No abstract

The influence of the provenance soil and vinification process on the wine multielemental composition was investigated. For this purpose, two different vineyards from the Douro wine district, Portugal, were selected. Monovarietal grapes from a 10 year old vineyard were used to produce a red table wine, in a very modern winery. Polyvarietal grapes from a 60-70 year old vineyard were used to produce a red fortified wine, similar to Port, through a traditional vinification process. The multielement compositions (Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cs, Cu, Fe, Ga, Hf, Li, Mn, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sr, Ti, Th, Tl, U, V, W, Y, Zn, Zr, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) of soil, grape juices (prepared in the laboratory), and samples collected in the different steps of each winemaking process were measured. Inductively coupled plasma mass spectrometry was used, after suitable pretreatment of the samples (by UV irradiation for liquid samples and high-pressure microwave digestion for soil). Both vinification processes influenced the multielement composition of the wines. Most of the elements presented similar or even lower concentrations in the wine as compared to that observed in the respective grape juice, probably as a result of precipitation or coprecipitation with suspended particles during fermentation and/or wine aging. Evidence of effective contamination during grape pressing, fermentation, and/or fining of wines (depending on the element) was observed for Cd, Cr, Cu, Fe, Ni, Pb, V, and Zn in the fortified wine and Al, Cr, Fe, Ni, Pb, and V in the table wine. Nevertheless, significant correlations were obtained between the multielement composition of the wine and the respective grape juice (R = 0.997 and 0.979 for the fortified and table wines, respectively, n = 31, P < 0.01), as well as between that in the wine (median of the two studied wines) and the provenance soil (R = 0.994, n = 19, P < 0.01), for the set of elements determined in common in the different types of samples. These results are promising concerning the usefulness of the elemental patterns of both soil and wine as fingerprints of the origin of the studied wines. Nevertheless, more wines from the same and other wine districts must be studied in order to consolidate this conclusion. The multielement compositions of the studied wines were compared with those of wines of different characteristics and origins, as well as with the respective legal threshold limit values, when available. Relatively low metal levels, below their threshold limit values, were found in all cases.

Marine microalgae (Emiliania huxleyi) were grown in seawater enriched only with nitrogen and phosphorus, without control of free metal concentrations using synthetic chelators. Complexing ligands and thiol compounds were determined by cathodic stripping volt-ammetry. Copper was added to these cultures, and ligands were produced in response to the copper addition. Parallel measurements of thiols showed that glutathione and other unidentified thiols (electrochemically similar to thioacetamide) were produced by the algae at rates and concentrations similar to those of the complexing ligands. Smaller amounts of thiols were produced when ligands including thiols were added to the culture. The results indicate that thiols can account for a major part or most of the copper-complexing ligands produced by these algae. Furthermore, a feedback mechanism exists in which the production of thiol-type complexing ligands is controlled by the free copper concentration, production already being stimulated by an increase of [Cu 2ϩ ] from 0.4 to 1.5 pM. Incubations with added exudates, thiols, and salicylaldoxime (SA) showed much reduced copper toxicity even though copper uptake was increased by the exudates and the SA.Culture experiments have shown that marine and freshwater phytoplankton release complexing ligands into culture medium (e.g., van den Berg et al. 1979;Imber and Robinson 1983), which may be important because the availability of metals to algae is known to depend on their chemical composition (e.g., Brand et al. 1983). Therefore, the interaction of phytoplankton with trace metals is reciprocal: the biota affect the trace metal chemistry and the trace metals affect the biota.Using marine algal cultures where the metal chemistry was controlled by a synthetic chelator (usually ethylenediaminetetraacetic acid [EDTA]), the biological uptake of copper has been shown to be related to the cupric ion concentration, [Cu 2ϩ ] (e.g., Brand et al. 1986); toxicity occurs at pM levels of Cu 2ϩ . The concentration of Cu 2ϩ is typically lowered by by 2-3 orders of magnitude by organic complexation in seawater to a [Cu 2ϩ ] of 0.03-0.3 pM, which is thought to be sufficiently high to meet algal nutritional requirements but is below copper toxicity levels (Sunda 1995).

Freshwater cyanobacteria produce several bioactive secondary metabolites with diverse chemical structure, which may achieve high concentrations in the aquatic medium when cyanobacterial blooms occur. Some of the compounds released by cyanobacteria have allelopathic properties, influencing the biological processes of other phytoplankton or aquatic plants. These kinds of interactions are more easily detectable under laboratory studies; however their ecological relevance is often debated. Recent research has discovered new allelopathic properties in some cyanobacteria species, new allelochemicals and elucidated some of the allelopathic mechanisms. Ecosystem-level approaches have shed some light on the factors that influence allelopathic interactions, as well as how cyanobacteria may be able to modulate their surrounding environment by means of allelochemical release. Nevertheless, the role of allelopathy in cyanobacteria ecology is still not well understood, and its clarification should benefit from carefully designed field studies, chemical characterization of allelochemicals and new methodological approaches at the "omics" level.

No abstract

Metal accumulation by Juncus maritimus and the role of this plant on the physical and chemical composition of sediments, from the Douro river estuary (NW Portugal), were investigated. The contents of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined (by atomic absorption spectrophotometry) in sediments, rhizosediments (those among plant roots and rhizomes), and different plant tissues (roots, rhizomes, leaves, and stems). Metal fractionation in sediments through sequential extraction was carried out and used for interpretation of sediment/J. maritimus interactions. Two estuarine sites with different characteristics were studied: site I displayed sandy sediment with lower organic matter and metals more weakly bound to it than site II sediment, which was muddy. At both sites, higher metal contents were observed in rhizosediments than in the surrounding sediment, but metals were more weakly bound to rhizosediment. Therefore, J. maritimus markedly influenced the sediments among its roots and rhizomes, changing metal distribution and speciation. Different patterns of both metal uptake and metal distribution among J. maritimus tissues were observed at the two sites. Plant bioaccumulation was only observed for Cd, Cu, and Zn, being similar for Cd atthe two sites and significantly higher for Cu and Zn (9 and 4 times higher, respectively) at site I. In conclusion, J. maritimus was shown to have potential for phytoextraction (or phytostabilization) of Cd, Cu, and Zn in estuarine environment. However, an eventual application of J. maritimus for this purpose will require a periodic removal of the plants together with their own rhizosediment.

No abstract

The environmental health-related relevance of cyanobacteria is primarily related to their ability to produce a wide range of toxins, which are known to be hazardous to many organisms, including human beings. The occurrence of cyanobacterial blooms has been related to eutrophic surface water. In the bloom-forming process the levels of phosphorus and nitrogen have been well documented but information regarding concentrations of other chemicals (inorganic, organo-metallic, and organic) is still incipient. Several contaminants, like trace metals, elicit a variety of acute and chronic toxicity effects, but cyanobacteria also have the capability to accumulate, detoxify, or metabolize such substances, to some extent. The role of cyanobacterial exudates has been proved a means of both nutrient acquisition and detoxification. In addition, cyanobacteria are effective biological metal sorbents, representing an important sink for metals in aquatic environment. Understanding the fundamental physicochemical mechanisms of trace metal bio-uptake by cyanobacteria in natural systems is a step towards identifying under what conditions cyanobacterial growth is favored and to ascertain the mechanisms by which blooms (and toxin production) are triggered. In this review the cyanobacterial interactions with metals will be discussed, focusing on freshwater systems.