Dissolved and particulate metals (Fe, Zn, Cu, Cd, Pb) in two habitats from an active hydrothermal field on the EPR at 13 degrees N

The distribution of Fe, Cu, Zn, Pb, Cd between the dissolved (<2 microm) and the particulate (>2 microm) fractions was measured after in-situ filtration in two hydrothermal habitats. The total metal concentration ranges exhibit a clear enrichment compared with the seawater concentration, accounting for the hydrothermal input for all the metals considered. Iron is the predominant metal (5-50 microM) followed by Zn and Cu. Cd and Pb are present at the nM level. At the scale studied, the behavior of temperature, pH and dissolved iron is semi-conservative whereas the other dissolved and particulate metals are characterized by non-conservative patterns. The metal enrichment of the >2 microm fraction results from the settlement and accumulation of particulate matter close to the organisms, acting as a secondary metal source. The enrichment observed in the dissolved fraction can be related to the dissolution or oxidation of particles (mainly polymetallic sulfide) or to the presence of small particles and large colloids not retained on the 2 microm frit. SEM observations indicate that the bulk particulate observed is characteristic of crystalline particles settling rapidly from the high temperature smoker (sphalerite, wurtzite and pyrite), amorphous structures and eroded particles formed in the external zone of the chimney. Precipitation of Zn, Cu, Cd and Pb with Fe as wurtzite, sphalerite and pyrite is the main process taking place within the area studied and is semi-quantitative. The distribution of the dominant observed fauna has been related to the gradient resulting from the dilution process, with the alvinellids worms colonizing the hotter and more variable part of the mixing zone, but also to the metallic load of the mixing zone. Dissolved and particulate metal concentrations are therefore necessary abiotic factors to be studied in a multiparametric approach to understand the faunal distribution in hydrothermal ecosystems.     

Distribution of Cd, Zn, Cu and Fe among selected tissues of the earthworm (Allolobophora caliginosa) and Eurasian woodcock (Scolopax rusticola)

We have measured the concentrations of heavy metals in soils, earthworms and tissues of woodcocks in Quaderna Valley, northern Italy. The soil concentration of metals analysed in this research is consistent with data reported by other authors for uncontaminated or slightly contaminated soils. In earthworms, metals were mostly accumulated in the encapsulating chloragogenous tissue; the positive correlation between Cu concentration in the soil and in earthworms is noteworthy. Heavy metal distribution in the tissues of woodcock showed that Cd accumulation in the kidney was linked to the diet. Cu and Fe were preferentially concentrated in the liver and Zn in the testis. Kidney Cd and Zn concentrations were higher in adults than in juveniles. In addition, a main kidney metallothionein isoform, containing Cd and Zn, was isolated. In the kidney, Cd levels were linearly correlated with the concentration of metallothionein. Of the investigated metals, Cd raises the greatest concern, due to the increasing soil contamination by human activities.     

Determination of Co,Cu, Fe,Hg, Mn,Sb, Se and Zn in milk samples

Concentrations of Co, Cu, Fe, Hg, Mn, Sb, Se and Zn in IAEA milk (dry) standard A-11 were re-evaluated with the help of instrumental and radiochemical neutron activation analysis (NAA). The results show reasonably good agreement for Co (5.1 ± 0.55 ng/g) and Zn (34 ± 2.5 μg/g), in relation to the recommended values. For Cu (374 ± 15 ng/g), Fe (2.4 ± 0.34 μg/g) and Mn (250 ± 20 ng/g); the results obtained are lower than the reported values.Cu, Mn, and Zn were cross-checked by atomic absorption spectrophotometry (AAS). The results, Cu = 331 ± 27 ng/g, Mn = 302 ± 62 ng/g, and Zn = 35 ± 1 μg/g, fall within the range of mean values obtained by NAA.For Hg and Se, using instrumental NAA, only upper limits could be indicated; because of the low levels of concentrations of Hg and Se on one hand, and high content of P (9100 μg/g) in A-11 milk standard on the other, NAA coupled with radiochemistry is to be preferred for these two elements.In pooled human milk, in addition to Cu and Mn (radiochemical) and Co, Fe, Sb and Zn (instrumental), Hg and Se could also be determined non-destructively because of the favourable Hg/P and Se/P ratios in this matrix.     

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.     

The spatial and temporal trends of Cd, Cu, Hg, Pb and Zn in Seine River floodplain deposits (1994-2000)

Fresh floodplain deposits (FD), from 11 key stations, covering the Seine mainstem and its major tributaries (Yonne, Marne and Oise Rivers), were sampled from 1994 to 2000. Background levels for Cd, Cu, Hg, Pb, and Zn were established using prehistoric FD and actual bed sediments collected in small forested sub-basins in the most upstream part of the basin. Throughout the Seine River Basin, FD contain elevated concentrations of Cd, Cu, Hg, Pb and Zn compared to local background values (by factors>twofold). In the Seine River Basin, trace element concentrations display substantial downstream increases as a result of increasing population densities, particularly from Greater Paris (10 million inhabitants), and reach their maxima at the river mouth (Poses). These elevated levels make the Seine one of the most heavily impacted rivers in the world. On the other hand, floodplain-associated trace element levels have declined over the past 7 years. This mirrors results from contemporaneous suspended sediment surveys at the river mouth for the 1984-1999 period. Most of these temporal declines appear to reflect reductions in industrial and domestic solid wastes discharged from the main Parisian sewage plant (Seine Aval).     

Long-term trends in accumulated metals (Cd, Cu and Zn) and metallothionein in bivalves from lakes within a smelter-impacted region

Temporal monitoring studies are needed to detect long-term trends in ecosystem health. In the present study, we tested metallothionein (MT) as a potential biomarker for long-term variations in trace metal levels in lakes subject to atmospheric metal inputs from a nearby copper smelter. Over a 13-year period, we estimated on several occasions ambient free Cd2+, Cu2+ and Zn2+ concentrations at the sediment-water interface in six lakes with contrasting metal levels, and measured metal and metallothionein concentrations in gills of bivalves (Pyganodon grandis) living in these lakes. All but one of the study lakes had comparable drainage ratios, so inter-lake differences in hydrological export of metals from contaminated watersheds to receiving waters were likely minimal. Declines in the metal emissions from the smelter (especially for Cd and Zn) during the 1980s led to appreciable decreases in both calculated free Cd2+ ion concentrations in the study lakes (-59+/-21% between 1989 and 1998) and accumulated Cd levels in their clam populations (-46+/-12% between 1989 and 2002). Taking all lakes into account, MT concentrations in bivalves have comparatively dropped by 44% (+/-10%) since 1989. In contrast to what we found for Cd, there were no significant reductions in the calculated free Cu2+ and Zn2+ concentrations in the various lakes during our study period (-2 and -10%, respectively, with 95% confidence intervals spanning zero). Overall, observed decreases in MT in bivalves over time were best correlated with similar decreases in both ambient and accumulated Cd levels (r = 0.77, P = 0.0003 and r = 0.79, P < 0.0001, respectively, both P-values corrected for temporal autocorrelation), suggesting that long-term trends in gill MT concentrations in P. grandis may be useful as predictors of temporal changes in environmental Cd contamination in lakes.     

Temporal trends of Cd, Cu, Hg, Pb and Zn in mussel (Mytilus galloprovincialis) from the Spanish North-Atlantic coast 1991-1999

Temporal trends for heavy metals (Cd, Cu, Hg, Pb and Zn) in mussel (Mytilus galloprovincialis) from the Galician and Cantabrian areas in Spain, where samples were yearly collected from 1991 to 1999, are presented. This study was carried out by the Centro Oceanográfico de Vigo of the Instituto Espa?ol de Oceanografia (I.E.O.) as part of the Spanish contribution to the Joint Assessment and Monitoring Programme (JAMP) of the OSPAR Convention. The experimental work and subsequent statistical treatment, following OSPAR procedures and guidelines, are described. In order to carry out the statistical treatment of the data, median values of the different shell length classes were used for each contaminant, year and area. The Kendall T-b correlation coefficient was used with the purpose of demonstrating the existence of a downward significant temporal trend in the pollution levels, according to the advice of ICES Working Group on Statistical Aspects of Environmental Monitoring. A decrease of copper levels was detected in Vigo, Pontevedra and Arosa, of mercury in Pontevedra and A Coru?a, of lead in Vigo, Pontevedra, A Coru?a and Bilbao and of zinc in Pontevedra and A Coru?a. However, a cadmium positive trend was registered at Ria de Vigo. No significant trends were detected in the other cases.     

Quantification of uncertainty in modelled partitioning and removal of heavy metals (Cu,Zn) in a stormwater retention pond and a biofilter

Strategies for reduction of micropollutant (MP) discharges from stormwater drainage systems require accurate estimation of the potential MP removal in stormwater treatment systems. However, the high uncertainty commonly affecting stormwater runoff quality modelling also influences stormwater treatment models. This study identified the major sources of uncertainty when estimating the removal of copper and zinc in a retention pond and a biofilter by using a conceptual dynamic model which estimates MP partitioning between the dissolved and particulate phases as well as environmental fate based on substance-inherent properties. The two systems differ in their main removal processes (settling and filtration/sorption, respectively) and in the time resolution of the available measurements (composite samples and pollutographs). The most sensitive model factors, identified by using Global Sensitivity Analysis (GSA), were related to the physical characteristics of the simulated systems (flow and water losses) and to the fate processes related to Total Suspended Solids (TSS). The model prediction bounds were estimated by using the Generalized Likelihood Uncertainty Estimation (GLUE) technique. Composite samples and pollutographs produced similar prediction bounds for the pond and the biofilter, suggesting a limited influence of the temporal resolution of samples on the model prediction bounds. GLUE highlighted model structural uncertainty when modelling the biofilter, due to disregard of plant-driven evapotranspiration, underestimation of sorption and neglect of oversaturation with respect to minerals/salts. The results of this study however illustrate the potential for the application of conceptual dynamic fate models base on substance-inherent properties, in combination with available datasets and statistical methods, to estimate the MP removal in different stormwater treatment systems and compare with environmental quality standards targeting the dissolved MP fraction.     

Critical budget of metal sources and pathways in the Seine River basin (1994-2003) for Cd, Cr, Cu, Hg, Ni, Pb and Zn

River basin metal pollution originates from heavy industries (plating, automobile) and from urban sources (Paris conurbation: 2740 km(2), 9.47 million inhabitants). The natural sources of metal have been found to be limited due to sedimentary nature of this catchment and to the very low river sediment transport (10 t km(-2) y(-1)). Several types of data have been collected to build the metal budget within the whole Seine River basin: field surveys, economical statistics and environmental models. Environmental contamination and related fluxes have been measured on atmospheric fallout, rural streams particles, and Seine River particles upstream and downstream of Paris and at river mouth. Metal pathways and budgets have been set up for (i) a typical cultivated area, (ii) a Paris combined sewer system, (iii) Paris conurbation and (iv) the whole catchment metal retention effect in floodplain and dredged material. Metal fluxes to the estuary have been decomposed into natural, urban domestic and other sources. The latter are within 1-2 orders of magnitude larger than waste water fluxes directly released into rivers according to an industrial census. These fluxes have been further compared to the annual use (1994-2003) of these metals. Metal excess fluxes exported by the river are now a marginal leak of metal inputs to the catchment (i.e. "raw" metals, metals in goods, atmospheric fallout), generally from 0.2 to 5 per thousand. However, due to the very limited dilution power in this basin, the contamination of particles is still relatively high. The Seine River basin is gradually storing metals, mostly in manufactured products used in construction, but also in various waste dumps, industrial soils, agricultural and flood plain soils.     

Trace metals: Cd, Cu, Pb and Zn in gelatinous macroplankton from the Northwestern Mediterranean

Gelatinous macroplankton organisms were collected in May 1984 in Villefranche-sur-Mer Bay and analysed for cadmium, copper, lead and zinc. Analyses were carried out by polarography for Cd, Cu and Pb and by flame atomic absorption for Zn. Phosphorus was also measured in the samples as a biomass parameter due to difficulties inherent in measuring dry weight of gelatinous organisms. The samples belong to the Tunicates, the Cnidarians (Hydromedusae, Siphonophores and Scyphomedusae), the Ctenophores and the Molluscs. Crustaceans living on some Tunicates were also sampled.As regards cadmium, copper and lead, mean concentrations did not show significant differences among the phyla studied: especially for Tunicates with mean values of 0.1 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹ and 0.9 ng Pb μg P⁻¹ and for Cnidarians with mean values of 0.5 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹ and 0.9 ng Pb μg P⁻¹ and for Cnidarians with mean values of 0.5 ng Cd μg P⁻¹, 2.0 ng Cu μg P⁻¹, 1.0 ng Pb μg P⁻¹. On the other hand, mean zinc concentrations were significantly lower in Tunicates (7.9 ng Zn μg P⁻¹) than in Cnidarians (36.8 ng Zn μg P⁻¹).Zinc seems to be preferentially concentrated in organisms which are rich in collagen, constituting the mesoglea, such as the Cnidarians, the Ctenophore and the gelatinous Mollusc studied, rather than in organisms rich in tunicin such as the Tunicates.     

Blood lead and its effect on Cd, Cu, Zn, Fe and hemoglobin levels of children

The levels of heavy metals, such as Pb, Cd, Cu, Zn and Fe, in whole blood samples of Mumbai and Hyderabad children have been determined. In the present study, 576 blood samples of children (3-6 years old) were collected during 1996-1998 and analyzed for heavy metal contents by anodic stripping voltammetry and atomic absorption spectrometry. The geometric mean concentrations of Pb, Cd, Cu and Zn in blood of Mumbai children were 8.0, 0.10, 86.5 and 398.9 microg dl(-1), while those for Hyderabad children were 13.3, 0.13, 100.6 and 483.4 microg dl(-1) respectively. The geometric mean concentrations of Fe in the blood of Mumbai and Hyderabad children were 21.9 and 34.5 mg dl(-1), respectively. Of the Mumbai children, 61.8% were found to have a blood lead concentration lcss than 10 microg dl(-1), while the corresponding proportion of Hyderabad children was 27.4%. Higher concentrations of Pb in the children's blood were observed at high traffic areas in both cities. A decreasing trend in the hemoglobin content with increasing blood lead levels was observed for Mumbai children. A good negative correlation (-0.61) between the blood lead and iron has been observed for Mumbai children The hemoglobin content of 85% of the study population was found to vary between 8 and 14 g%.     

Total metal concentrations and partitioning of Cd, Cr, Cu, Fe, Ni and Zn in sewage sludge

Application of the BCR three-step sequential extraction procedure to sewage sludge samples collected at an urban wastewater treatment plant (Dom ale, Slovenia) is reported. The total concentrations of Cd, Cr, Cu, Fe, Ni and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS) under optimised measurement conditions. Total acid digestion including hydrofluoric acid (HF) treatment and aqua regia extraction were compared in order to estimate the efficiency of aqua regia extraction for determination of total metal concentrations in sewage sludge. It was found experimentally that aqua regia quantitatively leached these heavy metals from the sewage sludge and could therefore be applied in analysis of total heavy metal concentrations. The total concentrations of 856 mg kg⁻¹ Cr, 621 mg kg⁻¹ Ni and 2032 mg kg⁻¹ Zn were higher than those set by Slovenian legislation for sludge to be used in agriculture. Total concentrations of 2.78 mg kg⁻¹ Cd, 433 mg kg⁻¹ Cu and 126 mg kg⁻¹ Pb were below those permitted in the relevant legislation. CRM 146R reference material was used to follow the quality of the analytical process. The results of the BCR three-step sequential extraction procedure indicate high Ni and Zn mobility in the sludge analysed. The other heavy metals were primarily in sparingly soluble fractions and hence poorly mobile. Due to the high total Ni concentration and its high mobility the investigated sewage sludge could not be used in agriculture.     

Observed and modeled seasonal trends in dissolved and particulate Cu, Fe, Mn, and Zn in a mining-impacted stream

North Fork Clear Creek (NFCC) in Colorado, an acid-mine drainage (AMD) impacted stream, was chosen to examine the distribution of dissolved and particulate Cu, Fe, Mn, and Zn in the water column, with respect to seasonal hydrologic controls. NFCC is a high-gradient stream with discharge directly related to snowmelt and strong seasonal storms. Additionally, conditions in the stream cause rapid precipitation of large amounts of hydrous iron oxides (HFO) that sequester metals. Because AMD-impacted systems are complex, geochemical modeling may assist with predictions and/or confirmations of processes occurring in these environments. This research used Visual-MINTEQ to determine if field data collected over a two and one-half year study would be well represented by modeling with a currently existing model, while limiting the number of processes modeled and without modifications to the existing model's parameters. Observed distributions between dissolved and particulate phases in the water column varied greatly among the metals, with average dissolved fractions being >90% for Mn, approximately 75% for Zn, approximately 30% for Cu, and <10% for Fe. A strong seasonal trend was observed for the metals predominantly in the dissolved phase (Mn and Zn), with increasing concentrations during base-flow conditions and decreasing concentrations during spring-runoff. This trend was less obvious for Cu and Fe. Within hydrologic seasons, storm events significantly influenced in-stream metals concentrations. The most simplified modeling, using solely sorption to HFO, gave predicted percentage particulate Cu results for most samples to within a factor of two of the measured values, but modeling data were biased toward over-prediction. About one-half of the percentage particulate Zn data comparisons fell within a factor of two, with the remaining data being under-predicted. Slightly more complex modeling, which included dissolved organic carbon (DOC) as a solution phase ligand, significantly reduced the positive bias between observed and predicted percentage particulate Cu, while inclusion of hydrous manganese oxide (HMO) yielded model results more representative of the observed percentage particulate Zn. These results indicate that there is validity in the use of an existing model, without alteration and with typically collected water chemistry data, to describe complex natural systems, but that processes considered optimal for one metal might not be applicable for all metals in a given water sample.     

Chemical substitution reaction between Cu(II) and Hg(II) and hydrous CdS(s)

The chemical reaction between hydrous CdS(s) and Cu(II) and Hg(II) were studied by electrophoretic mobility measurements and adsorption experiments. The results show that cation exchange, following readsorption of the released Cd(II) ions onto the freshly-formed CuS(s) and cadmium hydroxide precipitation reactions occur when CdS particles come into contact with these metal ions which have sulfide precipitates less soluble than CdS(s). The effect of organic ligands on the ion exchange reaction, exemplified by EDTA (a strong complexing ligand) and phthalic acid (a weak complexing ligand), was also investigated. Both organic compounds have little effect on the lattice ion exchange reaction unless a large amount of strong complexing agent is present in the system. The dissolution of CdS(s), however, is slightly hindered in the presence of weak complex former such as phthalic acid and greatly enhanced in the presence of strong complex former such EDTA.     

Release of toxic metals and metalloids from Los Rueldos mercury mine (Asturias, Spain)

The abandoned mercury mining works of "Los Rueldos" are located 20 km from Oviedo, along the northwestern border of the Asturian Central Coal Basin, in an area with intense tectonization. Hg mainly appears as cinnabar, but occasionally metacinnabar and native Hg are present; associated with Hg ore appear As-rich minerals (arsenopyrite, As-rich pyrite, realgar and scorodite). In the spoil heap, Hg content ranges from 14 to 2224 mg kg(-1), and As from 4746 to 62,196 mg kg(-1). Mine drainage and spoil heap leachates show acidic conditions (pH: 2.43-2.50), 2900-4600 mg l(-1) sulphate, 1.4-9.2 mg l(-1) As, 0.03-0.48 mg l(-1) Pb, and 3.6-14 microg l(-1) Hg. According to the analytical data and characteristics of the site, the application of corrective measurements to avoid the dispersion of contaminants in the environment must be considered.     

论西塔里木晚古生代弧形海相热水-火山热水沉积型铅锌（铜）矿区域成矿特征

西塔里木弧形晚古生代海相热水-火山热水沉积铅锌(铜)矿的蕴矿基础是恰尔隆-库尔良拉张坳陷带的一部分,奥依塔格裂陷槽,和西南天山柯坪断隆外缘(木兹都克)构造过渡带.这个弧形矿带的亚一级构造是弧顶区昆盖山北坡裂谷,属古隆外缘拉张坳陷带,产海相火山热水沉积型S、Cu、Zn、Au矿.弧西区塔木-卡兰古坳拉槽(夭折裂谷)产海相热水沉积型Pb、Zn(Cu)矿.弧东区西南天山木兹都克构造过渡带,产海相热水-火山热水沉积型Pb、Zu、Cu矿.这个弧形矿带中的矿产,其成矿与控矿构造具有一致性,成矿时代具有相对集中性、矿产生成具有迁移性、区域成矿特征具有可对比性,是新疆最为重要的铅锌成矿区带.     

Effects of two chelating agents (EDTA and DTPA) on the autochthonous vegetation of a soil polluted with Cu, Zn and Cd

Chelating agents are thought to be useful for the remediation of metal-polluted soils with adequate organic matter, but the effects of these substances on the plants or seed bank of plant communities that occur in the soils are relatively unknown. In this work, the effects of two chelating substances (EDTA and DTPA) on a wet grassland plant community affected by the presence of the abandoned copper mine "Fernandito" (Garganta de los Montes, Madrid) were compared. A microcosm bioassay (6 months) was designed using the soil's top layer containing the grassland's seed bank. This soil showed a high Cu pollution level, significant contents of Zn and Cd (1120, 190, and 15 ppm, respectively), a pH of 5 and an OM content of 6.2%. The soil was subjected to three different treatments: a) untreated soil (control), b) the addition of 1 g/kg EDTA, or of c) 1 g/kg DTPA. The results presented here are those related to the plant cover, species richness, aboveground and subterranean biomass and chemical composition of the most abundant plants. Neither EDTA nor DTPA caused intense negative effects on the plants rather they significantly increased the amount of copper accumulated in aboveground parts and roots. In particular, Agrostis castellana and Corrigiola telephiifolia extracted high amounts of copper when grown in the soil with added EDTA, although they showed some nutritional imbalances (lower P contents). In contrast, lower metal concentrations were detected in plants grown in the DTPA amended soil.     

Responses of antioxidant defenses to Cu and Zn stress in two aquatic fungi

Aquatic hyphomycetes are fungi that play a key role in plant litter decomposition in streams. Even though these fungi occur in metal-polluted streams, the mechanisms underlying their tolerance to metals are poorly documented. We addressed the effects of Zn and Cu in Varicosporium elodeae and Heliscus submersus by examining metal adsorption to cell walls, plasma membrane integrity and production of reactive oxygen species at metal concentrations inhibiting biomass production in 50% or 80%. The activity of the enzymes catalase, superoxide dismutase and glucose-6-phosphate dehydrogenase was measured to elucidate their role in coping with oxidative stress induced by metals at short- (14 h) and long- (8 days) term exposure. Results show that V. elodeae was more susceptible to the toxic effects induced by Cu and Zn than H. submersus, as indicated by more extensive inhibition of biomass production. Both metals, particularly Cu, induced oxidative stress in the two fungal species, as shown by the noticeable recovery of biomass production in the presence of an antioxidant agent. In both fungi, Cu induced a more severe disruption of plasma membrane integrity than Zn. Our studies on antioxidant defenses showed that catalase had a greater role alleviating stress induced by Zn and Cu than superoxide dismutase. Chronic metal stress also stimulated the production of NADPH, via the pentose phosphate pathway by increasing the activity of glucose-6-phosphate dehydrogenase. Our results suggest that the tolerance of aquatic hyphomycetes to Cu and Zn is associated with the ability of these fungi to initiate an efficient antioxidant defense system.     

Implications of short and long term (30 days) sorption on the desorption kinetic of trace metals (Cd, Zn, Co, Mn, Fe, Ag, Cs) associated with river suspended matter

The desorption kinetic of trace elements (Cd, Zn, Co, Mn, Fe, Ag, and Cs) associated with Loire river natural suspended particulate matter (SPM; 0.4-63 microm) was followed up on times varying from 0.5 h to 30 days, from SPM previously contaminated during 1 h, 24 h and 30 days. Long term sorption kinetics indicated that the difference between sorption occurring during the period 0-30 days (time investigated in this study) and the period 0-48 h (time often used for sorption experiments) ranges from few to 25% according to the element. Desorption kinetics show that, whatever the age of the complex formed during the sorption step, the release tends to equilibrium between complexed and dissolved elements equivalent to the equilibrium obtained for sorption after a given time. However, the time to get this equilibrium depends on the aging of the complex and on the element. All the above features indicate different types of complexes formation and strength of the binding according to the age of the complex and according to the element. Using a multi-compartmental model, simulating the transfer of metals between water and different types of particulate sites, the relationships between the parameters describing slow and rapid processes helped in explaining the "aging" effect observed.