Marine mammals from northeast Atlantic: relationship between their trophic status as determined by delta13C and delta15N measurements and their trace metal concentrations

The relationship between trophic position through delta13C and delta15N and trace metal concentrations (Zn, Cd, Cu and Hg) was investigated in the tissues of six marine mammal species from the Northeast Atlantic: striped dolphin Stenella coeruleoalba, common dolphin, Delphinus delphis, Atlantic white-sided dolphin Lagenorhynchus acutus, harbour porpoise Phocoena phocoena, white beaked-dolphin Lagenorhynchus albirostris, grey seal Halichoerus grypus stranded on French Channel and Irish coasts. White-beaked dolphins, harbour porpoises, white-sided dolphins, common and striped dolphins display the same relative and decreasing trophic position, as measured by delta15N values, along both the Irish and French channel coasts, reflecting conservative trophic habits between these two places. Hepatic and renal Cd concentrations were significantly correlated to muscle delta13C and delta15N values while Hg, Zn and Cu did not. These results suggest that Cd accumulation is partly linked to the diet while other factors such as age or body condition might explain Hg, Zn or Cu variability in marine mammals. Combined stable isotope and trace metal analyses appear to be useful tools for the study of marine mammal ecology.     

Using trace elements in skin to discriminate the populations of minke whales in southern hemisphere

Concentrations of 12 trace elements (V, Cr, Mn, Cu, Zn, Se, Rb, Sr, Cd, Cs, Ba, and Hg) were determined in liver and skin tissues of minke whales from various regions within the Antarctic Ocean. Cd concentrations in livers of southern minke whale were apparently higher than those in cetaceans from other regions, while Hg concentrations were lower. There were significant positive correlations between body length and concentrations of Cd and Hg in the liver. The concentrations of all trace elements in the skin were lower than those in other cetaceans reported previously. Significant positive correlations between liver and skin were found for Cr, Mn, Cu, Zn, Rb, Cd, and Cs, implying that the concentrations of these trace elements in the skin reflect those of internal organs. Large interannual variation of the accumulation pattern of trace elements in the skin was observed for the southern minke whales from Area V. There were significant differences in the skin element concentrations among Areas III, IV, and V, especially for males. Also, discriminant analysis between geographically two different groups collected during 1995/1996 austral summer season, based on the concentrations of trace elements in the skin, allowed for a correct classification of 90% of these minke whales. These results suggest that measurement of trace elements in skin samples could provide valuable information on the status of contamination and possible geographic differences in the accumulation levels in southern minke whales.     

Trace element bioaccumulation in reef fish from New Caledonia: Influence of trophic groups and risk assessment for consumers

Fourteen trace elements (Ag, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Se, V, and Zn) were analyzed in livers and muscles from 22 fish species from the New Caledonia lagoon, which is subjected to important chemical inputs due to intense land-based mining activities (New Caledonia is the third largest world producer of Ni). The results of this baseline research indicated that livers generally concentrated trace elements to a greater extent than muscles. Nevertheless, the overall trace element concentrations in both tissues were barely above the levels reported in fish and thus contamination at the local scale was poorly discriminated. Although these levels were low, preliminary risk assessment from a global health standpoint suggests that As would be an element potentially leading to exposure of concern for fish consumers. Based on the trace element concentrations in livers and the fish trophic preferences, some trends have been observed among trophic groups: Ag, Cu, Fe, Hg, and Zn concentrations were generally higher in liver of fish with the highest trophic position whereas Cd concentrations were lower in these groups. The use of the leopard coral grouper Plectropomus leopardus as a resident top predator allowed determining the geographical variations in contamination levels with significant differences for six out of the fourteen elements investigated. The sampling sites influenced by anthropogenic inputs were revealed by high Ag, Cd, Cu, Hg, and Pb concentrations. Such geographic differences also applied to Zn but surprisingly not for the typical elements associated with Ni mining, i.e., Co, Cr, Mn and Ni.     

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.     

Trace metal levels in fish and crustacea from Northeastern Mediterranean coastal waters

Some fish and crustacea caught near the northeastern Mediterranean coast of Turkey between 1977 and 1980 have been analysed by the AAS technique for their H Hg, Cd, Pb, Zn, Cu, Fe, Ni, Cr and Mn contents. In the crustacea Portunus pelagicus (crab) and Penaeus keratherus (shrimp), the two essential elements Zn and Cu, showed a linear correlation. Among the bony fish, Upeneus moluccensis (gold band goat fish), a member of the Mullidae family, and Portunus pelagicus showed a much greater tendency to accumulate Hg than other species. Although Cr concentrations in the sediments of the area studied were high, Cr levels in the organisms studied were found to be relatively low. The highly toxic metals Hg, Cd and Pb were found to be present in concentrations lower than those reported from other areas of the Mediterranean.     

Multivariate geochemical investigation of trace metal pollution in Kuwait marine sediments

Three multivariate procedures (cluster analysis, discrimination and classification) were used to identify and characterize various types of marine sediments in Kuwait. Samples from 201 offshore locations were first clustered into five types of sediments with different metal concentrations (Ag, Cd, Cr, Cu, Fe, Mn, Ni, Pb, V, Zn and Hg) and sedimentological characteristics (% TOC, carbonate, mean grain size and % size fraction < 63 μ). Discriminant functions were then developed in terms of trace metal concentrations to describe mathematically differences between the various sediment types. A classification procedure was also used to calculate the probability that each of 186 additional samples from coastal areas adjacent to suspected point sources of pollution may belong to each of the five sediment types. This analysis identified a sixth type of sediment dominating the area inside and near the entrance of Shuwaikh Port. Characterized by elevated levels of Ag, Cd, Cu, Hg, Pb and Zn, this type indicated the presence of a high level of metal pollution in the area.     

Concentrations of trace metals in the tissues of long-beaked common dolphins (<Emphasis Type="Italic">Delphinus capensis</Emphasis>) in the East Sea,Korea

Concentrations of trace metals (As, Cd, Cr, Cu, Pb, Hg, Se, and Zn) were determined in the livers, kidneys, muscles, intestines, and hearts of twelve long-beaked common dolphins (Delphinus capensis) from the East Sea, Korea, in 2006. All specimens were entangled in various commercial fishing nets or traps and as such are recorded as by-catch. The concentrations of Cu, Hg, Se, and Zn were much higher in the liver than in the kidney, muscle, intestine, or heart. Trace metals that accumulated in the liver were, in descending order: Zn > Hg > Cd > Se > Cu > As > Cr > Pb. In contrast, the concentration of Cd was higher in the kidney than in any other organs. The trace metals accumulated in the kidney were, in descending order: Cd > Zn > Cu > Hg > Se > As > Pb > Cr. No significant differences were found in the concentrations of As, Cr, or Pb in all the tissues examined.     

Trace metals and hydrocarbons in sediments from the Southampton water region,with particular reference to the influence of oil refinery effluent

The concentrations of a number of trace metals (Co, Ni, Cu, Zn, Ag, Cd and Hg) have been determined in sediments from cores collected in the Southampton Water region. Measurements of total hydrocarbons were also made on several of the cores. Markedly elevated concentrations of copper, up to 362 μg/g dry wt, were found in sediments which were collected close to the discharge points of oil refinery outfalls and which also showed concentrations of total hydrocarbons considerably greater than the background levels for the estuary. The results of selective chemical extractions showed that much of the copper was present in the non-lattice fraction of the sediment. Although the concentrations of Co, Ni, Zn and Cd were significantly correlated with those of copper in the core showing the highest concentrations of this element, these metals were not enhanced in comparison with the levels found in several other parts of the estuary. Variations in concentrations of metals in sediments throughout the estuary were not correlated with differences in organic carbon content.     

Natural and anthropogenic sources of Hg,Cd, Pb,Cu and Zn in seawater and sediment of Mljet National Park,Croatia

Distributions of Hg, Cd, Pb, Cu and Zn in seawater and sediment from Mljet National Park, Adriatic Sea are presented for the first time. Natural and anthropogenic factors play an important role in determining resultant trace metals' concentrations in the region. We place particular emphasis on the saline “lakes” of Malo Jezero and Veliko Jezero, which have restricted flows of seawater. In Malo Jezero lake, fresh karstic spring water generated by flooding, and weathering of dolomites are the main sources of naturally elevated Cd, Pb and Zn concentrations (20.7 ± 1.6, 289 ± 19, 1260 ± 0.08 ng L^?1, respectively); anthropogenic input is negligible. In Veliko Jezero lake enhanced Cu and Zn contents originate from anthropogenic input (tourism and agriculture). Distributions of the Pb and Zn in the water columns of both lakes are influenced by natural aragonite precipitation and sedimentation. Exceptionally high total Hg concentrations of 24.2 and 33.7 ng L^?1 in the water column of Malo Jezero, sampled during periods of high rainfall associated with strong eastern winds, suggest an airborne input. Total Hg concentrations in waters of both lakes are elevated because of inefficient mixing. Two different metal distribution patterns exist in the sediment columns. First, Hg, Pb, Cu and Zn show elevated concentrations in recent sediments due to anthropogenic input. Second, Cd content increases with depth due to reprecipitation via a downward redox boundary shift.Described natural processes, as well as anthropogenic influence, enhance levels of trace metals. Careful study followed by suitable interpretation based on geochemical data were necessary to distinguish natural from anthropogenic sources.     

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.     

Feeding ecology of five commercial shark species of the Celtic Sea through stable isotope and trace metal analysis

In order to trace their feeding habits, stable carbon and nitrogen isotope ratios (delta15N and delta13C), as well as trace metal concentrations (Zn, Cd, Fe, Cu, Se and Hg) were analysed in the tissues of five commercial shark species from the Celtic Sea: the tope shark Galeorhinus galeus, the black-mouthed catshark Galeus melastomus, the starry smooth hound Mustelus asterias, the spiny dogfish Squalus acanthias and the lesser-spotted dogfish Scyliorhinus canicula. Our results were compared to previously described stomach contents and isotopic composition of potential preys. Isotopic ratio delta15N suggested that tope sharks fed at a higher trophic level (16.7 per thousand in the muscle) than the other species, reflecting its piscivorous diet. The lower values of spiny dogfish (11.6 per thousand in the muscle) might be explained, amongst other things, by either its migratory behaviour or its preference for preys from lower trophic levels. Cd and Hg were correlated with isotopic ratios delta13C and delta15N, and were shown to be diet-related whereas Zn, Fe and Cu seemed much more linked to species-specific metabolism. Although this multidisciplinary approach is revealed as a useful tool for the study of shark ecology, the lack of known trophic fractionation suggests that isotopic data be compared to traditional diet analyses.     

Trace element distributions in coastal waters along the US-Mexican boundary: relative contributions of natural processes vs. anthropogenic inputs

Trace element concentrations (Pb, Cd, Mn, Fe, and Zn) were measured along four surface water transects across the continental shelf off Baja California, to evaluate the magnitude of heavy metal contamination in the coastal waters along the US-Mexican boundary. These initial measurements of trace elements in Mexican neritic waters revealed offshore concentration gradients, with the highest levels in coastal waters with high salinities and nutrient concentrations. There were also longshore gradients, with lower concentrations in the southern locations. Although the relative enrichment of metals detected at nearshore stations along the US-Mexican border appeared to correspond to wastewater discharges in that area, these trace metal enhancements were found to be primarily associated with physical oceanographic processes (upwelling and advection), rather than anthropogenic inputs. This was demonstrated both by metal-nutrient correlations and multivariate statistical analyses. Mass balance calculations also indicated that about 1% of Cd, 9% of Zn, and 29% of Pb were from urban discharges within the area.     

Some peculiarities of the trace-metal distribution in Baltic waters and sediments

Between 1980 and 1984 extensive studies were carried out in the Baltic Sea on trace metals (Cd, Co, Cu, Fe, Hg, Mn, Ni, Pb and Zn) in water, suspended matter and sediments. The results enabled the influence of different factors on metal distribution patterns to be considered. The vertical profiles of dissolved and particulate metals in waters of the central deep basins reflect influences caused by oxygen deficiency and anoxic conditions in near-bottom water layers. Peculiarities at Station BY15 in the Gotland Deep included high dissolved Fe, Mn and Co concentrations and remarkable enrichment of Zn (0.64%), Cd (51 μg g⁻¹) and Cu (0.15%) in particulate matter from the anoxic zone. Manganese-rich particles were accumulated above this layer.In fine-grained soft sediments below anoxic deep waters, maximum contents of Cd, Cu and Zn were observed, relative to other coring sites, between Bothnian Bay and Lübeck Bight. The Hg content in sediments probably reflects the joint flocculation with organic matter. Land-based sources seem to play the leading part for maximum lead contents.     

Potential adverse effects of inorganic pollutants on clinical parameters of loggerhead sea turtles (Caretta caretta): Results from a nesting colony from Cape Verde,West Africa

A large number of nesting loggerhead sea turtles (n = 201) were sampled to establish the blood levels of 11 elements (Cu, Mn, Pb, Zn, Cd, Ni, Cr, As, Al, Hg, and Se). Almost all of the samples showed detectable levels of these 11 elements, and Zn and Se exhibited the highest concentrations (median values as high as 6.05 and 2.28 μg/g, respectively). The median concentrations of the most toxic compounds, As, Cd, Pb, and Hg, were relatively low (0.38, 0.24, 0.06, and 0.03 μg/g, respectively). We also determined the haematological and biochemical parameters in a subsample of 50 turtles to evaluate the potential effects of these contaminants on clinical parameters and found several associations. Our study reinforces the usefulness of blood for the monitoring of the levels of contaminating elements and their adverse effects on blood parameters in sea turtles.     

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.     

Elemental composition of zooplankton in the Kara Sea and the bays on the eastern side of Novaya Zemlya

The chemical composition of zooplankton in the Kara Sea Basin has been studied. Independent samplings of the open sea and the Blagopoluchie and Tsivol’ki bays of Novaya Zemlya testify to the similarity of the distribution pattern of all the studied elements. The chemical composition of samples is predominated by organic carbon (49.5 ± 4.8% of dry weight). The other most important constituent elements are Na, P, S, K, Mg, and Ca. Their average total concentrations are 4.82 ± 0.1%. From an analysis of the composition of major and trace elements of zooplankton in the Kara Sea and the bays of Novaya Zemlya, three groups of elements have been specified: with similar (С_org, K, S, P, Al, Ti, Sc, Cd, Se, Cs, and Rb), lower (Na, Ca, Mg, Fe, Mn, Zn, Sr, Ba, B, Cu, Pb, Cr, Ni, V, Co, Sb, Mo, Ag, Be, Ga, and Hg), and higher (Li, As, and U) contents compared to their mean concentrations in ocean zooplankton.     

Inhibitory effects of divalent metal ions on liver microsomal 7-ethoxyresorufin O-deethylase (EROD) activity of leaping mullet

The purpose of the present study was to elucidate in vitro effects of Hg(2+), Zn(2+), Ni(2+) and Cd(2+) on cytochrome P4501A1 (CYP1A1) dependent EROD activities in leaping mullet liver microsomes. Fish captured from the most polluted part of Izmir Bay, had highly elevated EROD activities, and induced CYP1A1 protein levels as determined by Western blotting. Although all of the metal ions caused inhibition of the initial velocity of the reaction, Hg(2+) and Cd(2+) exhibited much higher inhibitory effect at lower concentrations and they were evidently more potent inhibitors than others. The inhibitor concentration giving 50% inhibition (IC(50) values) of Zn(2+), Ni(2+), Cd(2+) and Hg(2+) of initial EROD activity were 107, 16, 1.3 and 0.15 micromolar, respectively. Glutathione (GSH) at 0.5 mM final concentration, completely reversed Ni(2+) and Cd(2+) inhibition of EROD activity indicating the protective action of GSH.     

羊栖菜不同部位微量元素含量测定及健康风险评价

运用电感耦合等离子体质谱 (inductively coupled plasma mass spectrometer, ICP MS)分析3个不同养殖区域成熟期羊栖菜（Sargassum fusiforme）主茎、侧茎、生殖托、气囊等部位中As、Cd、Cr、 Cu、Ni、Pb和Zn的含量,以揭示羊栖菜中这些微量元素在不同部位的分布特征。结果表明,羊栖菜具有较强的微量元素富集能力,不同部位的微量元素富集能力存在差异,主要富集在生殖托和气囊中。结果表明,各站位间As、Cd、Cr和Cu在各部位的分布特征较为相似,而Ni、Pb和Zn在各部位中的分布特征存在差异。羊栖菜对As的富集系数最高,对Cr的富集系数最小。根据健康风险评价结果,除了两个站位的生殖托外,摄入羊栖菜不会对人体产生健康风险,但是相对而言,茎干的食用风险更低。     

The distribution of zinc,nickel, manganese,cadmium, copper,and iron in some surface waters from the world ocean

Determinations of Zn, Ni, Mn, Cd, Cu, and Fe have been carried out on 51 near-shore and 38 open-ocean surface seawaters from various regions of the World Ocean.The concentrations of the trace metals have been established in the open-ocean waters, and have been used as “baselines” to evaluate trace-metal enhancement in near-shore regions. The factors by which the trace metals are enriched in near-shore regions vary from one element to another and, according to the highest concentration factors found, decrease in the order Zn = Mn > Cd = Cu = Ni.These elements exhibit differences in their distributions between near-shore and open-ocean waters, and they have been divided into two types on this basis: Type I, in which the largest number of samples in both shelf and open-ocean waters lie in the same concentration range. Zinc, cadmium, and copper are Type I elements. Type 2, in which the largest number of samples of near-shore waters lie in a higher concentration range than the largest number of samples of open-ocean waters. Nickel and manganese are Type 2 elements.The concentrations of Mn, Cd and Zn are similar in open-ocean surface waters from the South Atlantic and Indian Ocean, but Cu and Ni have higher concentrations in the former ocean.There is considerable variation in the concentrations of the trace metals in near-shore surface waters from various regions of the World Ocean. These variations are discussed in detail.     

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.