Metal distribution and metallothionein in loggerhead (Caretta caretta) and green (Chelonia mydas) sea turtles

The first aim of our study was to determine the concentrations of selected trace elements (Zn, Cu, Fe, Mn, Cd and Pb) in tissues of green turtles from Tortuguero National Park on the North Caribbean coast of Costa Rica and of loggerheads from the Mediterranean Sea. Zn, Cu, Fe, Mn and Cd were present at detectable concentrations in all samples and showed clear organotropism, whereas Pb was not always over the detection limit and did not show any particular tissue distribution. The two species presented significant differences: Cu and Cd in liver and kidney of Chelonia mydas were significantly higher with respect to the concentrations found in Caretta caretta. The second and major goal of our study was to evaluate hepatic and renal metallothionein (MT) as a biomarker of environmental metal exposure. The present paper is the first to describe and quantify MT in kidney and liver of loggerhead turtles and in kidney of green turtles. MT concentrations were higher in green than in loggerhead turtles. In addition, positive correlations were found between Cu and Cd concentrations and Cu-MT and Cd-MT in liver and kidney in both species, suggesting a pivotal role of MT in metal storage and detoxification. The quantification of metals and MT in liver and kidney may be a valid biomarker of metal exposure in the aquatic environment to assess the health of marine sea turtles as long as accurate analytical methods are adopted.     

Partitioning of trace metals before and after biological removal of metals from sediments

Metal removal by biological solubilization in three strongly contaminated sediments was carried out in a two-liter stirred bioreactor. Biological treatment yielded metal removal efficiencies in the range of 11-30%, 43-57%, 60-79%, 61-90%, 18-21%, 0-10% for Pb, Cu, Zn, Cd, Ni and Cr, respectively. The treated sediments were then rinsed with a NaCl solution (0.5 M), resulting in an increase by nearly 47% in Pb removal for the three sediments, while for other metals (Cu, Zn, Cd, Ni, Cr), the NaCl rinse did not seem to allow any significant increase in metal solubilization. A standard procedure of sequential selective extraction (SSE) was applied to the sediments before and after each treatment. With regard to Pb, Zn and Cd, the carbonate bound fractions (2/3 sediments) represented 18-42% of metals prior to treatment, while the iron and manganese oxides bound fraction constituted 39-60% of metals for the three sediments. Between 90 and 100% of Pb, Zn and Cd removed by the process came from the fractions bound to carbonates and from those bound to Fe and Mn oxides. The organic matter and sulfide bound fractions contained 65-72% of total Cu present before treatment and the process removed, on average, 63% Cu present in this fraction. In contrast, Ni and Cr were found mainly in the residual fractions (50-80%). Finally, this biological treatment did not solubilize Cr appreciably, while removal of Ni mostly originated from the carbonate and Fe/Mn oxides fractions (70-80%).     

Metallothionein and metal levels in cytosol of liver, kidney and brain in relation to growth parameters of Mullus surmuletus and Liza aurata from the Eastern Adriatic Sea

Two wild fish populations (Mullus surmuletus (striped red mullet) as a bottom, and Liza aurata (golden grey mullet) as a pelagic species, were sampled in Kastela Bay, Middle Dalmatia. Metallothionein (MT) and metal content (Cu, Zn, Cd) was determined in heat-treated supernatants (S50) of fish tissues. MT levels were statistically different in liver and kidney of sampled species, with highest value in kidney of M. surmuletus (31.1 +/- 7.96 micrograms mg-1 proteins). Metal levels are statistically different between all tissues. Highest metal concentrations are in liver cytosols, especially of Cu in L. aurata (6.46 +/- 3.45 micrograms ml-1 S50). High positive correlation of MT and cytosolic metals is established with Zn in liver of M. surmuletus (0.95) and with Cu in liver of L. aurata (0.69). Total length, body weight and age are mostly correlated biometric parameters with MT and soluble metal concentrations. MT and metal levels increase with age in liver cytosol of both species.     

Seasonal and time variability of heavy metal content and of its chemical forms in sewage sludges from different wastewater treatment plants

Sewage sludges obtained from seven wastewater treatment plants from the province of Salamanca, Spain, were periodically sampled to determine seasonal and time variation of their elemental composition over 2000 to 2002. The aim of this paper was to provide additional insight to evaluate the potential environmental impact following soil incorporation of these materials as amendments. Aqua regia extractable metals (pseudo total content) of Cd, Cr, Cu, Ni, Pb and Zn were determined and furthermore, the main chemical forms of metals within the sludge were evaluated using a five-step fractionation procedure. All the studied sludges displayed high fertility properties due to their richness of OC, P and K. Total mean concentrations of Cd, Cr, Cu, Ni, Pb and Zn in the sludges were within the regulation of the Spanish legislation. Using an multifactor analysis of variance, significant differences between Cr, Cu, Ni, Pb and Zn pseudo total contents (p<0.01) of sludges at different sites were found while the Cd content was statistically similar. Also significant differences were found between these pseudo total contents of heavy metals in samples collected along the time after three years (0.001相似文献   

Evaluation of metal concentrations in edible vegetables grown in compost amended soil

Agricultural uses of compost usually have a positive effect on the yield of vegetable crops for human consumption. However, compost that contains heavy metals can transfer these components to soils and plants. To evaluate the contamination levels of metals in soil, compost, and edible vegetables, the Mn, Zn, Pb, Cd, Cu, and Ni total contents were measured. Metal availability in soils, as well as other variables – the pH, CEC (cation exchange capacity), total nitrogen, organic carbon, particle size distribution and mineralogy of the clay fraction – were examined in the soil samples. The analysed compost samples were produced from urban solid waste, cattle manure, and edible vegetable and tree pruning residues. The values of pH, CEC, total nitrogen, organic matter, exchangeable hydrogen and carboxylic groups were measured in the compost samples. Of the six metals examined in the soils, in general, Mn and Zn attained the highest concentrations, followed by Cu. Relatively high Mn, Zn, Cu, Cd and Pb concentrations were found in the soils. Metal concentrations extracted with DTPA were below the critical levels in soils, i.e. the levels above which toxicity is likely. In general, Zn, Pb, Cd, Cu and Ni concentrations in compost were lower than those reported by other workers, while Mn levels were within the range for this metal in compost. The results showed that there was an effect of the vegetable type (p < 0.01) for all the parameters examined. High Pb concentrations were found in lettuce and chive as compared with the tolerance limit for this metal in fresh vegetables in Brazil. Cadmium concentrations were also enhanced in the fresh vegetables compared with the typical concentrations of metals in plants. Zinc, Cu, Cd, and Ni concentrations were lower than the tolerance limits established for foods by the Brazilian legislation.     

Implication of heavy metals distribution for a municipal solid waste management system--a case study in Shanghai

Heavy metal contamination in municipal solid waste (MSW) is of increasing concern. The occurrence and distribution of heavy metals in MSW and their implications for the integrated MSW management system in mega-cities have been investigated by means of material flow analysis based on a case study of Shanghai in China. A good statistical basis was provided through a one-year monitoring program on the mass and metals composition of the waste from three MSW treatment facilities. The results showed that the main heavy metals in the MSW were Zn, Cr, Cu, and Pb (on average >100 mg kg(-1)), followed by Ni, Cd, and Hg. The MSW contained higher levels of Cu and Ni in metals, Cr and Pb in plastics, and Pb and Zn in the inorganic fractions. Regardless of the sources, the statistically similar heavy metal contents in the organic fractions indicated that effective blending and diffusion of heavy metals had taken place throughout the MSW collection, transfer, transportation, and storage, leading to cross-contamination of the waste fractions. PU (composed of putrescible waste and miscellaneous indistinguishable particles) contributed the majority of the heavy metals to the MSW, followed by plastics, as a result of the predominance in the overall composition of PU and plastics rather than from differences in their heavy metal contents. Therefore, manual or mechanical separation of some significantly heavy metal-rich fractions alone is not sufficient to reduce the heavy metal contents in the MSW. Source separation of organic waste and the diversion of tailored inorganic waste such as hazardous components, construction and demolition waste, etc., are proposed to control the heavy metal contamination in MSW. For the mixed MSW management system, physicochemical fractionation to exclude particles containing high levels of heavy metals can be conducted.     

Metal content of dandelion (Taraxacum officinale) leaves in relation to soil contamination and airborne particulate matter.

The global distribution of the common dandelion (Taraxacum officinale Weber, sensu lato; Asteraceae), along with its ability to tolerate a wide range of environmental conditions, make this 'species' a particularly attractive candidate to evaluate for its value as a biological monitor of environmental metal contamination. To examine the metal content of dandelion leaves in relation to environmental metal levels, the concentrations of eight metals (Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) were analyzed in leaf and soil samples collected at 29 sites in the mid-western United States differentially impacted by pollution. Sites were chosen primarily to cover a range of annual mean 24-h airborne particulate matter < or = 10 microm (hereafter, PM10) exposure, with PM10 levels varying from those found in isolated rural areas to levels typical of the most industrialized urban locations in the mid-western United States. A positive. significant correlation was detected between soil concentrations of each metal and measures of PM10 at a site, signifying that airborne particulate matter is a good indicator of soil metal contamination. Leaf concentrations of four of the eight metals (Cr, Mn, Pb and Zn) examined were found to increase significantly as the soil levels of these metals increased, but the percentage of the total variation explained by the relationship in these cases was generally low. This latter finding, along with the lack of a significant relationship between leaf and soil concentrations for the four other metals, indicate that the factors affecting metal absorption from the soil by dandelions are complex and that, aside from soil metal concentrations, other soil, plant and/or other environmental factors affect metal uptake. There was also no evidence that leaf metal concentrations were positively correlated with PM10. In addition, the concentrations of some metals (Cu, Fe, Mn, Pb and Zn) were significantly higher in leaves collected in the fall compared to those collected at the same sites in the spring. These findings suggest that dandelions may not be a particularly effective tool for quantifying levels of environmental metal contamination, at least on the scale of pollution typifying industrialized urban areas of the mid-western United States.     

Estuarine capacity in removal of trace metals from contaminated river water, Southern Caspian Sea

In the present investigation, the flocculation of dissolved Cd, Cu, Ni, Pb, Mn and Zn with initial concentrations of 1, 2.5 and 5 mg/L in Tadjan River water during mixing with the Caspian Sea water has been studied in order to determine estuarine capacity to remove dissolved metals in the accidental contamination of the river. The flocculation process was investigated on a series of mixtures with salinities ranging from 0.1 to 11 p.p.t. The flocculation rates were indicative of the nonconservative behaviour of Cd, Cu, Ni, Pb, Mn and Zn during estuarine mixing. The order of the final flocculation rate of dissolved metals at 1, 2.5 and 5 mg/L of initial metal concentrations in the river water is as follows:Cu (99%)>Cd (95%)>Zn (88%)>Mn (85%)>Pb (83%)>Ni (73%), Cu(95.6%)>Pb(92.4%)>Cd (90%)>Zn(88.4%)>Mn (81.6%)>Ni(78.8%) and Cd (100%)>Cu(88%)>Ni (85.2%)>Pb (84%)>Zn (83.2%)>Mn (81.2%), respectively. The results also revealed that removal of dissolved metals is not influenced by pH changes and precipitation processes. The flocculation rates revealed that the overall dissolved metal pollution loads may be reduced to about 70% up to about more than 90% during estuarine mixing of Tadjan River with the Caspian Sea water.     

Transformation of metals speciation in a combined landfill leachate treatment

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter > 0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction < 0.45 μm were considered as dissolved.     

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Influence of a salt marsh plant (Halimione portulacoides) on the concentrations and potential mobility of metals in sediments

Influence of Halimione portulacoides, commonly found in temperate salt marshes, on sediment metal contents, speciation and potential mobility in case of sediment re-suspension was evaluated. Both colonized and non-colonized sediments were studied for total Cd, Cu, Pb and Zn contents and metal fraction exchangeable to water collected in situ. Sediment elutriates, prepared with water collected from each site, were used to simulate a sediment re-suspension phenomenon. As the characteristics and degree of contamination of sediments may influence system behaviour, salt marshes of two Portuguese estuaries, Cavado (NW coast) and Sado (SW coast), were studied. Cu, Pb and Zn contents higher than ERL (quality guideline, effect range-low) were observed, indicating potential risks for living organisms. Strong Cu-complexing organic ligands, also determined in both water and elutriates, were higher in rhizosediment elutriates, at concentrations similar, or even higher, to those of Cu. Such ligands condition metals speciation in the water column and probably also metal bioavailability. From rhizosediment significant amounts of Cu and Zn were transferred to the aqueous phase, concentrations 2-8 times higher than concentrations present in water. In contrast, elutriates of non-colonized sediment removed metals from water, Cu and Zn levels in elutriates being 2-6 times lower than initial ones. Cd and Pb levels in water and elutriates were not measurable in most cases. Results clearly indicate that metals potential solubility in the rhizosphere of plants was markedly higher than that in the surrounding sediment. The obtained results indicated that H. portulacoides presence (and probably other salt marsh plants) may cause a marked increase in metals concentrations in dissolved phase (pore water or even water column if rhizosediment is re-suspended). As salt marsh plants may be abundant in temperate and subtropical estuaries and costal lagoons, this phenomenon should not be disregard in future studies towards the sustainable management of such environments.     

Sub-cellular partitioning of Zn, Cu, Cd and Pb in the digestive gland of native Octopus vulgaris exposed to different metal concentrations (Portugal)

Concentrations of Zn, Cu, Cd and Pb and their sub-cellular distributions were determined in composite samples of digestive glands of the common octopus, Octopus vulgaris caught from two areas of the Portuguese coast characterised by contrasting metal contamination. Minor contents of Zn (1%), Cu (2%), Cd (6%) and Pb (7%) were found in the insoluble fraction, consisting of nuclei, mitochondria, lysosomes and microsome operationally separated from the whole digestive gland through a sequential centrifugation. A tendency for linear relationships between metal concentrations in nuclei, mitochondria, lysosomes and whole digestive gland was observed. These relationships suggest that despite low metal content organelles responded to the increasing accumulated metals, which means that detoxifying mechanism in cytosol was incomplete. Poorer correlations between microsome and whole digestive gland did not point to metal toxicity in the analysed compartments. However, the high accumulated Cd indicated that O. vulgaris is an important vehicle of this element to its predators in the coastal environment.     

Anthropogenic contamination and risk assessment of heavy metals in stream sediments influenced by acid mine drainage from a northeast coalfield,India

The total concentrations and chemical partitioning of heavy metals in streambed sediments, collected around the Jaintia Hills coal deposit of northeast India, were studied using pollution indices and multivariate techniques to evaluate the risk and contamination levels from heavy metals and their possible origins. Results show that sediments close to mining sites have low pH (<4), high organic carbon, and contain significant amounts of Fe-oxyhydroxide phases (mainly, goethite and schwertmannite), which implies direct impact of coal mine drainage. The average concentrations of Fe, Cu, Co, Cd, Cr, and Zn exceeded the World average, and in some cases, Cd, Cu, Ni, and Cr concentrations exceeded the threshold effects level, which suggests they will be toxic to aquatic biota. Contamination factors (CF) show that the sediments are low to highly contaminated with Cd, Cu, Mn, Pb, Fe, and Zn and low to moderately contaminated with Co, Cr and Ni. The pollution load index (PLI), degree of contamination index (C _deg) and Nemerow integrated pollution index (NIPI) show that the sediments are moderately to highly contaminated, with the extent of pollution greatest nearest to the collieries. The potential ecological risk index (RI) shows low to considerable ecological risk from heavy metals in the sediments, with Cd having the high potential of risk, which also agrees with the risk assessment code (RAC). Multivariate statistical analysis suggests that the concentrations of the heavy metals in stream sediments are strongly influenced by Fe-oxyhydroxide phases and organic carbon derived from anthropogenic sources, mainly coal mining activities. Although a significant proportion of the Cd, Mn, and Ni in the sediments are partitioned into exchangeable and organic fractions, a sizable amount of metals are also found in the Fe–Mn fraction, suggesting that Fe-oxyhydroxides play a dominant role in controlling metal mobility in these stream sediments.     

Short-term effects of biosolid and municipal solid waste applications on heavy metals distribution in a degraded soil under a semi-arid environment

Digested biosolid (SS) and municipal solid waste (MSW) were surface-applied to a degraded carbonated soil, under semi-arid environment, at rates of 0 and 80 Mg/ha, to determine the changes in organic matter and in the distribution of heavy metals in the topsoil, 1 year after its application. Waste application slightly increased the organic matter content and improved the composition of humic fractions in the treated soils, mainly in the MSW amended plots. A sequential extraction method (Tessier et al., 1979) was used to determine the distribution of Cd, Cr, Cu, Ni, Pb and Zn in both the waste and the amended.soils. Waste application had little effect on the total concentration of Ni and Cr in the treated soils as a consequence of the low availability of these metals in the wastes. A considerable increase of Cd, Cu, Pb and Zn was observed as a consequence of the high content and/or high availability of these metals in the wastes. The more labile fraction (exchangeable fraction) of all metals studied increased slightly (< 1.5 mg/kg) when SS and MSW were added. However, a remarkable increase in the Fe/Mn oxide fraction of Cd, Cu and Pb and in the organic fraction of Zn were noted in treated plots, this increase being higher in the MSW treated soils.     

Trace elements in soils and plants in temperate forest plantations subjected to single and multiple applications of mixed wood ash

Wood ash, a by-product generated in power plants, can be used to fertilize forest plantations to replenish nutrients lost during harvesting. Although wood ash generally contains low levels of trace metals, release of some of these may occur soon after ash application in acid soils. The risk of heavy metal contamination associated with application of mixed wood ash was assessed in six Pinus radiata D. Don plantations, on two types of mineral soil differing in texture, drainage and CECe. Four of the stands received a single application of 4500 kg ha(-1) (March 2003), and in the other two stands the same treatment was applied over three consecutive years (2003-2005). Trace metal (Cd, Cr, Cu, Mn, Ni, Pb, Zn) concentrations were monitored throughout the 3 years in different components of the forest ecosystem--soil solid fraction, soil solution, tree needles, ground vegetation and different mushroom species. Repeated applications of wood ash led to moderate increases in soil extractable Mn and Zn, and Mn in all mushrooms species. However, the maximum concentrations did not reach levels potentially harmful to organisms. Concentrations of Zn, Cu and Cd decreased in some mushroom species, probably because of increased soil pH caused by the treatment. Heavy metal concentrations in tree needles and ground vegetation were not altered. Although the risk of heavy metal contamination appears to be low, the long-term effects of wood ash application must be assessed.     

Speciation of lead, copper, zinc and antimony in water draining a shooting range—Time dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.)

The speciation of Pb, Cu, Zn and Sb in a shooting range run-off stream were studied during a period of 23 days. In addition, metal accumulation in gills and liver, red blood cell ALA-D activity, hepatic metallothionine (Cd/Zn-MT) and oxidative stress index (GSSG/ tGSH levels) in brown trout (Salmo trutta L.) exposed to the stream were investigated. Fish, contained in cages, were exposed and sampled after 0, 2, 4, 7, 9, 11 and 23 days of exposure. Trace metals in the water were fractionated in situ according to size (nominal molecular mass) and charge properties. During the experimental period an episode with higher runoff occurred resulting in increased levels of metals in the stream. Pb and Cu were mainly found as high molecular mass species, while Zn and Sb were mostly present as low molecular mass species. Pb, Cu and Sb accumulated on gills, in addition to Al origination from natural sources in the catchment. Pb, Cu and Sb were also detected at elevated concentration in the liver. Blood glucose and plasma Na and Cl levels were significantly altered during the exposure period, and are attributed to elevated concentrations of Pb, Cu and Al. A significant suppression of ALA-D was detected after 11 days. Significant differences were detected in Cd/Zn-MT and oxidative stress (tGSH/GSSG) responses at Day 4. For Pb the results show a clear link between the HMM (high molecular mass) positively charged Pb species, followed by accumulation on gills and liver and a suppression in ALA-D. Thus, high flow episodes can remobilise metals from the catchment, inducing stress to aquatic organisms.     

Geochemistry of trace metals in a fresh water sediment: field results and diagenetic modeling

Concentrations of Fe, Mn, Cd, Co, Ni, Pb, and Zn were determined in pore water and sediment of a coastal fresh water lake (Haringvliet Lake, The Netherlands). Elevated sediment trace metal concentrations reflect anthropogenic inputs from the Rhine and Meuse Rivers. Pore water and sediment analyses, together with thermodynamic calculations, indicate a shift in trace metal speciation from oxide-bound to sulfide-bound over the upper 20 cm of the sediment. Concentrations of reducible Fe and Mn decline with increasing depth, but do not reach zero values at 20 cm depth. The reducible phases are relatively more important for the binding of Co, Ni, and Zn than for Pb and Cd. Pore waters exhibit supersaturation with respect to Zn, Pb, Co, and Cd monosulfides, while significant fractions of Ni and Co are bound to pyrite. A multi-component, diagenetic model developed for organic matter degradation was expanded to include Zn and Ni dynamics. Pore water transport of trace metals is primarily diffusive, with a lesser contribution of bioirrigation. Reactions affecting trace metal mobility near the sediment-water interface, especially sulfide oxidation and sorption to newly formed oxides, strongly influence the modeled estimates of the diffusive effluxes to the overlying water. Model results imply less efficient sediment retention of Ni than Zn. Sensitivity analyses show that increased bioturbation and sulfate availability, which are expected upon restoration of estuarine conditions in the lake, should increase the sulfide bound fractions of Zn and Ni in the sediments.     

Historical perspective of heavy metals contamination (Cd, Cr, Cu, Hg, Pb, Zn) in the Seine River basin (France) following a DPSIR approach (1950-2005)

The Driver-Pressures-State-Impact-Response approach is applied to heavy metals in the Seine River catchment (65,000 km(2); 14 million people of which 10 million are aggregated within Paris megacity; 30% of French industrial and agricultural production). The contamination pattern at river mouth is established on the particulate material at different time scales: 1930-2000 for floodplain cores, 1980-2003 for suspended particulate matter (SPM) and bed-sediments, 1994-2003 for atmospheric fallout and annual flood deposits. The Seine has been among the most contaminated catchments with maximum contents recorded at 130 mg kg(-1) for Cd, 24 for Hg, 558 for Pb, 1620 for Zn, 347 for Cu, 275 for Cr and 150 for Ni. Today, the average levels for Cd (1.8 mg kg(-1)), Hg (1.08), Pb (108), Zn (370), Cu (99), Cr (123) and Ni (31) are much lower but still in the upper 90% of the global scale distribution (Cr and Ni excepted) and well above the natural background values determined on pre-historical deposits. All metal contents have decreased at least since 1955/65, well before metal emission regulations that started in the mid 1970's and the metal monitoring in the catchment that started in the early 1980's. In the last 20 y, major criteria changes for the management of contaminated particulates (treated urban sludge, agricultural soils, dredged sediments) have occurred. In the mid 1990's, there was a complete shift in the contamination assessment scales, from sediment management and water usage criteria to the good ecological state, now required by the 2000 European Directive. When comparing excess metal outputs, associated to river SPM, to the average metal demand within the catchment from 1950 to 2000, the leakage ratios decrease exponentially from 1950 to 2000 for Cd, Cr, Cu, Pb and Zn, meanwhile, a general increase of the demand is observed: the rate of recycling and/or treatment of metals within the anthroposphere has been improved ten-fold. Hg environmental trajectory is very specific: there is a marked decontamination from 1970 to 2000, but the leakage ratio remains very high (10 to 20%) during this period. Drivers and Pressures are poorly known prior to 1985; State evolution since 1935 has been reconstructed from flood plain cores analysis; Impacts were maximum between 1950 and 1970 but remained unknown due to analytical limitation and lack of awareness. Some Responses are lagging 10 y behind monitoring and have much evolved in the past 10 y.     

Heavy metals in the tissues of common dolphins (Delphinus delphis) stranded on the Portuguese coast.

The concentrations of Hg, Sn, Cr, Zn, Ni, Co, Cd, Mn, Fe and Cu were determined in the liver, kidney and muscle of 24 common dolphins stranded on the Portuguese coast between 1995 and 1998. Nitric acid was used to extract the metals from the tissues for analysis by inductively-coupled plasma/atomic emission spectroscopy (ICP/AES). Those metals with relatively higher concentrations included Fe, Zn and Hg, particularly in liver. Other metals including Cr, Ni and Cd tended to show much lower levels, or were even undetected (e.g. Co). Different metals seemed to show different temporal trends, although due to substantial variations of the mean concentrations for each year obtained, such temporal pattern has to be studied further. Total Hg concentration in the kidney, muscle and particularly liver, were higher in females than in males. Total Hg concentrations in all the organs increased with body length of dolphins, whilst those of Zn and Cu in muscle decreased with dolphin length. A strong correlation was found between essential metals Zn and Cu in muscle, possibly resulting from sequestration of these metals by metallothionein. In addition, significant co-associations existed between the same metal (e.g. Hg, Sn and Zn) in different organs.     

Lichen (Xanthoria parietina) biomonitoring of trace element contamination and air quality assessment in Pisa Province (Tuscany, Italy)

In the northern part of Pisa Province (Tuscany, Italy), the use of lichens as both airborne trace element biomonitors and air quality bioindicators is described. The following elements were analysed in Xanthoria parietina: As, Cd, Cr, Ni, Pb, V, Zn and Hg, and the results are compared with those we previously obtained in Livorno Province (Tuscany) using the same lichen species. The results identify spots of different environmental metal contamination and air quality. Median values of Pb, V and Ni concentrations were much lower than those of Livorno Province, with maximum values even nine times lower. Arsenic contamination was also lower, while Cd, Hg and Zn levels were similar in the two areas. In Pisa Province, the highest levels of contamination were recorded for Zn, Pb, Cr and Ni, and a degree of agreement was found between air quality and metal concentrations in lichens. The air quality in Pisa Province is better than in Livorno Province, even if the different climatic and orographic features of the two areas may influence the presence of lichen species and thus an assessment of air quality.