Mytilus californianus as an indicator of heavy metals on the northwest coast of Baja California, Mexico.

Samples of Mytilus californianus were analyzed to determine the spatial and temporal distribution of Ag, Al, Cd, Cr, Cu, Mn, Pb and Zn concentrations on the northwest coast of Baja California and to compare the results with levels reported for California, USA. The samples were collected at eight sites from the US-Mexican border to San Quintín, BC (300 km south of the border) in February and July 1982 and 1994. During both years, north-south gradients in the concentration of Ag and Pb were observed, with the highest values close to the US-Mexican border (Ag = 0.60-1.54 and Pb = 0.21-2.89 micrograms g-1) and the lowest in the southern part of the study area (Ag = 0.05-0.10 and Pb = not detectable-0.03 microgram g-1). The Ag and Pb gradients suggest that their distributions are affected by anthropogenic activities close to the US-Mexican border. South-north gradients in the concentration of Cd (minimum = 0.59-2.16 and maximum = 2.61-12.93 micrograms g-1), for both 1982 and 1994, were observed. The geographic annual means of Pb for California (average of six stations along the entire state) were significantly higher than those of this study (average of the eight sampling sites) in 1982 and 1994. Cu in California was significantly greater than that of this study only in 1994. Cluster analyses on all metals indicate three similar geographic zones in 1982 and 1994, suggesting a relative consistency in the processes that determine the spatial variability of the concentration of some metals in M. californianus on the northwest coast of Baja California.     

Metal distributions and their fluxes at the coastal boundary of a semi-enclosed ria

Water column samples have been collected in the outer channel of the Ferrol Ria (NW Spain) during four occasions over a tidal cycle. The objective was to study the exchange of dissolved and particulate Cd, Cu, Pb and Zn and particulate Al, Fe and Si between the ria and the adjacent coastal waters. This study provides the first extensive dataset on dissolved and particulate metal concentrations in the water column of a Galician ria. Typical concentrations of dissolved Cd (96 ± 31 pM), Cu (8 ± 4 nM), Pb (270 ± 170 pM) and Zn (21 ± 10 nM) were similar than in other European Atlantic shelf and coastal waters. The fraction of metals in the particulate phase followed the trend: Pb > Cu Zn > Cd. The outgoing water from the ria was enriched in dissolved and particulate Cu, Pb and Zn compared with incoming waters, whereas Cd concentrations were similar for both waters. The suspended particulate matter was composed of a mixture of marine and continental material. The latter end-member was found to arise from the metal-rich ria bed sediments, which is diluted by the dominant metal-poor marine end-member. The net output flux of Cu from the channel is balanced by the freshwater inputs to the ria, and the net Zn flux gave a positive output to coastal waters. For Pb, the net flux to the coastal waters is less than that input from the rivers, as a result of its particle reactivity and deposition in sediments. On the contrary, a net input flux of dissolved Cd from coastal waters was observed, highlighting the oceanic source of this metal in the Galician rias. Results from the budget calculations are in agreement with the differential geochemical behavior of these elements in coastal waters.     

Trace metals in seawater and copepods in the ocean outfall area off the northern Taiwan coast

The distribution, partitioning and concentrations of trace metals (Cd, Cr, Cu, Fe, Mn, Pb and Zn) in seawater, including dissolved and particulate phases, and in copepods in the ocean outfall area off the northern coast of Taiwan were investigated. Normalization of metal concentrations to the background metal concentration to yield relative enrichment factors (EF), which were used to evaluate the contamination of dissolved and particulate trace metals in seawater around the ocean outfall. The EF results indicated that the outfall area was significantly contaminated by dissolved Fe and Zn, and by particulate Fe, Cr, Cu, Pb and Zn. In addition, most trace metals were chiefly in the particulate phase. The average percentage of total metal concentrations (dissolved plus particulate phases) bound by suspended particulate matter followed the sequence Al(95%) = Mn(95%) > Pb(88%) > Cu(86%) > Fe(72%) > Zn(32%) > Cr(17.5%) > Cd(3.4%). Therefore, metal contamination is better evaluated in solid phase than in the dissolved phase. The concentration ranges of trace metals in the copepods, Temora turbinata, Oncaea venusta and Euchaeta rimana, near the outfall were: Cd, 0.23-1.81 microg g(-1); Cr, 16.5-195 microg g(-1); Cu, 14-160 microg g(-1); Fe, 256-7255 microg g(-1); Mn, 5.5-80.8 microg g(-1); Pb, 2.6-56.2 microg g(-1); Zn, 132-3891 microg g(-1); and Al, 0.21-1.13%. Aluminum, and probably Fe, seemed to be the major elements in copepods. The concentrations of trace metals in copepods, especially Temora turbinata, near the outfall were generally higher than those obtained in the background station. The mean increase in bioconcentration factor of metals in copepods ranged from 4 to 7 and followed the sequence Al(6.4) > Cu(6.2) > Fe(6.0) > Zn(5.7) > Pb(5.6) > Cr(5.5) > Cd(5.1) > Mn(4.7). Therefore, marine copepods in the waters of northern Taiwan can accumulate trace metals over background concentrations and act as contamination indicators.     

Biomonitoring of trace metals using transplanted mussels, <Emphasis Type="Italic">Mytilus galloprovincialis</Emphasis>, in coastal areas around Ulsan and Onsan Bays,Korea

Mediterranean (blue) mussels (Mytilus galloprovincialis) collected from a reference site were transplanted to 15 stations in coastal areas around Ulsan and Onsan Bays, an extensively metal polluted area in Korean coastal waters, to assess metal contamination in the coastal oceans of Korea. During the biomonitoring periods (June 30 to July 20, 2003; 21 days), transplanted mussels, seawater, and particulate materials were collected for analysis of 15 metals (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Se, Sn, and Zn). Transplanted mussels showed metal enrichment compared to initial concentrations and spatial gradients consistent with dissolved and/or particulate metal concentrations in seawaters. Based on Q mode factor analysis, stations were clustered into three groups. The first group, located on Onsan Bay, showed high Ag, Cd, Cu, Hg, Pb, Sb and Zn enrichment, presumably arising from non-ferrous metal refineries and chemical industries in this area. The second group was located near the mouth of the Oehwang River and was enriched in Co from petrochemical industries. The third group comprised a site intermediate between Group 1 and Group 2, an isolated station with independent metal sources located in Jangsaengpo harbor, where a number of ship repairing and building companies operate, and a less contaminated station near a small fishing village. Metal accumulation rates (%·day^-1) in mussels were estimated to be between 8% (Cr) and 281% (Pb), based on accumulated metal concentrations over 21 days. The active biomonitoring technique using M. galloprovincialis demonstrated here is a useful monitoring method because it reflects the present status of seawaters; furthermore, physiological factors can be standardized, and bioavailable and time-integrated metal concentrations can be obtained. Furthermore, this method can be applied even in coastal seawaters so heavily contaminated that living organisms would not normally survive.     

Trace element concentrations in Coastal Hawaiian waters

The objective of this work is to characterize the concentrations of selected trace elements (V, Mn, Ni, Fe, Co, Cu, Zn, Se, As, Mo, Cd, Pb, U) in diverse nearshore (50 m), coastal (1.5 km) and seawater well environments within the Hawaiian Archipelago using robust analytical methods that are appropriate for metals analyses in seawater. The sampling sites include locations having varying type, quality and quantity of freshwater input. In most coastal and nearshore cases, the trace element concentrations approximate values characteristic of offshore waters. Concentrations of trace elements in coastal waters that were enriched through either urban or agricultural inputs declined sharply within a short distance from shore; this is taken to indicate the predominant importance of physical mixing/advective processes along with particle scavenging in these dynamic areas. Trace element levels in seawater wells did not evidence any concentration trends consistent with island age suggesting little or no impact of island weathering on metal concentrations; concentration differences among wells appeared to be more dependent on well depth, redox conditions, and/or salinity. Sampling also targeted nearshore locales where ciguatera fish poisoning is prominent because of suggested linkages between trace element concentrations and aberrant dinoflagellate growth. Nearshore stations where ciguatera is prevalent failed to show clearly different trace element levels except for two prominent locales which showed elevated Mn and Fe concentrations.     

THE CONCENTRATION AND DISTRIBUTION OF TRACE METALS IN THE SURFACE WATERS OF XIAMEN HARBOR

Dissolved, weakly and strongly bound particulates Cu, Pb, Zn, Cd, Co, Ni and Fe have been measured in the surface water sampled from eleven stations in Xiamen Harbor by clean laboratory methods and GFAAS. The average concentrations found in dissolved fractions are Cu: 0.41±0.12; Pb: 0.014±0.008; Zn: 0.084±0.043; Cd: 0.022±0.004; Co: 0.009±0.004; Ni: 0.15±0.02; and Fe: 0.15± 0.02 μg/kg, which make up 62%, 6%, 12%, 85%, 5%, 25% and <1% of the total metals in the surface water respectively. The results are mucn lower than those reported previously in the coastal waters of China. Industrial sources of trace metal contamination are likely responsible for the distribution of trace metals.     

Metal uptake in zebrafish embryo-larvae exposed to metal-contaminated sediments

Heavy metal contamination in coastal and estuarine regions of inner Tolo Harbour, as well as some river and nullah areas, is one of the major water-pollution issues in Hong Kong. Zebrafish (Danio rerio) embryo-larvae was used to study metal uptake from coastal sediments collected from Fo Tan River (industrial area, Sha Tin), Tai Po River (residential area, Tai Po) and Wu Kai Sa (rural area, Tolo Harbour). Exposure experiments (7-days) were carried out using different concentrations (0.1%, 0.5%, 1% and 0% as control) of sediments that were added to aquaria containing fertilized zebrafish eggs until they hatched to become larvae. Uptake of heavy metals (Cd, Cu, Pb and Zn) was determined in whole embryo-larvae following exposure. Significant levels of Cd, Cu, Pb and Zn were detected in the embryo-larvae exposed to sediments from Tai Po River. However, significant levels of only Cd and Cu were found in embryo-larvae exposed to sediments from Fo Tan River.     

Eelgrass (Zostera marina L.) as an indicator organism of trace metals in the Limfjord,Denmark

The concentrations of Pb, Cu, Cd and Zn were determined in above- and belowground parts of eelgrass (Zostera marina L.) at forty stations in a shallow, brackish water area (the Limfjord, Denmark). The concentrations of the trace metals were significantly elevated near the cities of Aalborg (Pb, Cu) and Struer (Cd). Trace metal concentrations in above and belowground parts of eelgrass were log-normal distributed and the concentrations of Cd, Cu and Zn in aboveground parts were significantly higher than in belowground parts. Furthermore, a significant correlation between trace metal concentrations in above- and belowground parts was found. The background level of trace metal concentrations in eelgrass in the Limfjord was estimated.The application of eelgrass as a monitoring organism is discussed; it is suggested that the concentration of some trace metals in above- and belowground parts of eelgrass may be used as a measure of the bioavailable fraction of these trace metals in ambient and interstitial water (sediment), respectively.     

胶州湾水生系统中Pb、Zn 的分布特征及其在生物体中的浓缩

利用在胶州湾采集的47组同站位多介质样品,进行了痕量金属Pb、Zn及其它环境因子的化学成分测试,讨论了胶州湾水-沉积物-生物系统中Pb、Zn的生物地球化学总体特征及其在各介质平面上的分布,揭示了胶州湾水-沉积物-生物系统对陆源物质输入的响应.垂向上表层沉积物是Pb、Zn组分的富集带,该系统中的生物相对于其所处水环境具有显著的富集作用,生物体中Pb、Zn生物浓缩系数分别为36、935;横向上,Pb、Zn在底层水和沉积物介质中的分布主要受控于河口,即高值区分布于胶州湾的各个主要河口区,特别是在沉积物中金属组分浓度的高值区主要集中分布于胶州湾的东部.而孔隙水中Pb、Zn的高值主要分布于水交替较弱的海域,如红岛前缘.但生物体中的痕量金属组分化学场空间分布规律与上述各介质的化学场均不吻合,亦即是生物体中痕量金属组分的浓度与其所处环境中的同名金属组分浓度无关.作者认为,生物对痕量金属组分的富集并不简单地取决于它所处环境介质中同名金属组分的总量,而存在形态上的选择性.通过回归分析揭示了孔隙水对生物体中Pb、Zn的富集贡献较大.     

Dissolved Cu, Pb, Zn and Cd in the South China Sea surface waters

The understanding of the distribution of trace heavy metals in the world ocean has greatlyimProved in the past decades. But most of the data are of vertical profiles of certain stations(Bruland, l980; Paul et al., l992; RObert et al., l990) and large--scale study of temporaland spatial variability of trace heaVy metals in the ocean is rather few. In fact, affected by ver-tical mixing by upwelling or convection, biogenic removal, atmospheric fallout and continentalinput frorn rivers, the dist…     

The accumulation of Zn, Se, Cd, and Pb and physiological condition of Anadara trapezia transplanted to a contamination gradient in Lake Macquarie, New South Wales, Australia

The benthic bivalve, Anadara trapezia, was collected from a 'clean' reference site and transplanted along a suspected trace metal contamination gradient in Lake Macquarie, NSW. At monthly intervals, Zn, Se, Cd and Pb concentrations were measured in the surficial sediments and whole tissues of the cockle as well as their physiological condition (Scope for Growth). Zinc, Cd and Pb concentrations in sediments decreased together, southward, with the highest concentrations in the Cockle Bay area, suggesting that this is the main source of contamination. Zinc, Cd and Pb concentrations were near or above [ANZECC/ARMCANZ, 2000. National water quality management strategy paper 4. Australian and New Zealand Guidelines for Fresh and Marine Water Quality, Australian and New Zealand Conservation Council and Agriculture and Resource Management Council of Australia and New Zealand. pp. 3.5.-1-3.5-10] sediment quality guidelines at Cockle Creek, Warners Bay and Koorooa Bay. Significant differences in trace metal concentrations could not be attributed to grain size or Fe concentration differences. Se concentrations were highest in fine grain Fe rich sediments of Whiteheads Lagoon, and likely to be associated with power generation operations. Trace metal concentrations did not vary significantly over time. Zinc, Cd and Pb concentrations in the tissues of A. trapezia followed a similar pattern to that of sediments. Zinc and Pb concentrations in cockles and sediments were highly correlated, indicating significant exposure-dose relationships. Selenium concentrations in the tissues of A. trapezia were higher after transplantation to the lake, however, Se concentrations were similar in all transplanted cockles, indicating that Se in contaminated sediments is not the major source of Se to organisms. There was a decline in the physiological condition of A. trapezia transplanted to Lake Macquarie after a 90-day-period with marked differences in clearance rates and respiration rates at some locations and absorption efficiencies at all locations. The mean Scope for Growth value at the most contaminated location, Cockle Bay, was markedly lower than at other locations. A significant Zn exposure-dose response relationship indicates that Zn bioaccumulation is occurring in response to sediment contamination. A significant Cd exposure-response relationship indicates that Cd may be influencing the health of cockles. Significant Pb exposure-dose, exposure-response and dose-response relationships indicate that Pb probably is affecting the health of cockles in Lake Macquarie. Therefore, Zn, Cd and Pb concentrations in sediments are likely to be affecting the health of cockles in Lake Macquarie.     

Distribution of metal concentrations in sediments of the coastal zone of the Gulf of Riga and open part of the Baltic Sea

The comparison of spatial and temporal distribution of Hg, Cd, Pb, Cu, Ni, Zn, Mn and Fe concentrations in sediments from the Gulf of Riga and open Baltic Sea along the coastal zone is presented for the first time. There were considerable differences in Pb, Zn, Mn and Fe levels in sediment at various stations of the Gulf of Riga. A significant difference of Cd, Pb, Cu, Ni, Zn levels was found in sediments of various stations in the open Baltic coast. The amount of Cd, Pb, Cu, Ni, Zn and Fe levels also differed significantly in the sediments of the Gulf of Riga in different years. A considerable yearly difference in amount of Hg, Cd, Pb, Cu, Ni and Mn levels was found in sediments in the open Baltic coast. The essential highest values of Pb and Zn in coastal sediments of the open Baltic Sea are stated in comparison with the Gulf of Riga. The concentrations of other metals have only a tendency to be higher in coastal sediments of the open Baltic Sea in comparison with the Gulf of Riga. Natural and anthropogenic factors were proved to play an important role in determining resultant metals concentrations in the regions.     

Trace metal (Cd,Cu, Ni and Pb) cycling in the upper water column near the shelf edge of the European continental margin (Celtic Sea)

This study investigates the relative importance of processes that affect trace metal (TM) cycling in the upper water column at the shelf edge of the Celtic Sea on the western European continental margin. The examined processes include external inputs (by atmosphere and river), physical factors (upwelling, winter mixing and water mass advection) and biological processes (in situ uptake, regeneration and export to deep waters). The concentrations of dissolved Cd, Cu, Ni and Pb were measured with this aim in January 1994 and June 1995 at vertical stations across slope, including stations with upwelling, and in the surface waters along the Celtic Sea shelf. Additionally, deep sea (from sediment trap data) and atmospheric fluxes were estimated. The metal profiles over the slope off the Celtic Sea are quite similar to open ocean profiles already described in the northeast Atlantic, and the concentrations in surface waters are only slightly enriched compared to the nearby open ocean (1.2–1.3× for Cd and Ni). The external sources to the system appear to be of weak influence: the fluvial input is locally strong at the coast and then “diluted” along the large continental shelf; the atmospheric deposition is not significant at the annual scale in comparison to the metal content in the upper waters of the shelf edge (at least for Cd, Ni and Cu). In the upwelling zone, a significant increase in concentrations was observed in the summer surface mixed layer (×2 for nitrate and Cd and ×1.5 for Ni) in comparison to the non-upwelling zone. In winter, concentrations of bioreactive metals increased significantly in the surface waters in comparison to the low summer levels (×5 for nitrate and Cd). Our results suggest that upwelling and winter mixing act as regenerated sources that lead to the resupply of the bioreactive elements above the permanent thermocline with a low export to deeper waters. The tracing of the Mediterranean intermediate waters (MIW) from Gibraltar to the studied area shows indeed that its elemental content at the Celtic shelf edge is mainly due to the conservative mixing of the three “end-member” component waters which are thought to make up the MIW. The remineralization of organic matter within this water mass during its transport to the north would contribute only 20% of the nutrients and Cd concentrations recorded at the Celtic Sea shelf edge. According to the correlation found with nutrients in the 10–200-m layer, dissolved Pb would also be subjected to biological uptake and regeneration within the seasonal thermocline. Particulate scavenging removal of Pb would take place below the permanent thermocline throughout the water column.     

Trace metal concentrations in the Ross Sea and their relationship with nutrients and phytoplankton growth

Dissolved and particulate trace metal concentrations (dissolved Fe, Zn, Cd, Co, Cu and Ni; particulate Fe, Mn and Al) were measured along two transects in the Ross Sea during austral summer of 1990. Total Fe concentrations in southern Ross Sea and inshore waters were elevated >3.5 times that of northern waters. Dissolved Zn, Cd and Co concentrations were lower by factors of 4.5, 3.5 and 1.6 in southern surface waters relative to northern waters. Dissolved Cu and Ni concentrations were similar in both areas. Elevated Fe concentrations coincided with areas of increased productivity, phytoplankton biomass and nutrient drawdown, indicating that Fe is an important factor controlling the location of phytoplankton blooms in the Ross Sea. Particulate concentrations of Fe, Mn and Al indicate two possible sources of iron to the Ross Sea, resuspension of continental shelf sediments and iron incorporated in annual sea ice and released with meltwaters.     

Mobilization of metals from riverine suspended matter in seawater

Suspended matter from rivers in the Russian Far East was leached by seawater to assess the extent of Zn, Cd, Pb, and Cu release from the land-derived solids to estuarine and coastal waters. The concentration of solids in the leaching experiments was 0.25 g/l. The suspended matter used varied in metal content from background levels to heavily contaminated.The concentration of Zn, Cd, Pb, and Cu in the leaching solution after 1, 4, 24, 48, and 96 h was determined by anodic stripping voltammetry. Measurable Cd was transferred from river suspended matter to seawater with both background and elevated Cd concentrations, though the amount of Cd released was different. The increase in Zn and Pb in solution was observed only at the enriched concentration of metals in the suspended solids. The Cu transfer into solution was more pronounced from material with elevated Cu concentration, but the amount of degradable organic matter in the solid phase was more important.The losses of metals from the riverine solids varied from 60% to 80% of total concentration for Cd to negligible for Pb, independent of contamination. The Zn loss depended on the initial concentration in the solids and decreased from 11–16% for the heavily contaminated suspended matter to 3–8% for the moderately enriched ones and to negligible for the pristine solids. Cu loss varied from 1% to 30% of total content, with no clear dependence on concentration in the suspended matter.The significance of additional input of dissolved metals to estuarine and coastal waters from remobilization was assessed by comparison with the initial concentration of dissolved metals in river water. Such experiments could be used to assess the water quality impact of atmospheric fallout of contaminated solids and storm drainage from the urbanized areas, in addition to river suspended matter studies.     

Trends of trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) distributions at the oxic-anoxic interface and in sulfidic water of the Drammensfjord

Anoxic sulfidic waters provide important media for studying the effect of reducing conditions on the cycling of trace metals. In 1987–1988, dissolved and particulate trace metal (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) concentrations were determined in the water column of the anoxic Drammensfjord basins, southeastern Norway. The iminodiacetic acid type chelating resin (Chelex 100) was used for the preconcentration of trace metals. The trace metal concentrations were determined using atomic absorption spectrophotometry (AAS), differential pulse polarography (DPP), and differential pulse-anodic stripping voltammetry (DP-ASV).It was observed that the trace metals Mn and Fe were actively involved in the processes of redox cycling (oxidationreduction and precipitation-dissolution) at the O₂/H₂S interface. The dissolved concentrations of Mn, Fe and Co showed maxima just below the O₂/H₂S interface. The seasonal enhancement in the maxima of both dissolved and particulate Mn and Fe at the redox cline is mainly governed by the downward movement of water which carries oxygen. An association of Co with the Mn cycle was observed, while the total dissolved Ni was decreased by only 10–35% in the anoxic waters. The dissolved concentrations of Cu, Zn, Pb and, to a lesser extent, Cd decreased in the anoxic zone.     

南海表层水中的溶解态Cu,Pb, Zn,Cd

于1998年“南海海洋环境调查”外业工作期间在南海的各个站位,按照严格的防沾污措施采集了106个表层海水样品.采用溶剂萃取-石墨炉原子吸收法对样品中的痕量重金属Cu,Pb,Zn,Cd含量进行了分析测试.测得各重金属的平均值如下:Cu 0.100 μg/dm3,Pb 0.060μg/dm3,Zn 0.086 μg/dm3,Cd 0.007μg/dm3,接近世界大洋水的浓度水平.各重金属的空间分布呈现出海区周边含量高于中央,浓度有自近岸向远海逐渐减小的趋势.相关分析的结果表明各重金属夏季相关性优于冬季,Cu与Cd存在良好的正相关关系,并且首次在南海表层水发现Cu,Cd与营养盐的相关关系.将重金属浓度值作数理统计分析,得到它们在南海的基线值.     

Level and fate of heavy metals in the Changjiang estuary and its adjacent waters

Dissolved concentrations of Cu, Pb, Zn, and Cd were measured in the Changjiang estuary and its adjacent waters. The results indicate that the ranges of dissolved heavy metals in the studied waters are as follows: Cu = 1.0−6.9 μg/L, Pb = 0.10−0.39 μg/L, Zn = 3.2−9.1 μg/L, and Cd = 0.011−0.049 μg/L. The behavior of the dissolved Cu was essentially conservative, but a high scatter was observed for the high salinity samples, and it is the same with Zn and Pb. The overall concentrations of dissolved Cd increase with the salinity. There were no differences between the surface, middle, and bottom layer for Cu, Pb, Zn, and Cd. Seasonal changes of their averages were not obvious on the whole. River discharges, sedimentary dynamics, and biological processes might determine the profiles of heavy metals. The text was submitted by the authors in English.     

Sources of Cd, Cu, Ni and Zn in Portuguese coastal waters

In order to identify the major sources of trace metals (TM) in the Portuguese coastal waters, 58 surface water samples were collected during September 1988. The area sampled extended from the Tagus Estuary (down to a salinity of 25) to cape Ste Marie on the southern coast of Portugal. Dissolved metal concentrations in the fully marine waters ranged from 30 to 250 pM for Cd, 0.7–15 nM for Cu, 0.9–20 nM for Zn and 1.8–4.5 nM for Ni. Within the Tagus Estuary (salinity 25), concentrations increased to 3400 pM for Cd, 26 nM for Cu, 14 nM for Ni and 230 nM for Zn.The large-scale distribution of these metals is dominated by two strong continental sources, both probably linked to the exploitation of pyrite ores. In the Tagus Estuary, TM enrichments can be mostly attributed to a pyrite roasting plant located on the shore in front of Lisbon. Concerning the south Portuguese shelf waters, several hypotheses are proposed to explain their elevated metal concentrations. We particularly discussed the likely influence of the Tinto/Odiel rivers located 100 km eastward, an influence well known in the shelf waters of the Gulf of Cadiz. These rivers are extremely metal-rich because of acid mine tailings originating from their catchment. Between these two regions, upwelling of relatively metal-poor water largely contributes to the dilution of the continental inputs. Indeed, water exchanges on the shelf linked to the upwelling involve water fluxes 500 times higher than the Tagus River flow, and renew the coastal waters that are thus cleaned from terrestrial contamination. Contrary to many other upwelling systems in non-contaminated areas, the Portuguese upwelling does not act as a source of trace-metal enrichment of the continental margin waters.     

Metal and metalloid concentrations in the giant squid Architeuthis dux from Iberian waters

This study investigated 14 trace elements (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V and Zn) in the tissues of the giant squid Architeuthis dux from the Mediterranean and Atlantic Spanish waters. As for other families of cephalopods, the digestive gland and the branchial hearts of Architeuthis showed the highest concentrations of Ag, Cd, Co, Cu, Fe, Ni, Se, V and Zn, highlighting their major role in the bioaccumulation and detoxification processes. With the exception of Hg, the muscles showed relatively low trace element concentrations. Nevertheless, this tissue contained the main proportion of the total As, Cr, Hg, Mn, Ni, and Zn body burden because muscles represent the main proportion of the squid mass. These findings suggest that the metal metabolism is overall the same as other cephalopod families from neritic waters. In females, Zn concentrations increased in the digestive gland with the squid's weight likely reflecting physiological changes during sexual maturation. Comparing the trace element concentrations in the tissues of Architeuthis, higher Ag, Cu, Hg and Zn concentrations in the squid from the Mediterranean reflected different exposure conditions. In comparison to other meso-pelagic squids from the Bay of Biscay, Cd concentrations recorded in the digestive gland suggest that Architeuthis might feed on more contaminated prey or that it displays a longer life span that other cephalopods.