Trace metal behaviour in the Conwy estuary,North Wales

The distribution of trace metals Zn, Ni, Mn, Fe, Cu, Pb, Cd and Cr between suspended particulate matter (SPM) and water in the Conwy estuary, North Wales, has been studied in three surveys in 1998. Dissolved Cu and Mn showed some monthly variations. Most of the dissolved trace metals displayed a negative association with salinity, indicating rivers as a major source of inputs for them. Particulate Zn, Mn and Fe showed a decreasing concentration seaward, whilst the levels of Ni, Cu, Cr and Pb increased with salinity. SPM concentration was the most important variable significantly related to trace metal concentrations in SPM, with an inverse relationship between the two parameters. This was explained by the relative enrichment of trace metals in fine particles at low SPM concentrations and relative depletion of trace metals in coarse particles at high SPM concentrations. Particulate Zn, Mn and Pb were dominated by the fraction available to acetic acid (non-detrital), whilst particulate Ni, Fe and Cr were dominated by the fraction available to nitric acid (detrital). The partition coefficient of trace metals between SPM and water declined with increasing SPM concentration, consistent with the so-called "particle concentration effect". Such a phenomenon may be explained by the presence of fine particles (including colloids) enriched with trace metals at low SPM concentrations, and the salinity-induced desorption.     

Distribution and coassociations of trace elements in soft tissue and byssus of Mytilus galloprovincialis relative to the surrounding seawater and suspended matter of the southern part of the Korean Peninsula

The concentrations of Cd, Co, Cu, Cr, Fe, Hg, Mn, Ni, Pb, Sn, Ti and Zn were analyzed by AAS, ICP MS and AFS in soft tissues and byssal threads of Mytilus galloprovincialis from Masan Bay and Ulsan Bay, Korea. Spatial variations in metal concentrations were found. The levels of Cd, Pb, Hg, Cu, Zn, Co and Mn were very high in the mussels from Ulsan Bay (Sts. U1, U2) and comparable with elevated concentrations of these elements in Mytilus sp. reported to date for other geographical areas. Seasonal differences in some metal concentrations were also observed. These variations may be caused by factors such as: a large difference in seawater temperature, food supply for the mussel population and/or freshwater runoff of particulate metal to the coastal water and weight changes brought about by gonadal development and the release of sexual products. Pb, Cu, Zn, Co, Ni, Fe and Mn were more enriched in byssal threads than in the soft tissues, hence the byssus seems to be more sensitive in reflecting the availabilities of trace metals in the ambient waters. Concentrations of trace metals varied with respect to the size of mussels and season, depending on many factors like sexual development, and seawater temperature, etc. The levels of some trace metals in seawater, especially in suspended matter were correlated significantly with those in soft tissues and byssal threads. There were spatial variations in metal concentrations in the soft tissue and byssus attributed to different sources of trace elements located near the sampling sites. There were significant relationships between concentrations of some metals (Cd, Cu, Pb, and Zn) in mussel soft tissues and byssal threads and suspended matter. This suggests that M. galloprovincialis can be used as a sensitive biomonitor for the availabilities of trace elements in the coastal waters off Korea.     

Metals in a northern Nile Delta lake: water,suspended particulates,sediments, and biota

Lake Edku is one of the important fishing areas in the Nile Delta. It is exposed to different quantities of serious pollutants in particular metals. To overall appraise the risk and status of metals in the lake, a comprehensive study of total concentrations of cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), and zinc (Zn) in sediments and spatial-temporal variations of these metals in the dissolved and suspended particulates, and some tissues of Tilapias niloticus, was conducted from ten sampling sites during 2016. Results showed that none of the investigated metals exceeded the limits considered as hazardous for aquatic life in water. The highest concentrations of Cd, Cu, Ni, and Zn were observed in suspended particulate matter, which may precipitate on the surface of the sediments. Potential ecological risk analysis of the majority of the investigated metals in the sediment indicated that Lake Edku posed a low ecological risk. The estimated values of all metals in tissues of Tilapia niloticus were below the international permissible limits. Moreover, the potential risk of metals to human via the consumption of Tilapia niloticus was estimated using the weekly intake levels, which was lower than the WHO’s safe provisional tolerant weekly intake levels. These results prove the importance of performing measurements of contaminants in various compartments of Lake Ecosystem including sediment, biota, and suspended particulate matter for proper management.     

Mobility of heavy metals from polluted sediments of a semi-enclosed basin: in situ benthic chamber experiments in Taranto’s Mar Piccolo (Ionian Sea,Southern Italy)

In situ benthic flux experiments were conducted at two stations in the Mar Piccolo of Taranto (Italy), one of the most industrialised and contaminated coastal areas of the Mediterranean. Sediments of the two stations are notably different in their trace metal content, with a station closer to a Navy harbour showing higher mean concentrations of almost all investigated metals (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn). Conversely, both stations are characterised by significant Hg contamination, compared to the local baseline. Results of a sequential extraction scheme on surface sediments suggest a relatively scarce mobility of the examined metals (Zn > Ni > Cr > As > Cu > Pb). A Hg-specific extraction procedure showed that most of the element (93.1 %) occurs in a fraction comprising Hg bound to Fe/Mn oxi-hydroxides. Reduction of these oxides may affect Hg remobilisation and redistribution. Porewater profiles of dissolved trace metals were quite similar in the two sites, although significant differences could be observed for Al, Cu, Fe and Hg. The highest diffusive fluxes were observed for As, Fe and Mn. Mobility rates of several trace elements (Al, As, Cd, Cr, Cu, Fe, Hg, Mn, Ni, Pb, V and Zn) were directly measured at the sediment–water interface. Results from benthic in situ incubation experiments showed increasing dissolved metal concentrations with time, resulting in higher fluxes for Cu, Fe, Hg, V and Zn in the most contaminated site. Conversely, fluxes of Mn, Ni and Pb were comparable between the two stations. The estimated flux of Hg (97 μg m^?2 day^?1) was the highest observed among similar experiments conducted in other highly contaminated Mediterranean coastal environments. Benthic fluxes could be partially explained by considering rates of organic matter remineralisation, dissolution of Fe/Mn oxy-hydroxides and metal speciation in sediments. Seasonal and spatial variation of biogeochemical parameters can influence metal remobilisation in the Mar Piccolo area. In particular, metals could be promptly remobilised as a consequence of oxygen depletion, posing a serious concern for the widespread fishing and mussel farming activities in the area.     

The asiatic clam, Corbicula fluminea: An indicator of trace metal pollution in the Shatt al-Arab River, Iraq

The potential of Corbicula fluminea (Müller) as an indicator for trace metal pollution was investigated. Laboratory experiments show that Corbicula has the capability to accumulate and eliminate trace metals in relation to their concentrations in ambient water. However, an effect of individual size was observed. Seasonal variations in the concentrations of Cd, Co, Cu, Fe, Mn, Ni, Pb, V and Zn in Corbicula, water and particulate matter from the upper section of the Shatt al-Arab River were studied. Sediment samples were also analysed. Metal concentrations were determined by means of flameless AAS. It was found that Corbicula is a suitable bio-indicator for monitoring of trace metal pollution. Metal concentrations in Corbicula tissues correlated better with their corresponding concentrations in particulate matter than with the dissolved form. Temporal variations in metal concentrations were attributed to several factors, including fluctuations in metal inputs, and in geochemical and hydrological characteristics of the water. The obtained levels of trace metals were comparable to those reported for control sites, with the exception of Cd, Cu and Zn whose concentrations were higher in both Corbicula and particulate matter.     

Distribution of metals in a polluted aquifer: A comparison of aquifer suspended material to fine sediments of the adjacent environment

Metal concentrations were determined for groundwater suspended matter from a site in the coastal aquifer of Israel which has been irrigated with secondary sewage effluents since the 1960's. Suspended matter was collected from the aquifer saturated zone by pumping and by a multi-layer sampler. Fine sediments were collected from both the unsaturated and saturated zones of the contaminated aquifer, as well as from an adjacent uncontaminated environment. Ag, Cu, Fe, Mn and Zn were leached from the samples in three sequential chemical extractions which are taken to represent the carbonate, organic and oxide phases. Comparison of the aquifer samples to those of the adjacent environment showed that Fe and Mn are primarily enriched in non-mobile fine sediments and not in suspended matter, whereas the concentrations of Zu, Cu and Ag show up to an order of magnitude enrichment in the mobile suspended matter in groundwater. The enrichment of these metals in the suspended matter indicates that metals from sewage effluents and agricultural activities have reached the groundwater.     

Environmental impacts of coastal aquaculture in eastern mediterranean bays the case of astakos gulf,Greece

GOAL, SCOPE AND BACKGROUND: Over the last decade Greece has become a leading country in the EU as concerns the cage farming of seabream and seabass. A strong debate has risen, however, about the environmental impacts of aquacultures in the coastal areas. The present paper deals with this problem and it is based on measurements of physico-chemical parameters in the water column, particulate matter and sediments in the area of Astakos Gulf, a coastal embayment in western Greece where three big fish farms are currently operating. METHODS: Water samples were collected by using Hydro-Bios sampling bottles, whereas a prototype sediment trap was installed under a fish cage for the collection of particulate matter. Temperature, dissolved oxygen, pH and salinity were measured in situ using portable equipment. Nutrients were determined by standard spectrophotometric methods. Trace metals were determined by Atomic Absorption Spectrometry. Dissolved organic carbon was determined by a Shimadzu 5000A carbon analyzer, whereas organic carbon in sediments was determined titrimetrically. RESULTS AND DISCUSSION: No clear eutrophication incidents have been identified, although the water column near the fish farms was enriched in nutrients and organic carbon. A sludge 'blanket' covers considerable parts of the seabed and is enriched in colloidal organic carbon and trace metals (Cd, Cu, Fe and Zn) that come from unused fish food. The biodegradation of this sludge leads to the development of anoxic conditions followed by the formation of undesirable gases, precipitation or remobilization of metals and the extinction of benthic fauna. CONCLUSION: The operation of fish farms at the coastal area of Astakos Gulf, and probably in similar Mediterranean gulfs, affects the marine environment, particularly in the vicinity of the cages. The most significant influence concerns the near-bottom water layer. The environmental impacts depend on the amount of food given to fishes, the mode of feeding, the fish density in cages, the annual production and the years of unit operation. The hydrology and the geomorphology of the area are also critical factors for its environmental quality. RECOMMENDATION AND OUTLOOK: The success of the fish-farming sector in the Mediterranean is accompanied by environmental and, in some extents, by social and marketing problems. These problems, derived from the rapid development of fish farming, can be solved only through an integrated management, using methods such as environmental impact assessment, risk assessment, economic evaluation, vulnerability assessments, resource accounting, cost-benefit analysis and outcome-based monitoring.     

Metal concentrations in Kandalaksha Bay, White Sea (Russia) following the spring snowmelt

Elevated concentrations of dissolved and particulate Cd, Cu, Pb and Zn have been determined in the waters of Kandalaksha Bay (White Sea, Russia), following the ice melt in the spring of 2000. Dissolved metal maxima in the surface waters were observed at some stations and concentrations generally decreased with depth. The suspended particulate matter (SPM) comprised a non-lithogenic fraction in the range 12-83%, and had elevated metal concentrations that showed no trend with depth or salinity and was compositionally distinct from the sediments. A log-linear relationship existed between the concentrations of metals in sediments and in SPM and their respective Al concentrations, indicating a source of metal-rich particles, with low Al content, to the Bay. The results suggest that Kandalaksha Bay has been impacted by industrial activity on the Kola Peninsula and that restricted water exchange will hinder its recovery from metal contamination.     

Contamination status and potential release of trace metals in a mangrove forest sediment in Ho Chi Minh City,Vietnam

Can Gio district is located in the coastal area of Ho Chi Minh City, southern Vietnam. Discharge of wastewater from Ho Chi Minh City and neighboring provinces to the rivers of Can Gio has led to concerns about the accumulation of trace metals (As, Cu, Cr, Ni, Pb, and Zn) in the coastal sediments. The main objective of this study was to assess the distribution of As, Cu, Cr, Ni, Pb, and Zn in surface and core sediments and to evaluate the contamination status in relation to local background values, as well as the potential release of these selected trace metals from sediments to the water environment. Sediment characteristization, including determination of fine fraction, pH, organic matter, and major elements (Al, Fe, Ca, K, Mg, and S), was carried out to investigate which parameters affect the trace metal enrichment. Fine fraction and Al contents were found to be the controlling proxies affecting the distribution of trace metals while other sediment characteristics did not show any clear influence on trace metals’ distribution. Although As concentrations in the sediments were much higher compared to its reference value in other areas, the enrichment factor based on local background values suggests minor contamination of this element as well as for Cr, Cu, and Pb. Risk assessment suggested a medium to very high risk of Mn, Zn, and Ni under acidification. Of importance is also that trace metals in sediments were not easily mobilized by organic complexation based on their low extractabilities by ammonium-EDTA extraction.

     

Octanol-solubility of dissolved and particulate trace metals in contaminated rivers: implications for metal reactivity and availability

The lipid-like, amphiphilic solvent, n-octanol, has been used to determine a hydrophobic fraction of dissolved and particulate trace metals (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) in contaminated rivers. In a sample from the River Clyde, southwest Scotland, octanol-solubility was detected for all dissolved metals except Co, with conditional octanol-water partition coefficients, D(ow), ranging from about 0.2 (Al and Cu) to 1.25 (Pb). In a sample taken from the River Mersey, northwest England, octanol-solubility was detected for dissolved Al and Pb, but only after sample aliquots had been spiked with individual ionic metal standards and equilibrated. Spiking of the River Clyde sample revealed competition among different metals for hydrophobic ligands. Metal displacement from hydrophobic complexes was generally most significant following the addition of ionic Al or Pb, although the addition of either of these metals had little effect on the octanol-solubility of the other. In both river water samples hydrophobic metals were detected on the suspended particles retained by filtration following their extraction in n-octanol. In general, particulate Cu and Zn (up to 40%) were most available, and Al, Co and Pb most resistant (<1%) to octanol extraction. Distribution coefficients defining the concentration ratio of octanol-soluble particle-bound metal to octanol-soluble dissolved metal were in the range 10(3.3)-10(5.3)mlg(-1). The presence of hydrophobic dissolved and particulate metal species has implications for our understanding of the biogeochemical behaviour of metals in aquatic environments. Specifically, such species are predicted to exhibit characteristics of non-polar organic contaminants, including the potential to penetrate the lipid bilayer. Current strategies for assessing the bioavailability and toxicity of dissolved and particulate trace metals in natural waters may, therefore, require revision.     

Bottom sediments of the Arabian Gulf--III. Trace metal contents as indicators of pollution and implications for the effect and fate of the Kuwait oil slick

The trace metal contents of 71 core samples collected in 1992 from the bottom sediments of the Arabian Gulf are used to determine the regional distribution of concentration and pollution levels of these substances in the region. Chronic contamination was recorded in seven locations: the northwestern area (Fe), the northeastern area (Fe, V and Ni), the north-central area (V and Ni), the central area (Fe, Pb, V and Ni), the south-central area (Cu), the eastern area (Cu) and the southeastern area (Fe, V and Ni). Present-day contamination was identified in three locations only: the north-central area (V), the central area (Pb, V and Ni) and the southeastern area (Fe, V and Ni). Diversified natural and anthropogenic inputs may have provided the sources of this contamination. The V/Ni ratios of recent marine sediments cannot be used in identifying oil spillages or in oil-sediment correlation studies. Positive correlations are found between increasing trace metal concentration and decreasing carbonate content and grain size, verifying that adsorption onto muds is the primary mechanism of trace metal concentration in marine sediments. Correlations with TOC (total organic carbon) contents indicate that organic matter is a significant concentrator only in the case of Pb and Cu. With the exception of the Fe contamination in the northwest area due to river transport, all chronic and present-day trace metal concentrations are within the permissible natural background levels in the western offshore areas, including the two areas thought to be polluted by the Kuwait oil slick, thereby supporting the idea that airborne fallout from oil fires was deposited in a limited coastal area between Kuwait and Bahrain, and verifying that the oil slick had minimal effect on the state of pollution by trace metals in the Arabian Gulf.     

Trace element contamination of Norwegian Lake sediments

Concentrations of Sb, Hg, Bi, Cd, Mo, As, Co, Ni, Cr, Cu, V, Pb and Zn in surface and preindustrial sediments from 210 lakes in Norway were used for studying modern atmospheric depositions of these elements. Surface sediments had considerably higher concentrations of Sb, Hg, Bi, Cd, As, Pb than preindustrial sediments. The differences decreased with latitude and altitude. A multivariate analysis including the trace elements and the major constituents (organic matter, Si, Al, Fe and Mn) of surface sediments suggested the following relationships: Sb, Hg, Bi, As, and Pb formed a group with strong associations to organic matter. Ni, Cr and Cu formed a second group, weakly associated to the inorganic sediment fraction (Si and Al). Zn and Cd formed a third group with weak associations to organic matter. Co was associated to Mn, whereas Mo and V showed no important covariations with any other trace elements or major components.     

Spatial and seasonal variation of major and trace elements in settling particulate matter in an estuarine-like archipelago area in the Northern Baltic proper

This study describes the spatial and the seasonal variation of flux and concentration of 11 metals (Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Zn), organic matter and C and N in settling particulate matter collected with sediment traps during seven interconnective, continuous periods totalling 15 months. Ten sediment traps were placed out along the metropolis-affected fresh water outflow of Lake M?laren, out through a non-tidal estuarine-like region with a low salt content, through the Stockholm archipelago to the Baltic. The metal concentrations of the particles were analysed with AAS using the flame technique and the amounts of C and N were determined with elemental analysis (CHN). The flux of particulate matter and of all metals decreased rapidly outwards in a gradient from the innermost stations. The distribution and composition of the particles were dominated by variations in the runoff from Lake M?laren and by the seasonal dependence on primary production. However, they were also influenced locally by the supply of nutrients via water treatment plant effluents and probably by the special sedimentation conditions in the mixing zones and by resuspension. The concentrations of Cu, Hg, Pb and Cd in the interior of the area under investigation were the most elevated of the elements and decreased markedly further out in the archipelago, indicating local anthropogenic input. Zn, Cr and Fe also showed signs of supply from the urbanized environment. The flux of most of the metals studied displayed both spatial and seasonal correlation with the weight (TPM) of the material, whereas seasonal variation of Cd was correlated to its volume (TPV) and concentration of organic matter (POM, PC and PN).     

Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

Trace metal distribution in sediments of the Pearl River Estuary and the surrounding coastal area, South China

Surface sediments and sediment cores collected at the Pearl River Estuary (PRE) and its surrounding coastal area were analysed for total metal concentrations, chemical partitioning, and Pb isotopic compositions. The distribution of Cu, Cr, Pb, and Zn demonstrated a typical diffusion pattern from the land to the direction of the sea. Two hotspots of trace metal contamination were located at the mixed zone between freshwater and marine waters. The enrichment of metals in the sediments could be attributed to the deposition of the dissolved and particulate trace metals in the water column at the estuarine area. The similar Pb isotopic signatures of the sediments at the PRE and its surrounding coastal area offered strong evidence that the PRE was a major source of trace metals to the adjacent coastal area. Slightly lower (206)Pb/(207)Pb ratios in the coastal sediments may indicate other inputs of Pb in addition to the PRE sources, including the inputs from Hong Kong and other parts of the region.     

Dry deposition (downward, upward) concentration study of particulates and heavy metals during daytime, nighttime period at the traffic sampling site of Sha-Lu, Taiwan

Downward, upward dry deposition fluxes and total suspended particulate of particulate heavy metals (Fe, Pb, Zn, Cu, Mg and Mn) were measured in daytime and nighttime period in Sha-Lu, a small city in the central Taiwan during summer period of 2003. The results showed that the total suspended particulate concentrations of particulate mass in the daytime period (averaged 996.2 g/m3) were higher than in nighttime period (averaged 560.7 g/m3). And the downward dry deposition fluxes (averaged 54.07 g/m2s) were about two times as that of upward dry deposition fluxes (averaged 26.48 g/m2s) in the daytime period. Furthermore, the average downward dry deposition fluxes (averaged 26.22 g/m2s) were also about two times as that of upward dry deposition fluxes (averaged 12.11 g/m2s) in the nighttime period. In addition, the average downward dry deposition fluxes are greater than the upward dry deposition fluxes for all the heavy metals in either daytime or nighttime period. The proposed reasons are that the wind speed and concentration difference for daytime and nighttime period lead to these results at the traffic sampling site of central Taiwan. In addition, the deposition velocity for mass, heavy metals (Fe, Pb, Zn, Cu, Mg and Mn) during daytime and nighttime period were also calculated. The average daytime dry deposition velocity for downward particulate mass, upward particulate mass, Fe, Pb, Zn, Cu, Mg and Mn were 5.56, 2.66, 1.71, 0.18, 1.06, 0.24, 0.47 and 0.11 (cm/s), respectively. And the average nighttime dry deposition velocity for downward particulate mass, upward particulate mass, Fe, Pb, Zn, Cu, Mg and Mn were 4.70, 2.11, 1.66, 0.18, 0.86, 0.23, 0.32 and 0.07 (cm/s), respectively at traffic sampling site of central Taiwan.     

Trace metal enrichments in core sediments in Muthupet mangroves, SE coast of India: application of acid leachable technique

Core sediments from Mullipallam Creek of Muthupet mangroves on the southeast coast of India were analyzed for texture, CaCO(3), organic carbon, sulfur and acid leachable trace metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd). Textural analysis reveals a predominance of mud while CaCO(3) indicates dissolution in the upper half of the core, and reprecipitation of carbonates in reduction zones. Trace metals are diagenetically modified and anthropogenic processes control Pb and, to some extent, Ni, Zn and Fe. A distinct event is identified at 90 cm suggesting a change in deposition. Strong relationship of trace metals with Fe indicates that they are associated with Fe-oxyhydroxides. The role of carbonates in absorbing trace metals is evident from their positive relationship with trace metals. Comparison of acid leachable trace metals indicates increase in concentrations in the study area and the sediments act as a sink for trace metals contributed from multiple sources.     

Assessment of acid leachable trace metals in sediment cores from River Uppanar, Cuddalore, Southeast coast of India

An acid leachable technique is employed in core samples (C1, C2 and C3) to develop a baseline data on the sediment quality for trace metals of River Uppanar, Cuddalore, southeast coast of India. Acid leachable metals (Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn and Cd) indicate peak values at the sulphidic phase and enrichment of metals in the surface layers are due to the anthropogenic activities. Association of trace metals with Fe, Mn indicates their adsorption onto Fe-Mn oxyhydroxides and their correlation with S indicate that they are precipitated as metal sulphides. Factor analysis identified three possible types of geochemical associations and the supremacy of trace metals along with Fe, Mn, S and mud supports their geochemical associations. Factor analysis also signifies that anthropogenic activities have affected both the estuarine and fresh water regions of River Uppanar.     

Microscale investigations of the fate of heavy metals associated to iron-bearing particles in a highly polluted stream

As it flows through a dense steelmaking area, the Fensch River does transport iron-rich particles and colloids, displaying high contents in metallic contaminants (Zn, Cr, Pb, Cu, Ni, and As). Chemical analysis using inductively coupled plasma mass spectrometry (ICP-MS) was carried out on three compartments—waters, suspended materials, and sediments—along the river linear. The variations of metallic trace element concentrations along the river were shown to be partially related to external inputs (industrial and domestic wastewaters and urban surfaces leaching). However, some discrepancies of element partitioning were evidenced. Pb, Cu, and Mn tend to concentrate in suspended particulate and in dissolved fraction, while Cr and As follow the trend of Fe and concentrate within sediments of the most downstream station, just before the junction with Moselle waters. Zn appears strongly associated to iron-rich particles, resulting in a decrease of its concentration in waters for the last station. Along the Fensch linear, the variation of metal partitioning between water and particulate phases is accompanied with strong modifications of the nature and mineralogy of iron-rich particles, as evidenced by microanalyses using electron and X-ray beams. The combination of bulk analyses using ICP-MS and microanalyses applied to the three compartments allowed us to propose a three-step process “settling–weathering–resuspension” to explain Zn partitioning.     

Twentieth century overview of heavy metals in the Galician Rias (NW Iberian Peninsula)

The 18 Galician Rias, comprising 25% of the Iberian Peninsula coastline, form a unique system within the European continental Atlantic coast and provide a useful reference area for studies of metals. These rias are sensitive to anthropogenic influence due to the socioeconomic importance generated in these areas by industry, aquaculture, port activities, fishing, tourism and, accordingly, several islands lying within close proximity to the rias have recently been declared natural parks. Aquaculture in the Galician Rias is a growth industry and in 2000 the rias supported 3386 mussel rafts producing 2.5 x 10(8) kg year(-1), i.e. 40% of European Union total seafood production. The Galician Rias are partially stratified estuaries with positive residual circulation with fresh (runoff lower than 100 m3 s(-1) and salt water mixing inside the basins. This behaviour has direct consequences on metal fluxes whereby the rias behave as a barrier and accumulate metals in the sediments. Metals tend to deposit close to point sources and remobilization occurs inside the ria, leading to a seaward decrease in metal concentration. With the exception of the Ulla (Arosa Ria) and Eume (Ares-Betanzos Ria) head rivers and the Lagares river (Vigo Ria) the available data suggest that riverine freshwater inputs are not the main source of contamination. Metal studies reported in the literature mainly relate to Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn, and to a lesser extent Hg and Sn. Studies of other harmful metals such as Ag, Se and As are notably lacking. In addition, the studies have been localized and mainly restricted to the surface sediment. Data of heavy metals in the dissolved phase, suspended particulate matter and biota is scarce in the mainstream literature and should be considered in the future research. From the entire Galician coast, data from seven rias of socio-economic importance form the bulk of the published work. There is an urgent need to standardize procedures, employ 'clean' procedures to avoid contamination of samples and regular assessment of analytical accuracy with CRMs in order that results can be compared among the scientific community and produce reliable results. The continuation of coastal environmental studies requires an enlargement of the sampling locations as well as systematic and periodic analysis of known pollution sources in order to decide whether coastal regeneration action is needed. Studies dedicated to metals in the water column are lacking and need more attention in future research. The majority of the available data correspond to the fluvial front (30%) at ria head and, to a lesser extent, to the oceanic front (3%), under summer upwelling events. Current awareness of the rias suggests that they are not contaminated although there is some evidence of important localized anthropogenically induced enrichments at the outflow of the Lagares River (Pb, Zn), the San Simón inlet (Pb) and near to the harbor (Pb, Zn, Cu) in the Vigo Ria, the inner part (Cu, Zn, Hg, Pb) of the Pontevedra Ria, the Ulla River estuary (Cu, Cr, Mn, Ni; Zn) in the Arosa Ria, the inner zone (Cu, Pb, Zn) of the Coru?a Ria, the Ferrol Ria (Zn) and the Eume Estuary (Zn, Mn, Ni, Co) in the Ares-Betanzos Ria. In addition, TBT enrichment has been found along the Galician coast, being highest in the industrial bays (Vigo, Coru?a and Ferrol). Nevertheless, it is important to point out the lack of information concerning the relationship between metal concentrations in different fractions of sediments and/or water and their bioavailability and toxicity on biota in order to confirm metal contamination dangers. The present paper reviews all the information published on metals in the rias up to the year 2000 and takes a biogeochemical standpoint, i.e. metal presence in the ria reservoirs: water column, suspended particulate matter, sediments and biota, as well as the fluvial and oceanic frontiers.