on the geoaccumulation index of target heavy metals, the middle reach of River Po has to be considered as moderately polluted with Cd (1相似文献   

Characterization of heavy metal concentrations in the sediments of three freshwater rivers in Huludao City, Northeast China

Wuli River, Cishan River, and Lianshan River are three freshwater rivers flowing through Huludao City, in a region of northeast China strongly affected by industrialization. Contamination assessment has never been conducted in a comprehensive way. For the first time, the contamination of three rivers impacted by different sources in the same city was compared. This work investigated the distribution and sources of Hg, Pb, Cd, Zn and Cu in the surface sediments of Wuli River, Cishan River, and Lianshan River, and assessed heavy metal toxicity risk with the application of two different sets of Sediment Quality Guideline (SQG) indices (effect range low/effect range median values, ERL/ERM; and threshold effect level/probable effect level, TEL/PEL). Furthermore, this study used a toxic unit approach to compare and gauge the individual and combined metal contamination for Hg, Pb, Cd, Zn and Cu. Results showed that Hg contamination in the sediments of Wuli River originated from previous sediment contamination of the chlor-alkali producing industry, and Pb, Cd, Zn and Cu contamination was mainly derived from atmospheric deposition and unknown small pollution sources. Heavy metal contamination to Cishan River sediments was mainly derived from Huludao Zinc Plant, while atmospheric deposition, sewage wastewater and unknown small pollution were the primary sources for Lianshan River. The potential acute toxicity in sediment of Wuli River may be primarily due to Hg contamination. Hg is the major toxicity contributor, accounting for 53.3-93.2%, 7.9-54.9% to total toxicity in Wuli River and Lianshan River, respectively, followed by Cd. In Cishan River, Cd is the major sediment toxicity contributor, however, accounting for 63.2-66.9% of total toxicity.     

Heavy metals in sediments,soils, and aquatic plants from a secondary anabranch of the three gorges reservoir region,China

We investigated the occurrence of cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb), Znic (Zn), iron (Fe), manganese (Mn), and magnesium (Mg) in sediments, as well as in related soils and aquatic plants in the Liangtan River, a typical secondary anabranch of the Yangtze River in the Three Gorges Reservoir Region (TGRR) of China. We found that sediments accumulated more metals than soils and aquatic plants. Concentrations of the nine metals in sediments and soils followed the same sequence, while their concentrations in aquatic plants followed a different sequence. Potential adverse effects of contaminated sediments on benthic fauna were evaluated, and the results showed that the toxic effect on benthic organisms followed the sequence Zn?>?Ni?>?Cr?>?Cu?>?Cd?>?Pb. The potential ecological risk index analysis indicated that Cd in sediments had considerable ecological risk, whereas Cr, Cu, Zn, Ni, and Pb had low ecological risk. The potential ecological risk index (RI) of the heavy metals in sediments of the Liangtan River was 174.9, indicating moderate ecological risk. The transfer factor trend of metals for aquatic plants showed that Cd and Ni had the most and least accumulation, respectively. For Cu, Cd, Mg, Pb, and Cr, a significant positive correlation of the metal concentrations was observed between sediments and soils, but no correlations (excluding Cr) were detected between sediments and aquatic plants. Our study indicated that anthropogenic input may be the primary source of metal contamination in the Liangtan River, and that Zn and Cd pollution in the Liangtan River should be further explored.     

Assessment of heavy metal contamination in Hindon River sediments: a chemometric and geochemical approach

The aim of this study was to assess the level of heavy metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) in the surface sediments of the Hindon River, India that receives both treated and untreated municipal and industrial discharges generated in and around Ghaziabad, India. Mean metals concentrations (mg kg⁻¹) were in the range of; Cu: 21.70-280.33, Cd: 0.29-6.29, Fe: 4151.75-17318.75, Zn: 22.22.50-288.29, Ni: 13.90-57.66, Mn: 49.55-516.97, Cr: 17.48-33.70 and Pb: 27.56-313.57 respectively. Chemometric analysis was applied to identify contribution sources by heavy metals while geochemical approaches (enrichment factor and geo-accumulation index) were exploited for the assessment of the enrichment and contamination level of heavy metals in the river sediments. Chemometric analysis suggested anthropic origin of Cu, Cd, Pb, Zn, and Ni while Fe showed lithogenic origin. Mn and Cr was associated and controlled by mixed origin. Geochemical approach confirms the anthropogenic influence of heavy metal pollution in the river sediments. The study suggests that a complementary approach that integrates chemometric analysis, sediment quality criteria, and geochemical investigation should be considered in order to provide a more accurate appraisal of the heavy metal pollution in river sediments. Consequently, it may serve to undertake and design effective strategies and remedial measures to prevent further deterioration of the river ecosystem in future.     

Heavy metal concentrations in sediments from Manila Bay, Philippines and inflowing rivers

Concentrations of Fe, Mn, Zn, Cu, Pb, Ni, Cd and Co were determined in surface and core sediments collected from Manila Bay and in surface sediments from inflowing rivers. Core profiles revealed highly fluctuating and enriched Pb, Cd, Zn and Cu concentrations on the surface, suggestive of recent inputs coming from anthropogenic sources. Concentrations of Pb, Zn, and to a lesser extent Cu and Cd were higher in riverine sediments as compared with marine sediments, which may be attributed to the proximity of these riverine sites to pollutant sources. Comparison of metal concentration levels obtained with other areas in the world revealed elevated values for Pb and Cd, indicating a considerable amount of pollution in the area. Continuous monitoring and further studies of the area are recommended to ascertain long-term effects that may have not yet been reached.     

Heavy metals in coastal wetland sediments of the Pearl River Estuary, China

Sediment quality in coastal wetlands of the Pearl River Estuary was concerned since the wetlands were used for land reclamation, aquaculture and wildlife protection, and meanwhile served as one of the main ultimate sinks for large amount of heavy metals discharged from the rapidly developing Pearl River Delta. Total concentrations of heavy metal, such as Zn, Ni, Cr, Cu, Pb, and Cd, and their chemical speciation were investigated. Results showed that the sediments were significantly contaminated by Cd, Zn and Ni with concentration ranges of 2.79-4.65, 239.4-345.7 and 24.8-122.1mg/kg, respectively. A major portion (34.6-46.8%) of Pb, Cd, and Zn was strongly associated with exchangeable fractions, while Cu, Ni and Cr were predominantly associated with organic fractions, residual, and Fe-Mn oxide. Cd and Zn would be the main potential risk and the sediment quality is no longer meeting the demand of the current wetland utilization strategies.     

Heavy metal and organic contaminants in mangrove ecosystems of China: a review

China’s rapid economic growth has been accompanied by increasing environmental pollution. Mangrove ecosystems are now facing greater pollution pressures due to elevated chemical discharges from various land-based sources. Data on the levels of heavy metals and organic pollutants in mangrove compartments (sediments, plants, zoobenthos, and fish) in China over the past 20 years have been summarized to evaluate the current pollution status of the mangrove ecosystem. Overall, the Pearl River and Jiulong River estuaries were severely polluted spots. Concentrations of Cu, Zn, Cd, and Pb in mangrove sediments of Guangdong, Fujian, and Hong Kong were higher than those from Guangxi and Hainan. The pollution status was closely linked to industrialization and urbanization. The highest concentrations of polycyclic aromatic hydrocarbons (PAHs) were found in mangrove sediments from Hong Kong, followed by Fujian and Guangdong. Mangrove plants tend to have low-enriched ability for heavy metals and organic pollutants. Much higher levels of Pb, Cd, and Hg were observed in mollusks.     

Distribution and fractionation of heavy metals in the Tisa (Tisza) River sediments

Introduction In this work, sediments of the River Tisa (Tisza) are studied to assess their environmental pollution levels for some major heavy metals, as well as to predict the investigated elements’ mobility on the basis of their association type with the substrate. The Tisa River catchments area is a subbasin of the River Danube. Part of this river, 166 km long, belongs to the Serbian province of Vojvodina, before it flows into the Danube. It has been chosen for our investigation, because it has been exposed to intense pollution in the last decades. Materials and Methods The river sediment samples were collected at 32 locations. The proportions of sand, silt and clay fractions were determined. The sequential extraction procedure following a modified Tessier method was applied for speciation of the metal forms in the collected samples. The metal concentrations of Zn, Cd, Pb, Ni, Cu, Cr, Fe and Mn in extracts were determined by atomic absorption spectroscopy. Results and Discussion Granulometric analysis showed that some 50% of the Tisa River sediments were silt and clay, while the rest was sand with quartz, as the main constituent. The average metal content of the surface river sediment samples for every fraction of sequential extraction was presented and discussed in relation to pH, Eh and metal fractionation. The average metal content from the Tisa River sediments, obtained as an average of the metal’s concentration released in all five sequential extraction fractions was compared with: average metal contents of the Tisa River sediments in Hungary, metal content in soils formed on the Tisa River alluvium of Vojvodina, average metal content in soils of Vojvodina, and average metal content in soils of Hungary. An assessment of metal pollution levels in Tisa River sediments was made by comparing mean values for obtained results for the Tisa River sediments with the freshwater sediment’s Quality Guidelines as published by US EPA, Environment Canada and soil standards for Serbia. Conclusion According to US EPA and Canadian Quality Guidelines for freshwater sediments, the concentration of heavy metals in Tisa sediments were: (a) much higher than defined concentrations below which harmful effects on river biota are unlikely to be observed, (b) below defined concentrations above which harmful effects on river biota are likely to be observed. The concentration levels of Pb, Ni, Cu and Cr in Tisa River sediments are safe when compared with Serbian MAQ (Maximum Allowed Quantity) standards for soils, but they are unsafe in the case of Zn and Cd. Recommendations and Outlook The quality of sediments in the Tisa River was on the border line between potentially polluted and polluted. This line could very easily be exceeded since the quality of sediments in the Tisa River in Hungary was already worse than in Serbia. These results indicated the need for further monitoring of heavy metals in that locality.     

Assessment of trace element pollution and ecological risks in a river basin impacted by mining in Colombia

Trace element pollution in rivers by anthropogenic activities is an increasing problem worldwide. In this study, the contamination and ecological risk by several trace elements were evaluated along a 100-km stretch of the San Jorge River in Colombia, impacted by different mining activities. The increase of average concentration levels and range of trace elements in sediments (in μg/g) was as follows: Cu 6656 (454–69,702) > Cd 1159 (0.061–16,227) > Zn 1064 (102–13,483) > Ni 105 (31–686) > Pb 7.2 (5.1–11.7) > As 1.8 (1.0–3.2) > Hg 0.31 (0.12–1.37). Results showed that surface sediments could be classified as very high ecological risk index (RI > 600), associated with high contamination of Hg, Cd, and Cu, in stations close mining activities. Values for pollution load index indicate an environmental deterioration (PLI > 1), and sediment quality guidelines (SQGs) suggested that Cu, Ni, Zn, and Hg caused adverse biological effects. We further used pollution indices such as contamination factor (CF), enrichment factor (EF), and geoaccumulation index (Igeo) to assess the extent of contamination. According to these indices, discharges of hazardous chemicals over many years have resulted in a high degree of pollution for Cu, Pb, and Cd, with critical values in stations receiving wastes from mining activities. Multivariate statistical analysis suggested that Hg, Cd, Cu, and Zn derived from gold and coal mining, Ni and As were related from the mining of ferronickel and coal, respectively, whereas the high Pb load was attributed to diffuse source of pollution. In sum, our study provided the first detailed database on metal concentration and ecological risks to organisms in sediments of the San Jorge River Basin, and the current results also suggested future research for public health action.

     

Concentrations,spatial distribution,and pollution assessment of heavy metals in surficial sediments from upstream of Yellow River,China

Surface sediments were collected from 122 sites in the upstream of the Yellow River, China. The concentration of Fe, Mn, Cu, Ni, Zn, Cr, Pb, and Cd in sediments was investigated to explore the spatial distribution based on statistics and interpolation method. The results suggested that the concentrations of heavy metals were lower than potential effect levels (PEL). The samples above threshold effect level (TEL) for Pb and Zn were less than 10%, while almost 50% of samples for Ni exceeded PEL. Pb and Zn in sediments performed little or no adverse effects on the aquatic ecosystems. Higher concentrations of all heavy metals occurred in Qinghai and Gansu sections; the concentrations of Cu, Ni, and Zn were significantly higher than the Inner Mongolia section. Lower concentration of Fe, Mn, Cu, Ni, and Zn appeared in Qinghai section; the concentrations of Fe, Mn, Cr, and Pb manifested relatively steady and similar distributions and approximately decreasing tendency along the upstream of Yellow River.

     

重庆市清水溪河流沉积物重金属污染及潜在生态风险评价

采用单因子指数法和Hakanson潜在生态风险指数法,通过分析清水溪流域18个采样点沉积物中典型重金属污染物Cd、Cr、Cu、Pb和Zn的含量,定量确定了清水溪沉积物中重金属的污染程度和潜在生态风险程度。结果表明,清水溪流域污染非常严重,上中游河段受到重金属的高强度污染,主要的重金属污染因子为Zn,污染因子的高低顺序为：Zn>Cu>Cr>Cd>Pb;潜在生态风险指数RI平均值为255.58,清水溪处于高值潜在生态风险,且上中游河段潜在生态风险指数很高,主要的潜在生态风险因子为Cd,潜在生态风险因子的大小顺序为：Cd>Cu>Cr>Zn>Pb。     

Assessment of heavy metal pollution from a Fe-smelting plant in urban river sediments using environmental magnetic and geochemical methods

Environmental magnetic proxies provide a rapid means of assessing the degree of industrial heavy metal pollution in soils and sediments. To test the efficiency of magnetic methods for detecting contaminates from a Fe-smelting plant in Loudi City, Hunan Province (China) we investigated river sediments from Lianshui River. Both magnetic and non-magnetic (microscopic, chemical and statistical) methods were used to characterize these sediments. Anthropogenic heavy metals coexist with coarse-grained magnetic spherules. It can be demonstrated that the Pollution Load Index of industrial heavy metals (Fe, V, Cr, Mo, Zn, Pb, Cd, Cu) and the logarithm of saturation isothermal remanent magnetization, a proxy for magnetic concentration, are significantly correlated. The distribution heavy metal pollution in the Lianshui River is controlled by surface water transport and deposition. Our findings demonstrate that magnetic methods have a useful and practical application for detecting and mapping pollution in and around modern industrial cities.     

Geochemical and Pb isotopic evidence for sources and dispersal of metal contamination in stream sediments from the mining and smelting district of Príbram, Czech Republic

Stream sediments from the mining and smelting district of Príbram, Czech Republic, were studied to determine the degree, sources and dispersal of metal contamination using a combination of bulk metal and mineralogical determinations, sequential extractions and Pb isotopic analyses. The highest metal concentrations were found 3-4 km downstream from the main polymetallic mining site (9800 mg Pb kg(-1), 26 039 mg Zn kg(-1), 316.4 mg Cd kg(-1), 256.9 mg Cu kg(-1)). The calculated enrichment factors (EFs) confirmed the extreme degree of contamination by Pb, Zn and Cd (EF>40). Lead, Zn and Cd are bound mainly to Fe oxides and hydroxides. In the most contaminated samples Pb is also present as Pb carbonates and litharge (PbO). Lead isotopic analysis indicates that the predominant source of stream sediment contamination is historic Pb-Ag mining and primary Pb smelting (206Pb/207Pb=1.16), while the role of secondary smelting (car battery processing) is negligible.     

Characterization and spatial distribution of heavy metals in sediment from Cedar and Ortega rivers subbasin

The Cedar and Ortega rivers subbasin is a complex environment where both natural and anthropogenic processes influence the characteristics and distributions of sediments and contaminants, which in turn is of importance for maintenance, dredging and pollution control. This study investigated the characteristics and spatial distribution of heavy metals, including lead (Pb), copper (Cu), zinc (Zn) and cadmium (Cd), from sediments in the subbasin using field measurements and three-dimensional kriging estimates. Sediment samples collected from three sampling depth intervals (i.e., 0-0.10, 0.11-0.56 and 0.57-1.88 m) in 58 locations showed that concentrations of Pb ranged from 4.47 to 420.00 mg/kg dry weight, Cu from 2.30 to 107.00 mg/kg dry weight, Zn from 9.75 to 2,050.00 mg/kg dry weight and Cd from 0.07 to 3.83 mg/kg dry weight. Kriging estimates showed that Pb, Cu and Cd concentrations decreased significantly from the sediment depth of 0.10 to 1.5 m, whereas Zn concentrations were still enriched at 1.5 m. It further revealed that the Cedar River area was a potential source area since it was more contaminated than the rest of the subbasin. Comparison of aluminum (Al)-normalized metal concentrations indicated that most of the metals within the top two intervals (0-0.56 m) had concentrations exceeding the background levels by factors of 2-10. A three-dimensional view of the metal contamination plumes showed that all of the heavy metals, with concentrations exceeding the threshold effect level (TEL) that could pose a threat to the health of aquatic organisms, were primarily located above the sediment depth of 1.5 m.     

Accumulation of heavy metals in Typha angustifolia (L.) and Potamogeton pectinatus (L.) living in Sultan Marsh (Kayseri, Turkey)

Concentrations of heavy metals (Cd, Pb, Cr, Ni, Zn and Cu) were measured in bottom sediments, water and Typha angustifolia and Potamogeton pectinatus in Sultan Marsh. Sultan Marsh is one of the largest and most important wetlands in Turkey, Middle East and Europe, embodying saline and fresh water ecosystems and providing a shelter for 426 bird species. The organs of T. angustifolia have a larger quantity of the measured elements than the P. pectinatus. Considerably higher contents of Cd were found rather than in helophytes (P. pectinatus) in submerged plant (= emergent, T. angustifolia) species. The percentage of Cd in plant tissues points to a certain degree of water pollution in Sultan Mash. Analyses of water, bottom sediments and plant samples indicated that the Marsh were polluted with Pb, Cd, and partly with Cu and Zn. All sampling sites in the study area basin are generally more or less polluted when compared with the control values. Strong positive correlation was found between concentrations of Pb in water and in plants. Ni and Pb were accumulated by plants at a higher rate from bottom sediments than from water. Leaves of T. angustifolia accumulated less heavy metal than the corresponding roots. There was a significant relationship between Cd concentration in samples of plants and water pH value. It has been found that the tissues of T. angustifolia accumulate more heavy metals than the tissues of P. pectinatus. Therefore, all plants can be used as a biological indicator while determining environmental pressures; however, T. angustifolia is proved more appropriate for such studies.     

深圳市河流沉积物重金属污染特征及评价

分析了深圳市的深圳河、布吉河、龙岗河和茅洲河等4条河流沉积物中重金属的含量和富集状况,并对重金属污染的潜在生态危害进行了评价。结果表明：（1）1996-2003年,深圳河、布吉河、龙岗河和茅洲河沉积物中重金属的含量都有上升的趋势;布吉河和龙岗河沉积物中的重金属含量较高,特别是Cu、Zn和Cr的含量比其他两条河流高出较多,深圳河居中,茅洲河较小;这4条河流都以Cd、Cu、Cr和Zn的富集为主。（2）在研究时段内,这4条河流沉积物重金属污染的潜在生态危害指数（RI）都有上升的趋势;其中深圳河,布吉河和龙岗河的RI在多数年份都达到强或很强的程度,Cd、Hg、Cu为主要贡献元素;4条河流中,茅洲河受重金属污染最小,其RI为轻微或中等,只有Cd和Hg的生态危害系数为中等或强。针对深圳市河流沉积物中重金属的累积机理,建议通过改善区域水文条件、控制污染物的排放等措施加以控制和治理。     

Metal contamination and solid phase partitioning of metals in urban roadside sediments

This study was undertaken to assess the anthropogenic impact on metal concentrations of urban roadside sediments (N = 633) in Seoul city, Korea and to estimate the potential mobility of selected metals (Zn, Cu, Pb, Cr, Ni, and Cd) using sequential extraction. Comparison of metal concentrations in roadside sediments with mean background values in sediments collected from first- or second-order streams in Korea shows that Zn, Cu and Pb are most affected by anthropogenic inputs. The 206Pb/207Pb ratios of roadside sediments (range = 1.1419-1.1681; mean 1.1576 +/- 0.0068) suggest that Pb is mainly derived from industrial sources rather than from leaded gasoline. A five-step sequential extraction of roadside sediments showed that Zn, Cd and to a lesser degree Ni occur predominantly in the carbonate bound fraction, while Pb is highest in the reducible fraction, Cu in the organic fraction, and Cr in the residual fraction. It was found that the concentrations in the readily available exchangeable fraction were generally low for most metals examined, except for Ni whose exchangeable fraction was appreciable (average 15.2%). Considering the proportion of metals bound to the exchangeable and carbonate fractions, the comparative mobility of metals probably decreases in the order of Zn > Ni > Cd > Pb > Cu > Cr. As potential changes of redox state and pH may remobilize the metals bound to carbonates, reducible, and/or organic matter, and may release and flush them through drain networks into streams, careful monitoring of environmental conditions appears to be very important. With respect to ecotoxicity, it is apparent the Zn and Cu pollution is of particular concern in Seoul city.     

Heavy metal pollution in sediments of the Pasvik River drainage

The purpose of this paper is to study the regional impacts of heavy metals (Ni, Cu, Co, Zn, Cd, Pb, Hg) on the watershed of the Pasvik River. On the basis of sediment investigations at 27 stations of the watershed, background concentrations of the heavy metals, vertical distribution of heavy metals in sediments, heavy metal concentrations in surface sediments, contamination degree, and risk index were determined. The atmospheric emissions of Ni, Cu, Co, Zn, Cd and Hg from the smelters and waste waters from tailing dams and mines of the Pechenganickel Company are likely to be the main sources of increasing concentrations observed in recent sediments of the lower river reaches. Lead showed a different pattern from the other heavy metals--increasing Pb concentrations in the upper sediment layers towards the Norwegian side.     

Heavy metal pollution in China: Origin,pattern and control

GOAL, SCOPE AND BACKGROUND: Heavy metal is among one of the pollutants, which cause severe threats to humans and the environment in China. The aim of the present review is to make information on the source of heavy metal pollution, distribution of heavy metals in the environment, and measures of pollution control accessible internationally, which are mostly published in Chinese. METHODS: Information from scientific journals, university journals and governmental releases are compiled focusing mainly on Cd, Cu, Pb and Zn. Partly Al, As, Cr, Fe, Hg, Mn and Ni a included also in part as well. RESULTS AND DISCUSSION: In soil, the average contents of Cd, Cu, Pb and Zn are 0.097, 22.6, 26.0 and 74.2 mg/kg, respectively. In the water of the Yangtze River Basin, the concentrations of Cd, Cu, Pb and Zn are 0.080, 7.91, 15.7 and 18.7 microg/L, respectively. In reference to human activities, the heavy metal pollution comes from three sources: industrial emission, wastewater and solid waste. The environment such as soil, water and air were polluted by heavy metals in some cases. The contents of Cd, Cu, Pb and Zn even reach 3.16, 99.3, 84.1 and 147 mg/kg, respectively, in the soils of a wastewater irrigation zone. These contaminants pollute drinking water and food, and threaten human health. Some diseases resulting from pollution of geological and environmental origin, were observed with long-term and non-reversible effects. CONCLUSIONS: In China, the geological background level of heavy metal is low, but with the activity of humans, soil, water, air, and plants are polluted by heavy metals in some cases and even affect human health through the food chain. RECOMMENDATIONS AND OUTLOOK: To remediate and improve environmental quality is a long strategy for the polluted area to keep humans and animals healthy. Phytoremediation would be an effective technique to remediate the heavy metal pollutions.     

Impact of industrial and mine drainage wastes on the heavy metal distribution in the drainage basin and estuary of the Sado River (Portugal)

This paper presents results from a survey of the heavy metal distribution in sediments in the drainage basin and estuary of the Sado River (Portugal). In the drainage basin, heavy metals originate mostly from pyrite outcrop erosion and mining activities (Cd, Zn, Cu and locally Hg, Pg), and also from crust erosion (Sn, Ni, Ti, Zr). These sources are not correlated with the particulate organic carbon (POC) and so the metals are thought to be in inorganic forms in this area. Anthropogenic heavy metal sources (urban and industrial) are found in the lower estuary (Sn, Cd, Hg, Zn, Pb and Cu) along with high POC concentrations. In this zone, these metals are thought to be strongly adsorbed onto organic particles. Furthermore, organo-metallic species are likely to be present, as demonstrated in the case of Sn, since methyl- and butyl-tin species were detected in sediments from this area. This suggests the need for the detection of organo-metallic species to understand the heavy metal geochemical cycles. No long-term changes in metal concentrations are found in sediment cores, except in the middle estuary (Zn, Cu) due to the development of mining activities on an industrial scale in the 1860s.