Silicon in vascular plants: uptake, transport and its influence on mineral stress under acidic conditions.

MAIN CONCLUSION: So far, considerable advances have been achieved in understanding the mechanisms of Si uptake and transport in vascular plants. This review presents a comprehensive update about this issue, but also provides the new insights into the role of Si against mineral stresses that occur in acid soils. Such information could be helpful to understand both the differential Si uptake ability as well as the benefits of this mineral element on plants grown under acidic conditions. Silicon (Si) has been widely recognized as a beneficial element for many plant species, especially under stress conditions. In the last few years, great efforts have been made to elucidate the mechanisms involved in uptake and transport of Si by vascular plants and recently, different Si transporters have been identified. Several researches indicate that Si can alleviate various mineral stresses in plants growing under acidic conditions, including aluminium (Al) and manganese (Mn) toxicities as well as phosphorus (P) deficiency all of which are highly detrimental to crop production. This review presents recent findings concerning the influence of uptake and transport of Si on mineral stress under acidic conditions because a knowledge of this interaction provides the basis for understanding the role of Si in mitigating mineral stress in acid soils. Currently, only four Si transporters have been identified and there is little information concerning the response of Si transporters under stress conditions. More investigations are therefore needed to establish whether there is a relationship between Si transporters and the benefits of Si to plants subjected to mineral stress. Evidence presented suggests that Si supply and its subsequent accumulation in plant tissues could be exploited as a strategy to improve crop productivity on acid soils.

Improving bioavailability of phosphorous from cattle dung by using phosphatase immobilized on natural clay and nanoclay.

The high P retention of acidic Andisols makes necessary to increase our technological approaches in pasture management in the animal system production. Here, we evaluated the clay- or nanoclay-acid phosphatase complexes for improving phosphorus mineralization from degraded cattle dung. We implemented an immobilization mechanism of acid phosphatase (AP) using natural clays (allophanic and montmorillonite) and nanoclays as support materials. Also, we evaluated the mineralization of organic P containing in decomposed cattle dung with clay- and nanoclay-AP complexes by incubation studies. Clays and nanoclays were characterized by microscopy techniques as atomic force and confocal-laser scanning microscopy. We found that these support materials stabilized AP by encapsulation. Our results showed that immobilization on allophanic or montmorillonite materials improved both the specific activity (4-48%) and the V(max) (28-38%) of AP. Moreover, the enzyme had a better performance when immobilized on clay and nanoclay from Andisol than on montmorillonite materials. Phosphorous mineralization of cattle dung was regulated by water-soluble P present in the dung and P re-adsorption on allophanic materials. However, we were able to detect a potential capacity of AP immobilized on allophanic nanoclays as the best alternative for P mineralization. Further research with initially low water-soluble P containing organic materials is required to quantify the P mineralization potential and bioavailability of P from dung.

Activity stabilization of Aspergillus niger and Escherichia coli phytases immobilized on allophanic synthetic compounds and montmorillonite nanoclays.

The aim of this work was to study the stabilization of the activity of two commercial microbial phytases (Aspergillus niger and Escherichia coli) after immobilization on nanoclays and to establish optimal conditions for their immobilization. Synthetic allophane, synthetic iron-coated allophanes and natural montmorillonite were chosen as solid supports for phytase immobilization. Phytase immobilization patterns at different pH values were strongly dependent on both enzyme and support characteristics. After immobilization, the residual activity of both phytases was higher under acidic conditions. Immobilization of phytases increased their thermal stability and improved resistance to proteolysis, particularly on iron-coated allophane (6% iron oxide), which showed activation energy (E(a)) and activation enthalpy (ΔH(#)) similar to free enzymes. Montmorillonite as well as allophanic synthetic compounds resulted in a good support for immobilization of E. coli phytase, but caused a severe reduction of A. niger phytase activity.

Formation and properties of organo-phosphatase complexes by abiotic and biotic polymerization of pyrogallol-phosphatase mixtures.

In this paper, the catalytic efficacy of peroxidase and manganese oxide, both commonly present in soil, to catalyze the formation of pyrogallol-phosphatase complexes was compared. The influence of several factors (e.g., the concentration of pyrogallol, the amount of catalysts, the nature of manganese oxide, birnessite, or pyrolusite, the incubation time, and the pH) on the transformation of pyrogallol and the characteristics and properties of the pyrogallol-phosphatase interaction products were investigated. The pyrogallol transformation mediated by both catalysts was very fast and increased by increasing the catalyst concentration. The nature of the catalyst also influenced the size and the molecular mass of the formed complexes. When polymerization of pyrogallol occurred with high intensity, a loss of phosphatase activity occurred, and it strongly depended on the pH at which the process was carried out and the catalyst. In particular, with peroxidase, the phosphatase activity was much lower in either suspensions or supernatants and not measurable in the insoluble complexes as compared to that measured in the presence of manganese oxides.

Oxidative transformation of aqueous phenolic mixtures by birnessite-mediated catalysis.

The catalytic efficiency of birnessite in the removal of catechol, hydroxytyrosol, methylcatechol and m-tyrosol, four phenols commonly present in polluted wastewaters, was studied in mono-substrate solutions or in mixtures of two, three, and four substrates. In single phenolic solutions the transformation order of phenols was catechol>hydroxytyrosol>methylcatechol>m-tyrosol. With phenolic mixtures different responses were observed and the amount of each phenol transformed and the crossing effects among the various phenols depended on the type and number of phenols present in the mixture. In particular, general inhibitory effects were observed for hydroxytyrosol and m-tyrosol that were transformed less when present in combination with the other phenols. By contrast the effects by the presence of more than one phenol were basically annulled for catechol and methylcatechol at 24 h incubation in all the mixtures. A simultaneous, but often no stoichiometric, release of soluble Mn2+ in the reaction mixtures occurred. The multi-substrate systems were designed to mimic birnessite-mediated oxidative processes that could occur under field conditions. Therefore they could be of great interest to environmental and soil science. The use of birnessite as a potential tool for an effective detoxification and recovery of phenol-polluted systems could be also envisaged.

Oxidative transformation of natural and synthetic phenolic mixtures by Trametes versicolor laccase.

The efficiency of Trametes versicolor laccase in the transformation of phenols (caffeic acid, catechol, hydroxytyrosol, methylcatechol, protocatechuic acid, syringic acid, m-tyrosol, 3-hydroxybenzoic acid, 3-hydroxyphenylacetic acid, 2,6-dihydroxybenzoic acid, 4-hydroxybenzaldehyde) usually present in waste water, such as that derived from an olive oil factory, was investigated. According to their response to 24 h laccase action the 11 phenolic compounds were classified in three groups: reactive (88-100% transformation), intermediate reactive (transformation lower than 50%), and recalcitrant (not transformed at all). The enzyme was able to transform the 11 substrates even when they were present in a mixture and also toward a phenolic extract from a Moroccan olive oil mill waste water (OMW) sample. The disappearance of protocatechuic, 3-hydroxyphenylacetic, and 2,6-dihydroxybenzoic acids, and 4-hydroxybenzaldehyde was enhanced whereas that of caffeic acid and m-tyrosol was depressed when the phenols were present in the mixture. A reduction of enzyme activity occurred in single and/or complex phenolic mixtures after enzymatic oxidation. No correspondence between phenol transformation and disappearance of enzymatic activity was, however, observed. The overall results suggest that laccases are effective in the transformation of simple and complex phenolic mixtures.

Biodegradation of phenanthrene and analysis of degrading cultures in the presence of a model organo-mineral matrix and of a simulated NAPL phase.

Two mixed bacterial cultures (C(B-BT) and C(I-AT)) degraded phenanthrene when it was: (i) in the presence of either hexadecane as a non aqueous phase liquid or a montmorillonite-Al(OH)x-humic acid complex as a model organo-mineral matrix; (ii) sorbed to the complex, either alone or in the presence of hexadecane. The cultures had different kinetic behaviours towards phenanthrene with or without hexadecane. The degradation of Phe alone as well as that of Phe in hexadecane ended in 8 and 15 days with C(B-BT) and C(I-AT) cultures, respectively. Hexadecane increased Phe bioavailability for C(I-AT) bacteria which degraded Phe according to first-order kinetics. The same effect was observed for C(B-BT) bacteria, but with an initial 2 days lag phase and in accordance with zero-order kinetics. The presence of hexadecane did not affect the degradation of phenanthrene sorbed and aged on the complex by C(I-AT )culture. This capability was exhibited also after experimental aging of 30 days. The dynamics of the bacterial community composition was investigated through PCR-DGGE (denaturing gradient gel electrophoresis) of 16S rRNA gene fragments. Individual bands changed their intensity during the incubation time, implying that particular microbe's relative abundance changed according to the culture conditions. Isolation of phenanthrene and/or hexadecane degraders was in accord with cultivation-independent data. Growth-dependent changes in the cell surface hydrophobicity of the two cultures and of the isolates suggested that modulation of cell surface hydrophobicity probably played an important role for an efficient phenanthrene assimilation/uptake.

Bioremediation and monitoring of aromatic-polluted habitats.

Bioremediation may restore contaminated soils through the broad biodegradative capabilities evolved by microorganisms towards undesirable organic compounds. Understanding bioremediation and its effectiveness is rapidly advancing, bringing available molecular approaches for examining the presence and expression of the key genes involved in microbial processes. These methods are continuously improving and require further development and validation of primer- and probe-based analyses and expansion of databases for alternative microbial markers. Phylogenetic marker approaches provide tools to determine which organisms are present or generally active in a community; functional gene markers provide only information concerning the distribution or transcript levels (deoxyribonucleic acid [DNA]- or messenger ribonucleic acid [mRNA]-based approaches) of specific gene populations across environmental gradients. Stable isotope probing methods offer great potential to identify microorganisms that metabolize and assimilate specific substrates in environmental samples, incorporating usually a rare isotope (i.e., (13)C) into their DNA and RNA. DNA and RNA in situ characterization allows the determination of the species actually involved in the processes being measured. DNA microarrays may analyze the expression of thousands of genes in a soil simultaneously. A global analysis of which genes are being expressed under various conditions in contaminated soils will reveal the metabolic status of microorganisms and indicate environmental modifications accelerating bioremediation.

Mitigation of olive mill wastewater toxicity.

The toxicity of olive mill wastewaters (OMW) is commonly attributed to monomeric phenols. OMW were treated in an aerated, stirred reactor containing agricultural soil, where the oxidative polymerization of phenols took place. In 24 h, OMW monomeric phenols decreased by >90%. This resulted in a corresponding reduction in phytotoxicity, as measured by germination tests with tomato and English cress seeds, and in microbial toxicity, as measured by lag phase duration in Bacillus cereus batch growth. Soil germination capability after irrigation with OMW was assessed in long-term pot experiments. The relative germination percentage of tomato was higher when the soil was irrigated with treated OMW rather than with untreated ones, although it was lower than the control (e.g., soil irrigated with distilled water). At longer incubation times, a complete recovery of the soil germination capability was achieved with treated, but not with untreated, OMW.

Soil enzyme activities as affected by anthropogenic alterations: intensive agricultural practices and organic pollution.

The activity of a range of enzymes related to the cycling of the main biologically important nutrients C, N, P and S was investigated in cultivated and non-cultivated soils from various parts of Europe. Two agricultural sites from North Italy under continuous corn (Zea mays L.) with and without organic fertilization were compared. Two other agricultural sites from South Italy under hazel (Corylus avellana L.) never flooded or repeatedly flooded over by uncontrolled urban and industrial wastes were investigated. The non-cultivated soils were from Middle and South Europe with different pollution history such as no-pollution and pollution with organic contaminants, which is phenanthrene and other polycyclic aromatic hydrocarbons (PAHs). Agricultural soils showed significant differences in some of physical-chemical properties (i.e. organic C, total and labile phosphate contents, available Ca and Mg) between the two sites studied. Enzyme activities of hazel sites periodically flooded by wastes were mainly higher than in the hazel sites never flooded. Sites under many years of continuous corn showed dehydrogenase, invertase, arylsulphatase and beta-glucosidase activities generally lower than the soils under hazel either flooded or not by wastes. As compared to agricultural soils, non-cultivated soils heavily or moderately polluted by organic contaminants displayed much lower values or complete absence of enzymatic activities. Dissimilar, contradictory correlations between soil enzyme activities and the majority of soil properties were observed separately in the two groups of soils. When the whole set of enzyme activities and soil properties were considered, all significant correlations found separately for the groups of soils were lost. The overall results seem to confirm that no direct cause-effect relationships can be derived between the changes of a soil in response to a given factor and both the variations of the activity and the behaviour of the enzymes in soil.

Bioavailability of phenanthrene in the presence of birnessite-mediated catechol polymers.

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants and contribute to the pollution of aquatic and terrestrial environments. In soil, their fate may be affected by interactions with the soil biological community and soil colloids. This study was conducted to investigate the fate of phenanthrene (Phe), selected as a representative PAH, in simplified model systems, which simulate processes naturally occurring in soil. Phe was interacted with catechol (Cat), an orthodiphenol, and common intermediate in the microbial degradation of PAHs, and birnessite (Bir), an abiotic strong oxidative catalyst abundant in soil. Two experimental conditions were investigated: Cat (5 mM)+Bir (1 mg ml(-1))+Phe (0.05 mg ml(-1)) mixed at the same time and incubated for 24 h at 25 degrees C (Cat-Bir-Phe) and Cat+Bir incubated for 24 h at 25 degrees C before Phe addition and then incubated for a further 24 h (Cat-Bir+Phe). After incubation, the systems were analysed for residual Cat and Phe, supplied with a selected Phe-degrading mixed bacterial culture, and then the microbial degradation of Phe and the growth of cells were monitored. Complex phenomena simultaneously occurred. Cat was completely removed after a 24-h incubation with Bir, and no interference by Phe in the Bir-mediated transformation of Cat was observed. Elemental analysis and UV-Vis and Fourier transfer infrared spectra showed that Cat transformation by Bir produced soluble and insoluble polymeric aggregates involving Phe. The hydrocarbon also interacted with the surfaces of Bir either previously coated (Cat-Bir+Phe sample) or not by Cat polymers. When a Phe-degrading bacterial culture was added to the systems after Bir-mediated Cat polymerisation, a different behaviour was observed in terms of Phe consumption and bacterial growth, thus suggesting differentiated availability of Phe to the microbial cells. The hydrocarbon was completely transformed in the presence of Bir and/or Bir covered by Cat polymers. By contrast a reduced degradation was measured when the Phe was involved in the polymerisation of Cat and entrapped in the Cat polymers (Cat-Bir-Phe). Although Cat showed a toxic, lethal effect on the bacterial cells, microbial growth was observed in the presence of Cat and Cat polymers, as the only C source. The mechanism leading to the different availability of Phe in the presence of Cat and Bir is still not clear. Further investigations are requested to provide more insight into such a complex phenomenon.