Catalase and ascorbate peroxidase—representative H<Subscript>2</Subscript>O<Subscript>2</Subscript>-detoxifying heme enzymes in plants

Plants have to counteract unavoidable stress-caused anomalies such as oxidative stress to sustain their lives and serve heterotrophic organisms including humans. Among major enzymatic antioxidants, catalase (CAT; EC 1.11.1.6) and ascorbate peroxidase (APX; EC 1.11.1.11) are representative heme enzymes meant for metabolizing stress-provoked reactive oxygen species (ROS; such as H₂O₂) and controlling their potential impacts on cellular metabolism and functions. CAT mainly occurs in peroxisomes and catalyzes the dismutation reaction without requiring any reductant; whereas, APX has a higher affinity for H₂O₂ and utilizes ascorbate (AsA) as specific electron donor for the reduction of H₂O₂ into H₂O in organelles including chloroplasts, cytosol, mitochondria, and peroxisomes. Literature is extensive on the glutathione-associated H₂O₂-metabolizing systems in plants. However, discussion is meager or scattered in the literature available on the biochemical and genomic characterization as well as techniques for the assays of CAT and APX and their modulation in plants under abiotic stresses. This paper aims (a) to introduce oxidative stress-causative factors and highlights their relationship with abiotic stresses in plants; (b) to overview structure, occurrence, and significance of CAT and APX in plants; (c) to summarize the principles of current technologies used to assay CAT and APX in plants; (d) to appraise available literature on the modulation of CAT and APX in plants under major abiotic stresses; and finally, (e) to consider a brief cross-talk on the CAT and APX, and this also highlights the aspects unexplored so far.     

A review of regulatory decisions for environmental protection: part II - the case-study of contaminated land management in Portugal

This paper provides a case-study analysis of the challenges in the implementation of national soil policies, which was developed by the authors in Part I of the review of regulatory decisions for environmental protection [Rodrigues SM, Pereira ME, Ferreira da Silva E, Hursthouse A, Duarte AC. A review of regulatory decisions for environmental management: Part I-challenges in the implementation of national soil policies. Environ Int 2009. doi:10.1016/j.envint.2008.08.007]. The Portuguese case was selected as a case-study since specific regulatory decisions for contaminated land management are still in the early stages of development. Given the gap between the situation at the EU level and the state of Portuguese soil policy development, it is of merit to consider national contaminated land policy regimes already in place within the EU and to see if these provide a suitable basis to define the main challenges and research needs for the implementation of a Portuguese contaminated land management strategy. A framework combining the D-P-S-I-R (drivers-pressures-sources-impacts-responses) structure of policy evaluation with the Source-Pathway-Receptor approach to health risk assessment is proposed to derive an effective regulatory framework for managing contaminated land in Portugal, using available information and only to develop new data and research where knowledge gaps exist. Funding site clean-up and assigning liability were identified as relevant factors currently hampering site remediation. Most relevant research needs for the development of contaminated land management practices in Portugal are those associated to the definition of a risk assessment framework and setting guidelines for the evaluation of risks posed to both humans and ecosystems. Other relevant and innovative features are the integration of soil function analysis into site investigations and the definition of a framework that combines risk assessment with soil function analysis. The analysis of the Portuguese case also provides insight into the discussions needed for the effective development of regulatory decisions for contaminated land management in countries with no history of implementing specific soil policies.     

Indoor radon periodicities and their physical constraints: a study in the Coimbra region (Central Portugal)

Indoor radon activities were measured during a period of 6 months, as well as several physical environmental variables (temperature, pressure, humidity and rainfall). The location was a small room at an administrative building of the University of Coimbra, usually undisturbed by human activities and situated over bedrock of low-uranium Triassic red sandstones. A low average activity of radon was observed (36 Bq m⁻³), however showing a very well marked daily periodicity (10 ± 5 Bq m⁻³), with maximum values occurring more frequently between 9 and 10 a.m. Daily variations are shown to have no relation with earth tides, and their amplitudes exhibit a significant correlation with outdoor temperature; no dependence on barometric pressure was found. Rainfall disturbs the observed daily radon cycles through a strong reduction of their amplitude, but has no effect on the long-term variability of the gas concentration.     

Association between micronuclei frequency in pollen mother cells of Tradescantia and mortality due to cancer and cardiovascular diseases: A preliminary study in Sao José dos Campos, Brazil

The present study was designed to explore the correlation between the frequency of micronuclei in Trad-MN, measured across 28 biomonitoring stations during the period comprised between 11 of May and 2 of October, 2006, and adjusted mortality rates due to cardiovascular, respiratory diseases and cancer in Sao José dos Campos, Brazil, an area with different sources of air pollution. For controlling purposes, mortality rate due to gastrointestinal diseases (an event less prone to be affected by air pollution) was also considered in the analysis. Spatial distribution of micronuclei frequency was determined using average interpolation. The association between health estimators and micronuclei frequency was determined by measures of Pearson's correlation. Higher frequencies of micronuclei were detected in areas with high traffic and close to a petrochemical pole. Significant associations were detected between micronuclei frequency and adjusted mortality rate due to cardiovascular diseases (r = 0.841, p = 0.036) and cancer (r = 0.890, p = 0.018). The association between mortality due to chronic obstructive pulmonary diseases was positive but did not reach statistical significance (r = 0.640, p = 0.172), probably because of the small number of events. Gastrointestinal mortality did not exhibit significant association with micronuclei frequency. Because the small number of observations and the nature of an ecological study, the present findings must be considered with caution and considered as preliminary. Further studies, performed in different conditions of contamination and climate should be done before considering Trad-MN in the evaluation of human health risk imposed by air pollutants.     

Mercury in salt marshes ecosystems: Halimione portulacoides as biomonitor

Mercury concentrations were quantified in Halimione portulacoides (roots, stems and leaves) as well as in sediments from eight Portuguese estuarine systems, covering seventeen salt marshes with distinct degrees of mercury contamination. The concentration of mercury in the sediments ranged from 0.03 to 17.0 microg g(-1). The results show that the accumulation of mercury differed according to the organ of the plant examined and the concentration of mercury in the sediments. Higher mercury concentrations were found in the roots (up to 12.9 microg g(-1)) followed by the leaves (up to 0.12 microg g(-1)), while the stems had the lowest concentrations (up to 0.056 microg g(-1)). A linear model explained the relation between the concentrations of mercury in the different plant organs: roots and stems (R(adj)(2)=0.75), stems and leaves (R(adj)(2)=0.85) and roots and leaves (R(adj)(2)=0.78). However, the results show that the variation of mercury concentration in the roots versus mercury concentration in the sediments was best fitted by a sigmoidal model (R(adj)(2)=0.89). Mercury accumulation in the roots can be described in three steps: at a low range of mercury concentrations in the sediments (from 0.03 up to 2 microg g(-1)), the accumulation of mercury in roots is also low reaching a maximum concentration of 1.3 microg g(-1); the highest rates of mercury accumulation in the roots occur in a second step, until the concentrations of mercury in the sediments reach approximately 4.5 microg g(-1); after reaching this maximum value, the rate of mercury accumulation in the roots slows down leading to a plateau in the concentration of mercury in the roots of about 9.4 microg g(-1), which corresponds to a mercury concentration in the sediments of about 11 microg g(-1). A linear model explained also the accumulation of mercury in leaves versus the mercury concentration in the sediments (R(adj)(2)=0.88). Differences in responses of roots and leaves are explained by the dynamics of the plant organs: old roots are mineralised in situ close to new roots, while leaves are renewed. Previous studies have already shown that H. portulacoides is a bioindicator for mercury and the results from this work sustain that H. portulacoides may also be used as a biomonitor for mercury contamination in salt marshes. Nevertheless, caution should be taken in the application of the models, concerning the life cycle of the species and the spatial variability of the systems.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Determinants of dioxins and furans in blood of non-occupationally exposed populations living near Portuguese solid waste incinerators

Biomonitoring of dioxin body burden, as evaluated by PCDD/F levels in blood, has been carried out in a total of 138 adults from general population living in the vicinity of solid waste incinerators in Portugal. Measurements were performed included in cross-sectional surveys within two Environmental Health Surveillance Programs launched in response to ecotoxicological concern in relation to solid waste incinerators near Lisbon and in Madeira Island. Overall conclusion from first published results is indicative that dioxin exposure of global populations cannot be related to the emissions of these facilities, meaning that dioxin sources control seems to be effective in relation to both incinerators. Main objective of present work was to investigate potential determinants of dioxin levels in the studied populations. Findings from this investigation also suggest that incineration does not impact on dioxin blood levels of nearby residents. Follow-up of a small group of individuals (22) from Lisbon gives preliminary indication on temporal control effectiveness of the Lisbon facility. Regarding comparison between PCDD/F levels from Lisbon and Madeira communities, individuals from Lisbon show higher median PCDD/F levels, likely to be better explained by more highly polluted areas in Lisbon than by eventual differences in dietary habits of the studied groups. In fact, analysis performed on the diet of both groups (not detailed in the present study) does not show a statistically significant difference in relation to any of the most relevant foodstuffs in the context of dioxin exposure. Comparison between Lisbon and Madeira in relation to pattern of the single congeners for PCDD/Fs shows a very similar profile. The highest contributions to the PCDD/Fs toxicity came from 12378-PCDD, 23478-PCDF, Hexa-CDD, 2378-TCDD and Hexa-CDF.     

Biomonitoring of PCDD/Fs in populations living near portuguese solid waste incinerators: levels in human milk

In the context of two Environmental Health Surveillance Programs, launched in response to public and scientific concern in relation to waste incinerators located near Lisbon and in Madeira Island, two human biomonitoring projects have been started in Portugal, focussed in dioxins and dioxin-like compounds in human milk. Results from the undertaken studies have already provided data on the extent and pattern of dioxin body burden of both studied groups as well as a preliminary temporal trend of dioxin levels for the population residing near Lisbon incinerator. The present paper investigates difference between exposed and non-exposed subjects under study and, from a preventive perspective, possible covariates of the dioxin levels in human milk. Emissions from both incinerators appear to be well controlled as there is no increase of human body burden of dioxins as measured in human milk of individuals living near these facilities. Concerning other determinants of dioxin levels, results suggest confirmation of previously found significant age-dependent trend towards higher levels of dioxins in aged subjects. On the contrary, association between mother's levels of dioxins and parity lost significance. Apart from the issue of incineration, the general conclusion for the general population is that living in Lisbon as compared to Madeira results in higher milk dioxin levels and possible health risks. The profile of the single congeners for PCDD/Fs in human milk from Madeira and Lisbon shows similar contributions for 12378-PCDD, 23478-PCDF, 123678-HCDD and 2378-TCDD, that account altogether for about 84% of the total identified dioxin body burden in the studied groups.     

Metal and nutrient dynamics in a eutrophic coastal lagoon (Óbidos, Portugal): the importance of observations at different time scales

Water and sediment quality was monitored at four sites of Óbidos coastal lagoon (Portugal) in February, May, July and October 2006, covering different hydrological conditions. Concentrations of nutrients and metals increased in autumn/winter, particularly in an inner branch with symptoms of eutrophication that receives a small tributary contaminated by agro-industrial activities. Moreover, concentrations of PO₄ ^3?, Si(OH)₄ and Mn (diffusive gradients of thin films (DGT)-measured) varied inversely with salinity. Additionally, that branch was monitored over 26-h in July 2006 to assess variations of water quality parameters, nutrients and metals on short timescale. During the night, O₂ in water reached a minimum of 40% saturation followed by a pronounced increase of DGT-measured metals and nutrients in water column: Fe and Mn (ten times); Cr, Co, PO₄ ^3? and Si(OH)₄ (six times). Enhancements were also registered for metal/Al ratios in suspended particulate matter: Mn, Cr and Cd (four to six times); Fe, Ni and Co (1.5 times). The metal distribution coefficients calculated along the 26-h survey showed a maximum at daylight suggesting a preferential association of metals with suspended particles. Data recorded under different hydrological conditions and over the 26-h survey allowed to address the influence of external and internal sources on water quality. The results of this study highlight the importance of day/night cycles on the availability of nutrients and metals in eutrophic environments.     

Assessment of solar driven TiO2-assisted photocatalysis efficiency on amoxicillin degradation

The objective of this work was to evaluate the efficiency of a solar TiO₂-assisted photocatalytic process on amoxicillin (AMX) degradation, an antibiotic widely used in human and veterinary medicine. Firstly, solar photolysis of AMX was compared with solar photocatalysis in a compound parabolic collectors pilot scale photoreactor to assess the amount of accumulated UV energy in the system (Q _UV) necessary to remove 20 mg L^?1 AMX from aqueous solution and mineralize the intermediary by-products. Another experiment was also carried out to accurately follow the antibacterial activity against Escherichia coli DSM 1103 and Staphylococcus aureus DSM 1104 and mineralization of AMX by tracing the contents of dissolved organic carbon (DOC), low molecular weight carboxylate anions, and inorganic anions. Finally, the influence of individual inorganic ions on AMX photocatalytic degradation efficiency and the involvement of some reactive oxygen species were also assessed. Photolysis was shown to be completely ineffective, while only 3.1 kJ_UV?L^?1 was sufficient to fully degrade 20 mg L^?1 AMX and remove 61 % of initial DOC content in the presence of the photocatalyst and sunlight. In the experiment with an initial AMX concentration of 40 mg L^?1, antibacterial activity of the solution was considerably reduced after elimination of AMX to levels below the respective detection limit. After 11.7 kJ_UV?L^?1, DOC decreased by 71 %; 30 % of the AMX nitrogen was converted into ammonium and all sulfur compounds were converted into sulfate. A large percentage of the remaining DOC was in the form of low molecular weight carboxylic acids. Presence of phosphate ions promoted the removal of AMX from solution, while no sizeable effects on the kinetics were found for other inorganic ions. Although the AMX degradation was mainly attributed to hydroxyl radicals, singlet oxygen also plays an important role in AMX self-photosensitization under UV/visible solar light.