Singlet molecular oxygen—mediated photooxidation of monochloro and mononitrophenols. A kinetic study

A kinetic and mechanistic study on the aerobic dye sensitized photooxidation of the mono—nitro and chlorophenols was carried out. A singlet molecular oxygen mechanism operates in the photooxidation. Solvent and substituent effects, suggest the intermediacy of a complex with partial charge transfer character, as has been postulated for other phenols.

Chemical (reactive) and physical interactions of the substrates with singlet molecular oxygen were discriminated. Quantum yields for photooxidation (higher for the chlorophenols) range from 3 × 10^‐2 to 2 × 10^‐3, as measured by substrate or oxygen consumption. These values indicate the viability of a singlet molecular oxygen photooxidation as a way for the degradation of nitro and chlorophenol environmental contaminants.     

Ecological niche segregation among five toothed whale species off the NW Iberian Peninsula using ecological tracers as multi-approach

This study aims to assess niche segregation among the five main toothed whales that frequent the NW Iberian Peninsula waters: the common dolphin, the harbour porpoise, the bottlenose dolphin, the striped dolphin and the long-finned pilot whale. We used cadmium (Cd) and stable isotope ratios (δ¹³C and δ¹⁵N) as ecological tracers to assess degree of segregation in diet/trophic level and in foraging habitat, over various time-scales. δ¹³C values highlighted different habitats, while Cd concentrations highlighted feeding differences between oceanic and neritic species. Moreover, δ¹⁵N values suggest different trophic levels of prey targeted within oceanic and neritic species. Hence, results revealed long-term ecological segregation among five toothed whales that coexist in the NWIP and demonstrated the ability of ecological tracers to discriminate ecological niches among closely related species.     

Roe and red deer as bioindicators of heavy metals contamination in north-western Poland

The present paper examines the degree of environmental contamination in areas covered by the Natura 2000 programme, located in north-western Poland, with selected heavy metals based on their concentration in target organs of roe and red deer. Lead, cadmium, copper, iron, and zinc concentrations were determined by inductively coupled plasma–atomic emission spectrometry. Residues of lead and cadmium were found in most of the analysed samples of roe and red deer organs The concentration of cadmium in the organs of the animals studied was much higher than that of lead. The median for Pb in liver and kidneys was 0.055 and 0.092 μg/g dry weight (d.w.) in roe deer, and 0.067 and 0.081 μg/g d.w. in red deer, respectively. The median for liver and kidney cadmium was 0.770 and 6.139 μg/g d.w. in roe deer, and 0.422 and 6.365 μg/g d.w. in red deer, respectively. Our study has demonstrated that this area is laden with lead and cadmium. This is evidenced by the fact that maximum permissible levels of these elements in the organs of red and roe deer, which were used as bioindicators of environmental contamination, were exceeded.     

Heavy Metals in Macroalgae of Havana's Northern Littoral,Cuba

Copper, iron, lead, manganese, and zinc contents were determined in various phyla of macroalgae typical of the rocky mesolittoral zone of Cuba and widely distributed in the Caribbean Region. the samples were collected in different zones along the shores of Havana City which are more or less influenced by anthropogenic activities. Differences in metal contents were observed due to seasonal variations and differences between sampling sites. of the analyzed species, only one brown alga, Padina vickersiae is considered as a suitable candidate for the monitoring of metal contamination.     

Metal fractionation of cadmium, lead and arsenic of geogenic origin in topsoils from the Marrancos gold mineralisation, northern Portugal

The Marrancos gold mineralisation has a chemical assemblage of Fe–As–Se–Bi–Au–Ag–Te–(Cu–Pb–Zn–Sn–W). The −200 mesh of 144 topsoil samples was analysed by ICP–MS to determine total contents of 53 elements that include potentially harmful elements like Cd, As and Pb. The soil geochemistry shows that some trace elements occur in considerably high concentrations. On the basis of data for total metal concentrations, 10 topsoil samples were selected to carry out a metal fractionation study using a selective extraction method. A set of four leaches of increasing strength was used sequentially in the soil samples. Across the study area, there is some evidence of past mining and exploration activity, indicating that these soils may be locally disturbed. The shallow mineralised quartz veins were exploited for gold by the Romans. Several galleries were constructed during the 2nd World War, probably for the exploration of quartz–cassiterite–wolframite veins. However, the main mineralised body in depth was never explored. The results of metal fractionation show different partitions for the three elements. Total Cd concentrations in these soils are low, with a median value of 0.1 mg/kg. In average, 12% of total Cd is adsorbed by clays and/or co-precipitated with carbonates, and 19% is bounded to Fe–Mn oxyhydroxides. However, the low concentrations indicate that the metal does not represent an immediate risk to human health. For Pb, metal fractionation shows that, on average, 22% of Pb is adsorbed by amorphous Fe and Mn oxides, but the samples from the northern part of the area have the major fractions of Pb in soluble forms. The low probability of exposure in this part of the study area decreases the risk posed by this heavy metal. Total As concentrations in the Marrancos soils are extremely high. A large area has As concentrations above 1,000 mg/kg. For As, metal fractions in the sulphide phase vary between 84 and 98% in the studied samples. But one sample has 20% of total As in easily reducible forms, corresponding to a partial concentration of 1,800 mg/kg that has a high probability of being bioavailable. The most labile As forms occur at the southern part of the area, where the probability of exposure is higher and the risk of human health increases in the same order. From the three studied potentially harmful elements, As is certainly the element of concern.     

Joint use of data and modeling in coastal wave transformation

In the framework of a research project entitled ??BRISA??BReaking waves and Induced SAnd transport??, a methodology was devised to characterize the waves joining together in-situ measurements and numerical wave propagation models. With this goal in mind, a number of in-situ measurements were made, for selected positions in front of Praia de Faro (South Portugal), during four days (25th to 28th March, 2009) by using different types of equipments (e.g., resistive wave gauges, pressure sensors, currentmeters and a new prototype pore pressure sensor using optical fibre). Wave records were obtained simultaneously offshore (at a water depth of 11.7?m below mean sea level, MSL) and at the surf and swash zones. The data processing and analysis were made by applying classical time domain techniques. Numerical simulations of the wave propagation between offshore and inshore for the measurement period were performed with two numerical models, a 1D model based on linear theory and a nonlinear Boussinesq-type model, COULWAVE, both forced by the measured offshore wave conditions of 27th March 2009. Comparisons between numerical results and field data for the pressure sensors placed in the surf and swash zones were made and discussed. This approach enables to evaluate the performance of those models to simulate those specific conditions, but also to validate the models by gaining confidence on their use in other conditions.     

DNA damage in oral epithelial cells of individuals chronically exposed to indoor radon (<Superscript>222</Superscript>Rn) in a hydrothermal area

Hydrothermal areas are potentially hazardous to humans as volcanic gases such as radon (²²²Rn) are continuously released from soil diffuse degassing. Exposure to radon is estimated to be the second leading cause of lung cancer, but little is known about radon health-associated risks in hydrothermal regions. This cross-sectional study was designed to evaluate the DNA damage in the buccal epithelial cells of individuals chronically exposed to indoor radon in a volcanic area (Furnas volcano, Azores, Portugal) with a hydrothermal system. Buccal epithelial cells were collected from 33 individuals inhabiting the hydrothermal area (Ribeira Quente village) and from 49 individuals inhabiting a non-hydrothermal area (Ponta Delgada city). Indoor radon was measured with Ramon 2.2 detectors. Chromosome damage was measured by micronucleus cytome assay, and RAPD-PCR was used as a complementary tool to evaluate DNA damage, using three 10-mer primers (D11, F1 and F12). Indoor radon concentration correlated positively with the frequency of micronucleated cells (r _s = 0.325, p = 0.003). Exposure to radon is a risk factor for the occurrence micronucleated cells in the inhabitants of the hydrothermal area (RR = 1.71; 95% CI, 1.2–2.4; p = 0.003). One RAPD-PCR primer (F12) produced differences in the banding pattern, a fact that can indicate its potential for detecting radon-induced specific genomic alterations. The observed association between chronic exposure to indoor radon and the occurrence of chromosome damage in human oral epithelial cells evidences the usefulness of biological surveillance to assess mutations involved in pre-carcinogenesis in hydrothermal areas, reinforcing the need for further studies with human populations living in these areas.     

Changes in transport accessibility as a result of flooding: a case study of the Mazovia Province (Eastern Poland)

This paper presents the results of research investigating the impact of flooding on the temporal aspect of transport accessibility at national, regional and local levels in the Mazovia Province – an administrative region in Poland. For the purposes of this study the authors measured the theoretical journey times by private transport between settlement units for two variants: journeys made under normal circumstances, that is, without a flood; and journeys made during a flood event, which would necessitate diversions to avoid flooded road sections. This allowed the theoretical journey time differences to be calculated. It was assumed that vehicles move at the highest permissible speed along routes allowing the shortest travel times. The methods of accessibility assessment employed in this paper are based on distance measurements and use isochrones and a cumulative approach. Analysis carried out by the authors has shown that for interregional, intraregional and local journeys, the flooding of a part of the Mazovia region results in changes in travel times, but their absolute and relative magnitudes vary widely. It was found that in the case of national scale journeys the majority of relative journey time increases were no greater than three times the normal duration, while on a local scale they do not exceed 75%. For areas with a high risk of flooding there should be obligatory analyses of changes in transport accessibility; this would facilitate effective flood risk management. Appropriate traffic management in crisis situations would facilitate emergency and rescue services and help inhabitants and any other persons in flooded areas.     

The use of the shanny Lipophrys pholis for pollution monitoring: a new sentinel species for the northwestern European marine ecosystems

The contamination of aquatic ecosystems by organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) is a matter of great concern. Mussels have been extensively used as sentinel species in a large number of monitoring programs. However, the use of bivalves as the sole species has some limitations, because they are not as responsive as fish to Aryl Hydrocarbon Receptor agonists. Hence, for many marine areas, there is the need to validate new sentinel fish species that can be used in the assessment of pollution by organic contaminants. The shanny Lipophrys pholis is an intertidal fish that combines many characteristics required in a sentinel species: is abundant and easy to catch, has a wide geographical distribution and restrict home range. After larvae recruitment to the intertidal rocky shores, they remain in the same area for the rest of the life-cycle, thus reflecting local pollutants exposure. In order to evaluate the species sensitivity to organic contaminants under field conditions, L. pholis were collected at six sites reflecting different degrees of anthropogenic contamination. The induction of two biomarkers extensively validated in the assessment of PAHs contamination ethoxyresorufin-O-deethylase activity (EROD) and Fluorescent Aromatic Compounds (FACs) was evaluated. In parallel, mussels were collected at the same locations and levels of 16 PAHs and selected heavy metals determined. Overall, the specimens collected in the urban areas showed a significant induction of EROD and FACs (up to a six-fold induction) if compared with the reference sites. Additionally, a positive correlation was observed between the biomarkers and PAHs levels in mussel tissues. Even though further validation is currently in progress, the available data indicate that L. pholis is responsive to organic contaminants such as PAHs, suggesting its future integration in monitoring programmes designed to evaluate the presence of these contaminants in European marine ecosystems.     

Marine Protected Dramas: The Flaws of the Brazilian National System of Marine Protected Areas

This article discusses the current problems and issues associated with the implementation of a National System of Marine Protected Areas in Brazil. MPA managers and higher governmental level authorities were interviewed about their perceptions of the implementation of a national MPA strategy and the recent changes in the institutional arrangement of government marine conservation agencies. Interviewees’ narratives were generally pessimistic and the National System was perceived as weak, with few recognizable marine conservation outcomes on the ground. The following major flaws were identified: poor inter-institutional coordination of coastal and ocean governance; institutional crisis faced by the national government marine conservation agency; poor management within individual MPAs; problems with regional networks of marine protected areas; an overly bureaucratic management and administrative system; financial shortages creating structural problems and a disconnect between MPA policy and its delivery. Furthermore, a lack of professional motivation and a pessimistic atmosphere was encountered during many interviews, a malaise which we believe affects how the entire system is able to respond to crises. Our findings highlight the need for a better understanding of the role of ‘leadership’ in the performance of socio-ecological systems (such as MPA networks), more effective official evaluation mechanisms, more localized audits of (and reforms if necessary to) Brazil’s federal biodiversity conservation agency (ICMBio), and the need for political measures to promote state leadership and support. Continuing to focus on the designation of more MPAs whilst not fully addressing these issues will achieve little beyond fulfilling, on paper, Brazil’s international marine biodiversity commitments.