Heavy metal accumulation in Halimione portulacoides: intra- and extra-cellular metal binding sites

Salt marsh plants can sequestrate and inherently tolerate high metal concentrations found in salt marsh sediments. This work intended to understand the Halimione portulacoides (L.) Aellen strategies to prevent metal toxicity, by investigating the metal location in different plant organs and in the cell. A sequential extraction was performed on leaves, stems and roots of H. portulacoides in order to determine and compare the metal (Zn, Pb, Co, Cd, Ni and Cu) concentration in several fractions of the plant material (ethanolic, aqueous, proteic, pectic, polissacaridic, lenhinic and cellulosic). This study shows that all plant organs of H. portulacoides mostly retain metals in the cell wall (65% is the average for all studied metals stored in the root cell wall, 55% in the stems and 53% in the leaves), and the metal content in the intracellular compartment is much lower (21% in roots, 25% in stems and 32% in leaves). High levels of heavy metal in the sedimentary environment do not cause toxicity to H. portulacoides, because H. portulacoides immobilizes them in different cell compartments (cell wall+proteic fraction+intracellular) outside key metabolic sites.     

Mercury accumulation in surface sediments of salt marshes of the Bay of Fundy

Mercury contamination in Canada's Bay of Fundy is a priority concern because of elevated levels observed in fish, birds and wildlife. Salt marshes constitute an important part of the Bay's coastline and are potential stores of mercury for the region. We measured the amount of mercury accumulated over a 5-yr period from 1997 to 2002 in surface sediments of seven salt marshes along the New Brunswick coast of the Bay. The seven study sites extended from outer to inner Bay, spanning a gradient in tidal range (6-12 m) and sediment characteristics such as %LOI (4-29%) and sediment deposition rate (0.27-1.76 cm yr(-1)). In each study site, mercury was measured in low and high marsh areas. Sediment mercury concentrations ranged from 7 to 79 ng g(-1) and loading rates ranged from 0.1 to 1.1 mg m(-2). Total estimated 5-yr storage of mercury in salt marsh sediments of the Bay is 854+/-465 kg. We also compared sediment mercury loading to atmospheric inputs measured at a deposition monitoring station operating in New Brunswick from 1997 to 2002 and found that direct atmospheric deposition appears to be a minor input of mercury to these sediments. We are unaware of documentation of mercury loading in salt marshes on a bay-wide scale and over a constrained (5-yr) time period elsewhere.     

Mercury mobility in a salt marsh colonised by Halimione portulacoides

The present study intends to increase the knowledge on the mobility of mercury in a salt marsh colonised by Halimione portulacoides. Mercury distribution in the sediment layers and its incorporation into the plant biomass were assessed, as well as the potential export of mercury from the contaminated area to the adjacent environment. Mercury pools in the sediments ranged from 560 to 943 mg m(-2) and are largely associated with the solid fraction, with just a small amount being associated with the pore waters. Estimated diffusive fluxes of reactive mercury ranged from 1.3 to 103 ng m(-2) d(-1). Despite the above ground biomass values being comparatively higher than below ground biomass values, the mercury pools were much higher in the root system (0.06-0.16 mg m(-2) and 29-102 mg m(-2), respectively). The annual bioaccumulation of mercury in above ground tissues was estimated in 0.11 mg m(-2) y(-1), while in below ground biomass the values were higher (7 2mg m(-2) y(-1)). The turnover rates of H. portulacoides biomass suggest higher mercury mobility within the plant rhizosphere. Taking into account the pools of mercury in above ground biomass, the export of mercury by macro-detritus following the "outwelling hypothesis" is not significant for the mercury balance in the studied ecosystem. The mercury accumulated in the below ground part of the plant is quite mobile, being able to return to the sediment pool throughout the mineralisation process.     

Distribution of mercury in the aquatic environment at Almadén,Spain

The world's largest mercury mine is placed at Almadén, Spain. However, there is a lack of information about the environmental impact of these mining activities in the ecosystem that surrounds this area. The aim of this article is to document the concentration of mercury in waters, sediments and bivalves of the aquatic system impacted by historic mine wastes. Simultaneously, a comprehensive study has been undertaken to characterise this hydrosystem and to determine the influence of some major physico-chemical parameters on the fate of mercury. Samplings were carried out for the last few years. Concentration of mercury in waters ranged from not detectable to 20 microg/l. For the sediments study, samples have been taken both from contaminated and non-contaminated sites within the basin. The regional background mercury concentration is higher than values typically cited for natural backgrounds. At exposed sites the mercury concentrations between 5 and 1000 microg/g were measured. These values are one to four order of magnitude greater than regional background levels. In the comparison between the results obtained at the present moment and those available for the 1974-1977 period, a general diminution of mercury levels is observed. Mercury concentrations in fresh water bivalves ranged between 1 and 4 microg/g (d.w.), with around 30% as monomethylmercury. In the discussion of the implications for risk assessment data available for other areas affected both for mine activities and mercuriferous belt are included.     

Mercury in contaminated sediments and pore waters enriched in sulphate (Tagus Estuary,Portugal)

Three sediment cores, collected nearby the effluent of a chlor-alkali industry, were sliced in 0.5-cm layers and centrifuged for pore water extraction. Mercury, Fe and Mn were determined in the solids as total concentration, hydroxylamine extractable fraction and HCl extractable fraction. Sulphur was determined in the HCl extraction. Total and reactive mercury, chlorinity, S(2-), SO(4)(2-), total Fe, and total Mn were measured in pore waters. The solids contained 3.0-60 nmol g(-1) of total Hg and pore waters 70-5800 pM of total Hg and 1.8-76 pM of reactive mercury. Pore waters presented 2.3-94 times more sulphate than the overlying estuarine waters due to the input from the industry. In layers where hydroxylamine extractable Fe exhibited a broad maximum (precipitation of Fe-oxides) sulphate was reduced to S(2-). The competition between the high content of SO(4)(2-) and Fe(III) as electron acceptors, in chemical reactions occurring in the upper sediments, may explain the co-existence of S(2-) and Fe-oxides in the same layers. Mercury was detected in the hydroxylamine extracts (20-29 nmolg(-1)) in the layers where Fe-oxides were formed, and reactive dissolved Hg showed minimum concentrations. The excess of sulphate in pore waters favoured the abundant Fe-oxides in the upper solid sediments, which appear to work as a barrier limiting the escape of mercury to the water column.     

Accumulation and tissue distribution of mercury and selenium in striped dolphins (Stenella coeruleoalba) from the Mediterranean Sea (southern Italy).

Tissues and organs from Stenella coeruleoalba stranded along the Apulian coasts (southern Italy) during the period April-July 1991 were analyzed for their mercury and selenium content. Analysis showed considerable variations in the mercury concentration in the examined organs and tissues. The highest concentrations of mercury were found in the liver (from 2.27 to 374.50 microg g(-1) wet wt.). After the liver, lung, kidney, muscle and brain were the most contaminated, while the lowest mercury contamination was found in the melon. As mercury, the liver also showed the highest selenium levels. Liver samples were also analyzed for their methyl mercury contents. The role of selenium in detoxification process of methyl mercury has been discussed. Mercury concentrations related to geographic variations and pollution of the marine environment have been examined. The possible implications between mercury accumulation and dolphin death have also been discussed.     

EDTA and urease effects on Hg accumulation by Lepidium sativum

The phytoextraction process was conducted under laboratory conditions with the use of garden cress plants (Lepidium sativum). The experiment was carried out in a model soil, which was characterized before conducting the process. Inorganic forms of mercury (HgCl(2), HgSO(4), Hg(NO(3))(2)) were used for contamination of the soil. The phytoextraction process was conducted after EDTA application to the soil and after urease application. Also the influence of simultaneous addition of ethylenediaminetetraacetic acid (EDTA) and urease into the soil on phytoextraction process was measured. In all variants of phytoextraction process the total mercury concentrations in roots, stems and leaves of garden cress were determined. The result showed that garden cress accumulated mercury from soil. The overall maximum concentration of mercury in its compounds was found in roots of the plant. In all cases, before addition of urease and EDTA, the translocation process and distribution of mercury in the plant tissues were limited. The addition of urease caused an increase of enzyme activity in the soil and at the same time caused an increase of mercury concentration in plant tissues. Application of EDTA increased solubility of mercury and caused an increase of metal accumulation by plants. After simultaneous addition of EDTA and urease into the soil garden cress accumulated about 20% of total mercury concentration in the soil. Most of mercury compounds were accumulated in leaves and stems of the plants (46.0-56.9% of total mercury concentration in the plant tissues).     

Removal of pyrene from contaminated sediments by mangrove microcosms

The potential of mangrove wetland systems to remove pyrene from surface- or bottom-contaminated sediments was investigated by microcosm studies. The performance of two mangrove plant species, Kandelia candel and Bruguiera gymnorrhiza in pyrene removal was also compared. During the six-months experimental period, the growth of both species in the surface-contaminated microcosms was not significantly different from that in the bottom-contaminated ones, and was comparable to the control (without any pyrene contamination). At the end of six-months treatment, pyrene concentrations in contaminated sediments declined from an initial 3 microg g(-1) to less than 0.4 microg g(-1), indicating that pyrene was successfully removed by mangrove microcosms. Around 96.4% and 92.8% pyrene in microcosms planted with K. candel were removed from the surface- and bottom-contaminated sediments, respectively. The removal percentages were slightly lower in microcosms planted with B. gymnorrhiza. Significant accumulation of pyrene in roots was only found in microcosms having bottom-contaminated sediments, and pyrene concentrations were 3.05 microg g(-1) and 4.50 microg g(-1) in roots of K. candel and B. gymnorrhiza, respectively. These values were much higher than that in control microcosms (without pyrene contamination, root pyrene concentrations were 0.27 microg g(-1) for K. candel and 0.34 microg g(-1) for B. gymnorrhiza) and in microcosms with contaminated sediments placed at the surface layer. Nevertheless, the overall contribution of root accumulation and plant uptake to the removal of pyrene from contaminated sediments was insignificant.     

Macro, minor and toxic elemental uptake and distribution in Hypoxis hemerocallidea, "the African Potato"--an edible medicinal plant

The elemental uptake and distribution, in various parts of the admired herbal plant, Hypoxis hemerocallidea, the 'African potato' and its ability to accumulate elements in response to the growth soil quality are investigated. The total and exchangeable concentrations of twelve elements in the growth soils and their distribution in the roots, potato bulb and leaves of the plants grown under four different settings were compared. The typical concentrations of the twelve selected elements, in the bulb and leaves of the plant grown in a nursery pot (site 2) were (in microg g(-1)dry weight) Ca (8430 and 27075), Mg (2113 and 1566), Fe (66 and 150), Al (10 and 368), Zn (105 and 6.1), Mn (42 and 51), Cu (7.2 and 20.8), Ba (0.23 and 4.44), Co (0.20 and 0.42), As (2.05 and 24.56), Hg (0.92 and 1.82) and Cr (0.13 and 0.33). Except for Ca, Mg, Zn and Mn, the exchangeable cation concentrations in all the growth soils were low. Ca, Mg, Mn, Zn and As had bioaccumulation factors >1. Fe, Al and Co concentrations were high in the roots with little in the rest of the plant. High concentration of arsenic (approximately 13 microg g(-1) dry weight) with bioaccumulation factors of 7 and 20 were observed in the roots and leaves of the plant respectively (site 2), but the concentration of mercury in bulb was very low (0.92 microg g(-1) dry weight).     

Metal accumulation in aquatic macrophytes from southeast Queensland,Australia

To determine the extent of metal accumulation in some aquatic macrophytes from contaminated urban streams in southeast Queensland, plants were sampled from six sites, along with contiguous sediments. In all, 15 different species were collected, the most common genera being Typha (Cattails or Bulrushes) and Persicaria (Knotweeds). Before heavy metal analysis, plants were further separated into various morphological tissues, and five selected samples were separated into various physiological tissues. The cadmium, copper, lead and zinc content of the plants were analysed using flames AAS. In general, plant roots exhibited higher metal concentrations than the contiguous sediments. Of the metals of interest, only for zinc was there a relatively clear pattern of increasing accumulation in aquatic macrophytes with increasing sediment metal concentrations. Comparison between morphological tissues of the sampled plants found that roots consistently presented higher metal concentrations than either the stems or leaves, however unlike previous studies, this investigation revealed no consistent trend of stems accumulating more metals than the leaves. For Typha spp., metal concentrations followed the order of roots > rhizomes > leaves, while for Persicaria spp. the order was roots > leaves > stems. The submerged species Myriophyllum aquaticum accumulated the highest levels of metals overall (e.g. Zn 4300 micrograms g-1 dry weight and Cd 6.5 micrograms g-1), and the emergent macrophytes also exhibited relatively high metal contents in their roots. The leaves of the submerged and floating-leafed species collected contained relatively high quantities of the four metals of interest, compared with the leaves of emergent aquatic macrophytes. In the Typha rhizome and Persicaria stem samples analysed for internal variation in metal content, there was a pattern of increasing metal concentrations towards the external sections of the stem, both for subterranean stems (rhizomes) and above-substrate stems. For Persicaria stems, no clear pattern was observed for cadmium and lead, the two metals investigated that are not required by plants for survival.     

Total mercury and methylmercury in freshwater and salt marsh soils of the Mississippi river deltaic plain

Mercury entering wetland environments can be microbially methylated to methylmercury. The purpose of this study was to investigate the historical rate of mercury accumulation and distribution of total and methylmercury in soil profile of Louisiana coastal marshes. Two sediment cores each were taken from Louisiana freshwater marsh and salt marsh. Vertical accretion was determined using the 137Cs dating technique. Total and methylmercury were determined with depth in the soil profiles. The fresh marsh soil on a dry weight basis contained more total and methylmercury than the salt marsh. Average vertical accretion rates in freshwater marsh and salt marsh were 0.90 and 0.75 cm year(-1), respectively. Average total and methylmercury content (to a depth of 30 cm) was 140 and 4.19 microg kg(-1) and 80 and 1.34 microg kg(-1) for the fresh and salt marsh, respectively. Due to greater sediment input resulting in a higher bulk density the salt marsh contained more total mercury per m2 (to 30 cm depth) than the fresh water marsh (5340 microg m(-2) as compared to 2929 microg m(-2)). The amount of methylmercury per m2 to depth of 30 cm was approximately the same for each marsh.     

Mercury levels in the plumage of red-billed gulls Larus novaehollandiae scopulinus of known sex and age

Samples of 4-8 small body feathers were taken from 27 chicks and 35 adult red-billed gulls caught at their nests on the Kaikoura Peninsula, New Zealand, in December 1988. The adults had been ringed as chicks and were of known ages from 2 to 15 years old. Analysis of total mercury in the feather samples showed that levels were independent of sex and age in adults. Mean fresh weight concentration in adult body feathers was 2.4 microg g(-1). The lack of age accumulation of mercury in gull feathers contrasts with the well known age related accumulation of mercury in tissues of fish and marine mammals, but agrees with predictions of recent studies on mercury dynamics in birds. Mercury levels in chick feathers were about 80% of levels in adult feathers.     

Uptake and accumulation of mercury from dental amalgam in the common goldfish,Carassius auratus

In this study, the bioavailability and accumulation of mercury from external environmental exposure to mixed, cured, milled, sieved and proportioned dental amalgam was examined in the common goldfish, Carassius auratus. Fish were exposed to dental amalgam (particle size range from < 0.10 to 3.15 mm) in order to represent the particle size and distribution of that found within the typical dental office wastewater discharge stream. Experimental amalgam water loadings were 0 g/l, 0.5 g/l and 1 g/l in glass aquaria at 15 degrees C for 28 days. Fish tissues were sampled at 5 min and 28 days of exposure, and the liver, brain, muscle and whole body analyzed for total mercury using cold vapor atomic fluorescence spectroscopy. Mercury was found in several tissues examined and generally increased with exposure to higher amounts of dental amalgam. The highest levels were found in the whole body (17.68 +/- 5.73 microg/g) followed by the liver (0.80 +/- 0.16 microg/g) and muscle (0.47 +/- 0.16 microg/g). The lowest concentrations were seen in the brain (0.28 +/- 0.19 microg/g). Compared to controls, concentrations in the whole body, muscle and liver in fish exposed for 28 days to the highest concentration of amalgam were 200-, 233-, and 40-fold higher, respectively. This study shows that mercury from an environmental exposure to representative samples of dental amalgam typically found within the dental wastewater discharge stream is bioavailable to fish and may accumulate in internal tissues.     

The influence of Sarcocornia fruticosa on retention of PAHs in salt marsh sediments (Sado estuary, Portugal)

Depth concentration profiles of PAHs, organic carbon and dissolved oxygen in non-colonised sediments and sediments colonised by Sarcocornia fruticosa from Mitrena salt marsh (Sado, Portugal) were determined in November 2004 and April 2005. Belowground biomass and PAH levels in below and aboveground material were also determined. In both periods, colonised sediments were oxygenated until 15-cm, rich in organic carbon (max 4.4%) and presented much higher PAH concentrations (max. 7.1 microg g(-1)) than non-colonised sediments (max. 0.55 microg g(-1)). Rooting sediments contained the highest PAH concentrations. The five- and six-ring compounds accounted to 50-75% of the total PAHs in colonised sediments, while only to 30% in non-colonised sediments. The elevated concentrations of PAHs in colonised sediments may be attributed to the transfer of dissolved PAH compounds towards the roots as plant uptake water and subsequent sequestration onto organically rich particles. A phase-partitioning mechanism probably explains the higher retention of the heavier PAHs. In addition oxygenated conditions of the rooting sediments favour the degradation of the lighter PAHs and explain the elevated proportion of the heavier compounds. Below and aboveground materials presented lower PAH concentrations (0.18-0.38 microg g(-1)) than colonised sediments. Only 3- and 4-PAHs were quantified in aboveground material, reflecting either preferential translocation of lighter compounds from roots or atmospheric deposition.     

Mercury cycling in surface water, pore water and sediments of Mugu Lagoon, CA, USA

Mugu Lagoon is an estuary in southern California, listed as impaired for mercury. In 2005, we examined mercury cycling at ten sites within at most four habitats. In surface water (unfiltered and filtered) and pore water, the concentration of total mercury was correlated with methylmercury levels (R2=0.29, 0.26, 0.27, respectively, p<0.05), in contrast to sediments, where organic matter and reduced iron levels were most correlated with methylmercury content (R2=0.37, 0.26, respectively, p<0.05). Interestingly, levels for percent methylmercury of total mercury in sediments were higher than typical values for estuarine sediments (average 5.4%, range 0.024-38%, n=59), while pore water methylmercury Kd values were also high (average 3.1, range 2.0-4.2l kg(-1), n=39), and the estimated methylmercury flux from sediments was low (average 1.7, range 0.14-5.3ng m(-2) day(-1), n=19). Mercury levels in predatory fish tissue at Mugu are >0.3ppm, suggesting biogeochemical controls on methylmercury mobility do not completely mitigate methylmercury uptake through the food web.     

Influence of cadmium on antioxidant capacity and four microelement concentrations in tomato seedlings (Lycopersicon esculentum)

Tomato (Lycopersicon esculentum) seedlings were grown in four cadmium (Cd) levels of 0-10 microM in a hydroponic system to analyze the antioxidative enzymes, Cd concentration in the plants, and the interaction between Cd and four microelements. The results showed that there was a significant increase in malondialdehyde (MDA) concentration, and superoxide dismutase (SOD) and peroxidase (POD) activities in the plants subjected to 1-10 microM Cd. This indicates that Cd stress induces an oxidative stress response in tomato plants, characterized by an accumulation of MDA and increase in activities of SOD and POD. Root, stem and leaf Cd concentrations increased with its exposure Cd level, and the highest Cd concentration occurred in roots, followed by leaves and stems. A concentration- and tissue-dependent response was found in the four microelement concentrations to Cd stress in the tomato leaves, stems and roots. Regression analysis showed that there was a significantly negative correlation between Cd and Mn, implying the antagonistic effect of Cd on Mn absorption and translocation. The correlation between Cd and Zn, Cu and Fe were inconsistent among leaves, stems and roots.     

Distribution of PCDD/Fs and dioxin-like PCBs in sediment and plants from a contaminated salt marsh (Tejo estuary,Portugal)

Concentrations and profiles of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in sediment and plants collected from a salt marsh in the Tejo estuary, Portugal. The highest PCDD/F and dl-PCB concentrations were detected in uncolonized sediments, averaging 325.25?±?57.55 pg g^?1 dry weight (dw) and 8,146.33?±?2,142.14 pg g^?1 dw, respectively. The plants Sarcocornia perennis and Halimione portulacoides growing in PCDD/F and dl-PCB contaminated sediments accumulated contaminants in roots, stems, and leaves. It was observed that PCDD/F and dl-PCB concentrations in roots were significantly lower in comparison with stems and leaves. In general, concentration of ΣPCDD/Fs and Σdl-PCBs in H. portulacoides tissues were found to be twofold higher than those in S. perennis, indicating a difference in the accumulation capability of both species. Furthermore, congener profiles changed between sediments and plant tissues, reflecting a selective accumulation of low chlorinated PCDD/Fs and non-ortho dl-PCBs in plants.     

Geothermal power plants at Mt. Amiata (Tuscany-Italy): mercury and hydrogen sulphide deposition revealed by vegetation

At Mt. Amiata (Italy) geothermal energy is used, since 1969, to generate electricity in five plants with a nominal capacity of 88 MW. Anomalous levels of mercury characterise geothermal fluids of Mt. Amiata, an area renowned for its vast cinnabar deposits and for the mercury production carried out in the past. Mercury emission rates range from 300 to 400 g/h, or 3-4 g/h per MW electrical installed capacity. These emissions are coupled with a release of 7-8 kg/(h MW) of hydrogen sulphide (H2S). Mercury is discharged as Hg0 gaseous species and reaches the atmosphere with the non-condensable gas fraction. In this fraction, CO, is the major component (94-98%), H2S is around 1% and mercury concentration is as high as 1-10 mg/Nm3. Leaves of a spontaneous grass (Avena sterilis), at the end of the vegetative cycle, were used as mercury bioconcentrators to map deposition near geothermal power plants and to calculate the corresponding average levels of Hg0 in the air. Direct measurements of mercury and hydrogen sulphide vapours in the air reached by power plant emissions showed a ratio of about 1-2000. This ratio was applied to calculate average levels of hydrogen sulphide starting from mercury deposition mapping: typical concentrations of mercury and hydrogen sulphide were of the order of 10-20 ng/m3 and 20-40 microg/m3, respectively.     

Distribution of mercury in the organs and tissues of five toothed-whale species of the Mediterranean

Mercury levels were determined in the tissues and organs (lung, liver, kidney, skin, muscle, bone) of five toothed-whales stranded along the Corsican coast between November 1993 and February 1996. The species taken into consideration were the bottlenose dolphin Tursiops truncatus, the common dolphin Delphinus delphis, the striped dolphin Stenella coeruleoalba, the pilot whale Globicephala melas and the Risso's dolphin Grampus griseus. The variation in mercury levels between the different tissues and organs (lung, liver, kidney, skin, muscle, bone) of the cetacean species are discussed as regards storage, biotransformation and elimination. In all cases, the liver appears to be the preferential organ for mercury accumulation (with concentrations as high as 4250 microg Hg/g dw and 3298 microg Hg/g in the livers of Tursiops truncatus and Grampus griseus, respectively). The kidney and lung are the next organs in terms of mercury uptake followed by the muscle, bone and skin. The stomach contents of Grampus griseus and D. delphis were determined and consisted of cephalopods for Grampus griseus, and of sardines Sardina pilchardus and mackerels Trachurus sp. for D. delphis. Cephalopods had higher mercury concentrations (25.4 microg Hg/g dw) than fish (ca 1 microg Hg/g). These contents represent only one meal and mercury levels found in livers may integrate mercury uptake having occurred during the whole life span of animals.     

Halophyte vegetation influences in salt marsh retention capacity for heavy metals

We analysed concentrations of Cu, Cd and Pb in above and belowground tissues of the halophyte species Halimione portulacoides and Spartina maritima, as well as in sediments and pore water between the roots in a Tagus estuary salt marsh (Portugal). From these results we calculated the pools of metals in the compartments mentioned above. Relative percentages of accumulation in each pool were also determined. Our aim was to determine how the type of vegetation in the salt marsh affects overall metal retention capacity of the system. It was concluded that areas colonised by H. portulacoides are potential sources of Cu, Cd and Pb to the marsh ecosystem, whereas areas colonised by S. maritima are more effective sinks at least for Cu and Cd. Consequently, S. maritima seems to contribute more effectively to the stabilisation of metals in salt marsh sediments, reducing their availability to the estuarine system.