Accumulation and distribution of platinum and rhodium in the European eel Anguilla anguilla following aqueous exposure to metal salts

The platinum group metals (PGM) Pt and Rh are emitted into the environment mainly by catalytic exhaust gas converters of cars and by effluents of hospitals, which use Pt based anti-cancer drugs. However, there is still a lack of information on the availability of these precious metals to the biosphere. As PGM accumulate in sediments of aquatic ecosystems we focused our study on the uptake of the noble metals by European eels, Anguilla anguilla. Therefore, eels were exposed in tap water and humic water containing Pt(4+) and Rh(3+) at a concentration of 170 and 260 microg/l, respectively. After an exposure period of 6 weeks the mean Pt levels in bile, liver, kidney and intestine of the exposed eels ranged between 68 ng/g and 840 ng/g and the mean Rh levels between 35 ng/g and 155 ng/g whereas the PGM levels of the unexposed controls were below the detection limit of 50 ng/g for Pt and 5 ng/g for Rh. Rh was also taken up by gill and spleen. No PGM uptake was found for muscle and blood. The pattern of metal distribution within the eel differed between Pt and Rh and was dependent on the water type. Due to their accumulation capacity for PGM eels are suitable as accumulation indicators to detect PGM pollution in aquatic ecosystems.     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Comparison of palladium and platinum in environmental matrices: Palladium pollution by automobile emissions?

A new type of automobile catalyst based on an active Pd/Rh-layer is presently being introduced into the European market. Accordingly, in order to establish baseline information, this work attempts to assess the magnitude of Pd emissions by automobile catalysts to date. Thus, a survey is presented on Pd and Pt levels detected in polluted environmental matrices (grass, soil, dust, sludges) as available from the literature. Additionally, Pd data measured by selective preconcentration/GF-AAS-detection in polluted grass, in a time series of sewage sludge ashes back to 1972, in dust, as well as in urban rain are presented. Since the data basis from the literature is partly inconsistent, the possible impact of different analytical attempts on the data is discussed. The relationship between Pt and Pd concentration from most of the results is between 5 and 10 (Pt/Pd). However, relations down to 0.04 are also reported, thus implying anthropogenic Pd input from additional sources.     

Oxidative stress, liver biotransformation and genotoxic effects induced by copper in Anguilla anguilla L.--the influence of pre-exposure to beta-naphthoflavone

Fish are exposed in the aquatic ecosystems to different classes of pollutants. Polycyclic aromatic hydrocarbons (PAHs) and heavy metals represent two important classes of aquatic contaminants. Thus, one lot of European eels (Anguilla anguilla L.) was pre-exposed during 24 h to 2.7 microM beta-naphthoflavone (BNF; a PAH-like compound), and subsequently exposed during 24 h to 0, 1 and 2.5 microM copper (Cu). Additionally, another lot not pre-exposed to BNF was exposed to the same Cu concentrations. BNF pre-exposure promoted a significant increase in liver ethoxyresorufin O-deethylase (EROD) activity, but did not change the other responses investigated in eels. On the other hand, both Cu concentrations did not modify the liver EROD activity either in eels pre-exposed to BNF or not. Liver total cytochrome P450 was increased in eels exposed to Cu 2.5 microM, being significantly only in eels not pre-exposed to BNF. Free sulfhydryl group content was decreased by 1 and 2.5 microM in eels pre-exposed to BNF or not pre-exposed, being significant at 2.5 microM Cu in eels not pre-exposed compared to its control. Liver total glutathione (TG), reduced glutathione (GSH) and GSH/oxidized glutathione (GSSG) levels were slightly decreased by 1 and 2.5 microM Cu in eels pre-exposed to BNF, whereas a slight tendency to increase was observed in eels not pre-exposed. Thus, liver TG and GSH significantly decreased in 2.5 microM Cu BNF pre-exposed eels compared to eels not pre-exposed to BNF. Liver glutathione reductase and catalase activities were significantly inhibited by 1 and 2.5 microM Cu in eels pre-exposed to BNF, concomitantly with a slight liver glutathione peroxidase tendency to decrease. Lipid peroxidation was significantly increased by 1 microM Cu in eels either pre-exposed or not pre-exposed to BNF. Liver H(2)O(2) was significantly increased by 1 microM Cu in eels pre-exposed to BNF. Liver DNA integrity was significantly decreased by 1 and 2.5 microM Cu in eels pre-exposed to BNF. The oxidative stress and genotoxic effects induced by Cu in eels pre-exposed to BNF revealed that the metal effects are potentiated by previous exposure to BNF.     

Significance of platinum group metals emitted from automobile exhaust gas converters for the biosphere

Intention, Goal, Scope, Background  Following the introduction of automobile catalytic converters the platinum group metals (PGM) platinum (Pt), palladium (Pd) and rhodium (Rh) gain on increasing interest in environmental research as these metals are emitted with exhaust fumes into the environment. Consequently, elevated PGM levels were found in different environmental matrices uch as road dusts, soils along heavily frequented roads, sediments of urban rivers etc. Accordingly, the effects of increasing PGM emissions on the biosphere are controversially discussed. Objective  This paper summarizes the present knowledge on the biological availability of PGM to plants and animals. As biological availability is one of the most decisive factors determining the toxicologi-cal potential of xenobiotics, this information is very important to evaluate the possible threat of the noble metals to ecosystems. Results and Discussion  The availability of soluble as well as particle bound PGM to terrestrial plants was demonstrated in several studies. Experimental investigations revealed uptake of Pt, Pd and Rh also by aquatic plants. Additionally, the biological availability of the noble metals for animals has been verified in experimental studies using soluble metal salts, catalytic converter model substances, sediments of urban rivers, road dust or tunnel dust as metal sources. These studies refer mainly to aquatic animals. Beside of free living organisms, in particular worms parasitizing fish demonstrated a high potential to accumulate PGM. This could be of great interest in respect of biomonitoring purposes. Generally, for plants as well as for animals Pd turns out to be the best available metal among the PGM. Compared to other heavy metals, the biological availability of PGM from road dust to zebra mussels(Dreissena polymorpha) ranged between that of Cd and Pb. Conclusion  Especially chronic effects of PGM on the biosphere can not be excluded due to (1) their cumulative increase in the environment, (2) their unexpected high biological availability and bioaccumulation and (3) their unknown toxicological and ecotoxicological potential. However, it appears that acute effects on ecosystems due to anthropogenic PGM emission are not likely. Recommendation and Outlook  Research on environmental PGM contamination of the biosphere, especially the fauna, and on long-term toxiciry of low PGM concentrations is highly appreciated. These studies require very sensitive analytical techniques to determine PGM even in low sample amounts. Research has to be done in particular on reliable determination of (ultra) trace levels of Pd and Rh as the lack of data on these two metals is mainly due to analytical problems.     

Platinum and Palladium transfer to milk, organs and tissues after a single oral administration to lactating goats

Platinum (Pt) and Palladium (Pd) are massively used in catalytic converters, emitted with exhaust fumes and deposited on roadsides in particle sizes. If they are ingested by ruminants grazing in agricultural fields located along roads they may enter the food chain. The objective of this study is to assess the potential transfer of Pt (PtCl(2)) and Pd (PdCl(2)) towards milk, tissues (muscle) and organs (kidney, liver and mammary gland). Three lactating goats received orally a single dose of 200mg of Pd and 200mg of Pt at the beginning of the experiment. The milk was collected each day during eight days. On the eighth day, organs and tissues were sampled to analyse the metal concentrations by ICP-MS (quantification limit of 0.25ng/g for Pd and Pt, detection limit of 0.08ng/g). The experiment demonstrated a significant transfer of Pd and Pt to kidney. The detected concentration was, respectively, of 73.9ng/g DW and 268.5n/g DW (factor 22 and factor 73 compared to the control kidney). The amounts of metals were : in the liver,18.1ng/g DW for the Pd and 8.1ng/g DW for the Pt, in the mammary gland, 14.9ng/g DW fort the Pd and 2.5ng/g DW for the Pt and in the muscle, 4.9ng/g DW for the Pd and 0.6ng/g DW for the Pt. The Pd concentration detected in milk was higher (from 5ng/g DW to 9ng/g DW) than in control milk but the transfer factor remained very low (0.02%). The Pt in milk could not be detected because it was below the quantification limit (<0.25ng/g DW).     

Selective supercritical fluid extraction to identify aged sediment-bound PCBs available for uptake by eel

A naturally contaminated sediment was partially extracted with selective supercritical fluid extraction (SFE) to remove a fraction of supposedly bioavailable PCBs from the matrix. Eels (Anguilla anguilla) were cultured in systems with untreated and pre-extracted sediment, respectively, and it was shown that the SFE treatment selectively removed bioavailable PCBs from the sediment, since relative biota-to-sediment accumulation factors (BSAFs) for the eight studied PCB congeners were much lower in the pre-extracted than in the untreated system at the end of the study. Relative BSAF values decreased with about the same relative amount for all eight congeners, independent of the degree of chlorination and the initial concentration in the sediment. The results demonstrate the ability of SFE to selectively remove sediment-bound PCBs that are available for uptake by the eels, thus demonstrating the feasibility of using selective SFE to estimate bioavailability of PCBs in sediments.     

How accurately do semi-permeable membrane devices measure the bioavailability of polycyclic aromatic hydrocarbons to Daphnia magna?

Semi-permeable membrane devices (SPMDs) are passive samplers that have been designed to sample the bioavailable fractions of hydrophobic organic compounds in aquatic ecosystems. This study aims at evaluating the ability for SPMD to sample polycyclic aromatic hydrocarbons (fluoranthene, pyrene and benzo[a]pyrene) that are actually bioavailable to Daphnia magna. For that purpose, the SPMD-available fraction and the bioavailable fraction to D. magna are compared in controlled media with Dissolved Organic Matters (DOMs) from various origins and at different concentrations. The presence of all but one DOM reduces the accumulation of PAHs in SPMD or in D. magna. Moreover, this comparative laboratory study shows that in 10 cases on 13, the SPMD-available fraction is close to the available fraction to D. magna. When significant differences are observed between SPMD-available and bioavailable fractions, they remain less than 50% at DOM concentrations below 10 mg/l DOC, which corresponds to a maximum DOC concentration usually found in temperate rivers. This study confirms the suitability of the SPMD technique to monitor readily bioavailable hydrophobic contaminants in aquatic environments containing DOM from various origins and characteristics.     

Decabromodiphenylether and hexabromocyclododecane in wild birds from the United Kingdom, Sweden and The Netherlands: Screening and time trends

The brominated flame retardant decabromodiphenylether (DBDE) was analysed in wild birds to identify the most suitable species for monitoring time trends in DBDE contamination. This information was later used for the design of a 10-year trend study on DBDE in the European Union. DBDE was measured in muscle tissue, liver, and eggs from 10 terrestrial and four aquatic bird species. DBDE was detected in 47% of the terrestrial bird samples (nine species) and in 9% of the aquatic bird samples (six species). Peregrine falcon and sparrowhawk specimens were selected as most suitable species to determine temporal trends of DBDE. For sparrowhawks, no significant change in DBDE concentrations between 1973 and 2001 was found, although in later years more DBDE concentrations were above the detection limit. Peak DBDE levels measured in peregrines in 1995, were followed by a decline in concentrations until 2001. The same species were used for a trend study on hexabromocylcododecane (HBCD). Twenty-four percent of peregrine falcon eggs and 12% of sparrowhawk muscle samples demonstrated measurable HBCD residues. Three diastereomers of HBCD were analysed and the α-diastereomer was the predominant one in most samples. No clear time trends were observed for HBCD in either species. This study demonstrated that these DBDE and HBCD are bioavailable to birds of Northern Europe, although bioaccumulation seems to occur to a limited extent.     

Glutathione-dependent resistance of the European eel Anguilla anguilla to the herbicide molinate.

Eels of species Anguilla anguilla were exposed to 5/4 LC50 (41.8 mg/l) of the herbicide molinate for 96 h in a time to death (TTD) test. Glutathione content (GSx, GSH, GSSG), glutathione reductase (GR) and gamma-glutamyl transpeptidase (gamma-GT) activities were determined in the liver and muscle tissues of dead and surviving (intoxicated) animals and compared to control values (non-exposed eels). TTD was positively correlated to hepatic GSH, GSH:GSSG ratio, hepatic and muscular GR, but negatively correlated to muscular GSH, which was severely depleted. Furthermore, glutathione and enzyme activities were intercorrelated, especially GSH and GR. These results indicate that eels which were able to induce GR activity, increase GSH and maintain the GSH:GSSG ratio in the liver showed an extended survival under the oxidative stress generated by molinate than those that lost glutathione homeostasis.     

Predator-prey interactions between Synbranchus marmoratus (Teleostei: Synbranchidae) and Hypsiboas pulchellus tadpoles (Amphibia: Hylidae): importance of lateral line in nocturnal predation and effects of fenitrothion exposure

Environmental contaminants can disrupt interactions between aquatic species by altering community structure. We explored predator-prey interactions between marbled swamp juvenile eels (Synbranchus marmoratus; predator) and anuran tadpoles (Hypsiboas pulchellus; prey) in relation to two aspects: the importance of lateral line in the predator and whether the absence of light modifies predation rates; and the effect of a sub-lethal concentration of fenitrothion on both predator and prey. Eels were tested under two sensory conditions (lateral line intact and lateral line blocked by cobalt chloride) in dark conditions. Predation rates were evaluated using different treatments that combined predator and prey exposed or not to insecticide. Acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were also measured in muscle samples of eels and tadpoles to explore whether fenitrothion affects predator and prey differentially. Marbled swamp eels were more efficient in feeding on tadpoles during the night than during the day, showing that lateral line makes an important contribution to prey detection and capture. Regarding pesticide effects, short-term (6 h) exposure to an ecologically relevant fenitrothion dose of 2.5 mg L(-1) altered the predator-prey relationship by changing prey behaviour, reducing prey detection and therefore increasing tadpole survival. At this concentration, the outcome of the predator-prey relationship appears biased in favor of the exposed tadpoles, which were released from predation risk, despite their altered behaviour and the higher inhibition percentages of tail BChE (70%) and AChE (51%) than in control individuals. Our study involving these model species and agrochemicals demonstrates that fenitrothion affected the outcome of a predator-prey relationship. Further studies are needed, in these species and other native amphibians, to investigate the nature of the mechanisms responsible for the adverse effects of pesticides on antipredator behaviour and predation efficiency.     

Gemfibrozil modulates cytochrome P450 and peroxisome proliferation-inducible enzymes in the liver of the yellow European eel (Anguilla anguilla)

The human lipid regulator gemfibrozil (GEM) has been shown to induce peroxisome proliferation in rodents leading to hepatocarcinogenesis. Since GEM is found at biological active concentrations in the aquatic environment, the present study investigates the effects of this drug on the yellow European eel (Anguilla anguilla). Eels were injected with different concentrations of GEM (0.1 to 200 μg/g) and sampled 24- and 96-h post-injection. GEM was shown to inhibit CYP1A, CYP3A and CYP2K-like catalytic activities 24-h post-injection, but at 96-h post-injection, only CYP1A was significantly altered in fish injected with the highest GEM dose. On the contrary, GEM had little effect on the phase II enzymes examined (UDP-glucuronyltransferase and glutathione-S-transferase). Peroxisome proliferation inducible enzymes (liver peroxisomal acyl-CoA oxidase and catalase) were very weakly induced. No evidence of a significant effect on the endocrine system of eels was observed in terms of plasmatic steroid levels or testosterone esterification in the liver.     

Occurrence of platinum and additional traffic related heavy metals in sediments and biota

Non-point sources play an important role in metal emissions into surface waters. One of the most important non-point sources is automobile traffic. Recent studies determining traffic related heavy metals in surface waters have concentrated mainly on worst case scenarios by analyzing heavy metal loads in waters and sediments close to storm-water overflow inlets. The present study aims at identifying traffic related heavy metals in moderately polluted sites, as they occur in highly urbanized regions. Therefore, the concentrations of eight traffic related metals (Pt, Sb, Mo, Cd, Pb, Cu, Cr and Zn) were determined in sediment and crustacean samples from eight different aquatic habitats in the Ruhr district, Germany. Traffic related heavy metals could be identified in sediment and biota samples as a combination of heavy metals (Pt, Sb, Cd, Pb for sediments and Pt and Sb for crustacean samples). Pt concentrations received special attention due to the relatively recent occurrence of anthropogenically emitted Pt in the environment. At six sampling sites, Pt was detected in sediment and/or biota samples. The uptake of Pt compared to other traffic related heavy metals by Asellus aquaticus and Gammarus pulex is relatively high and can be compared with the uptake rates of essential metals like Zn.     

Lead contamination in tea garden soils and factors affecting its bioavailability

The consumption of heavy metals is detrimental to human health and most countries restrict the concentration of metals such as lead (Pb) in food and beverages. Recent tests have detected high Pb concentrations in certain commercial brands of tea leaves and this finding has raised concerns for both producers and consumers. To investigate what factors may be contributing to the increase in Pb accumulation in the tea leaves we collected tea leaves and soils from tea producing areas and analyzed them for Pb concentration, pH and organic matter content. The result showed the Pb concentration of 47% investigated tea leaves samples was beyond 2 mg kg(-1), the permissible levels given by China. The total Pb concentration in the surface and subsurface soil layers averaged 36.4 and 32.2 mg kg(-1), respectively which fall below of the 60 mg kg(-1) limit provided for organic tea gardens in China. The pH of the tea garden soils was severely acidic with the lowest pH of 3.37. Soils under older tea gardens tended to have a lower pH and a higher Pb bioavailability which was defined as the amount of lead extracted by CaCl2 solution than those under younger tea gardens. We found that the concentration of bioavailable Pb and the percentage of bioavailable Pb (bioavailable Pb relative to total Pb concentration) were positively correlated with soil H+ activity and soil organic matter content, and the organic matter accumulation contribute more effects on Pb bioavailability in these two factors. We conclude that soil acidification and organic matter accumulation could contribute to increasing Pb bioavailability in soil and that these could increase Pb uptake and accumulation in the tea leaves.     

Histopathological effects of chronic aqueous exposure to bis(tri-n-butyltin)oxide (TBTO) to environmentally relevant concentrations reveal thymus atrophy in European flounder (Platichthys flesus)

Although the use of tributyltin in antifouling paints has been banned, this compound is still a serious pollutant of the marine environment. This paper describes a unique study in which European flounder (Platichthys flesus) were chronically (8 months) exposed to bis(tri-n-butyltin)oxide (TBTO) in the water under controlled laboratory conditions. Residue levels in selected tissues (liver, muscle) and general health status indices were measured and the effects on several organs (gills, liver, mesonephros, ovary/testis, spleen, and gastrointestinal tract) were examined histopathologically. Additionally, morphometric analysis of the thymus was performed. The major finding is that exposure of flounder to 5 μg TBTO/l over a period of 8 months, resulting in body burdens comparable to high field levels, induced significant reduction of thymus volume, possibly affecting immunocompetence of the animals. Chronic exposure of European flounder to tributyltin is therefore likely to affect the general health status of this species in heavily polluted aquatic environments.     

Low levels of persistent organic pollutants (POPs) in New Zealand eels reflect isolation from atmospheric sources

Polychlorinated biphenyls (PCBs) and organic pesticides (i.e., DDTs) were measured in long finned eels (Anguilla dieffenbachii) in 17 streams on the west coast of South Island, New Zealand. Very low levels of PCBs and low levels of ppDDE were found. The concentrations of PCBs and ppDDE were not correlated within sites indicating that different processes determined the levels of the two pollutants in New Zealand eels. The PCBs probably originate from atmospheric transport, ppDDE levels are determined by land use and are higher in agriculture areas. The low contamination level of these aquatic systems seems to be a function of a low input from both long and short-range transport as well as few local point sources. No correlation could be found between lipid content and persistent organic pollutants (POPs) concentration (as shown in previous studies) in the eels which could be explained by low and irregular intake of the pollutants.     

Managing Swedish forestry’s impact on mercury in fish: Defining the impact and mitigation measures

Inputs of anthropogenic mercury (Hg) to the environment have led to accumulation of Hg in terrestrial and aquatic ecosystems, contributing to fish Hg concentrations well above the European Union standards in large parts of Fennoscandia. Forestry operations have been reported to increase the concentrations and loads of Hg to surface waters by mobilizing Hg from the soil. This summary of available forestry effect studies reveals considerable variation in treatment effects on total Hg (THg) and methylmercury (MeHg) at different sites, varying from no effect up to manifold concentration increases, especially for the bioavailable MeHg fraction. Since Hg biomagnification depends on trophic structures, forestry impacts on nutrient flows will also influence the Hg in fish. From this, we conclude that recommendations for best management practices in Swedish forestry operations are appropriate from the perspective of mercury contamination. However, the complexity of defining effective policies needs to be recognized.     

A review of neurotoxicity of microcystins

Cyanobacterial blooms-produced microcystins are secondary metabolites which can accumulate in the food chain and contaminate water, thus posing a potential threat to the health of aquatic animals and even humans. Microcystin toxicity affects not only the liver but also the other organs, i.e., the brain. The serious neurotoxicity effects caused by microcystins then lead to various symptoms. This review focuses on the neurotoxicity of microcystins. Microcystins can cross blood-brain barrier with the transport of Oatps/OATPs, causing neurostructural, functional, and behavioral changes. In this review, potential uptake mechanisms and neurotoxicity mechanisms are summarized, including neurotransmissions, neurochannels, signal transduction, oxidative stress, and cytoskeleton disruption. However, further researches are needed for detailed studies on signaling pathways and the downstream pathways of neurotoxicity of microcystins.     

Copper bioavailability in the rhizosphere of maize (Zea mays L.) grown in two Italian soils

In this study, potentially bioavailable copper was estimated in two soils (a fungicide polluted and a natural soil) using a passive sampling technique, DGT. As plants can alter copper mobility and bioavailability in the soil, the rhizosphere properties of Zea mays L. were investigated using rhizoboxes.

Compared to the total concentration, the soluble and the potentially bioavailable copper concentration in the bulk soils were generally low (less than 0.20% and 0.06% respectively), with a sixfold increase in the rhizosphere of the polluted soil. Our results suggest that maize cultivation in a polluted vineyard soil could increase the potentially available fraction of copper. DGTs showed a good sensitivity to soil properties and to root-induced changes in the rhizosphere, but the potentially bioavailable copper could not be related to the copper concentration in the above ground parts of maize. The results suggest that DGT may be used to predict some effects of the cultivation of polluted soils, for example, metal mobility and increased availability, but they cannot mimic the uptake of a tolerant plant.

For both soils, dissolved organic carbon (DOC) concentrations were threefold higher in the rhizosphere than in the bulk soil, whilst bioaccumulation in leaves and roots was not significant. DOC production, usually effective in ion mobilization and assimilation, may help also in the reduction of Cu uptake at toxic concentrations. The sequestration of available Cu in soil and soil solution by DOC seems to contribute to maize tolerance.