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.     

Charge‐transfer chromatographic study of the interaction of commercial pesticides with hydroxypropyl‐β‐cyclodextrin

The interaction between 33 commercial pesticides with hydroxypropyI‐β‐cyclodextrin (HPBCD) was studied by charge‐transfer reversed‐phase thin‐layer chromatography using aqueous sodium chloride solutions as eluents. Each pesticide interacted with HPBCD, their lipophilicity linearly decreased with increasing HPBCD concentration, the pesticide ‐ HPBCD complex (probably inclusion complex) always being more hydrophilic than the uncomplexed pesticide. In many cases the retention of pesticide increased with increasing concentration of salt in the eluent. This effect can be tentatively explained by the suppression of the dissociation of the polar groups in the solute molecules resulting in increased apparent lipophilicity. No significant correlation was found between lipophilicity and complex stability or between salting‐out effect and lipophilicity, that is other than hydrophobic forces are involved in the pesticide ‐ HPBCD interaction.     

Rainwater composition as a function of the cloud type

The influence of the type of clouds that produce precipitation in the rainwater composition was analyzed. Logroño, a remote station in the North of Spain was chosen for the analyses. Results prove that the rainwater composition from Cumulonimbus is different to the composition of the rainwater from the other clouds. In addition, the source of NO₃ ^? and SO₄ ^2? is studied in the different types of clouds. It is shown that the source is the soil except Stratocumulus formed from Cumulus in which the source is the gas‐particle conversion.     

Ground water pollution by pesticides at the watershed‐soil catena scale: Lindane at the lower Colorado river basin (Argentina)

The movement of Lindane from application points at the surface soil towards the underground water and further transport within this compartment at the watershed‐soil catena scale, was inspected by measurements of the pesticide concentration in soil water at a controlled experiment where it was applied at a usual label dose. The concentrations of Lindane in soil water and the upper phreatic level were also measured at successive dates in samples obtained from a net of phreatimeter probes distributed over the area (1,500 km²) of the lower Colorado River basin (Bs. Aires, Argentina). The location of cultivated‐irrigated areas within the watershed was inferred from NDVI (Normalized Difference Vegetation Index)‐1 km‐10 day AVHRR images obtained at successive dates during the irrigation season. Feasible paths of underground gravitational water flows were computed by means of a GIS‐simulation model on the basis of local terrain slopes and aspects. The pattern of Lindane distribution over the basin was explained on the basis of the distribution of diffuse sources, the patterns of percolation and groundwater flows and the thermodynamic characteristics of the pesticide.     

A regional-scale sustainable development index: the case of Baja California Sur,Mexico

Sustainable development, as a multi-dimensional concept, is difficult to measure. Some efforts using indicators and indices have appeared in recent years, but most were developed on a national scale. Use of sustainability indicators has proven valuable for attaining better management of the environment by minimizing information gaps and maximizing community capabilities in terms of economic, social, environmental, and institutional sustainability dimensions. However, at least in the case of developing countries, the potential exists that national sustainability measures, based on national level indicators, may mask problems in sub-national zones with highly unsustainable conditions. This paper proposes a methodology to evaluate sustainable development at a local level, the use of which could be helpful in comparing different regions within a country or even among different countries. National sustainability indicators should result from a combination (whether additive or proportional) of regional sustainability indicators, as developed in this paper.     

Evaluation of the use of bioaccumulation and biological effects tools in caged mussels,within the European Water Framework Directive

Bioaccumulation and biological effects of pollution were assessed in mussels (Mytilus galloprovincialis) caged for one month at three sites in the Oiartzun estuary (south-eastern Bay of Biscay, Spain) with the aim of evaluating their usefulness within the investigative monitoring defined in the European Union Water Framework Directive (WFD). The highest concentrations of organic contaminants determined in mussels' tissue were detected towards the inner part of the estuary but no gradient pattern was found for metal bioaccumulation. Population fitness responses measured as condition index, stress on stress and gonad index were similar in all caged mussels and did not follow the organic pollution gradient. However, biomarkers determined at tissue, cell and protein level (histopathology, micronuclei frequency, malondialdehyde levels and vitellogenin-like protein levels) revealed a higher stress syndrome at the inner part of the estuary showing signs of genotoxicity, oxidative stress and endocrine disruption. Overall, the integrated chemical–biological approach in connection with mussel caging technique proved to be a useful tool to assess environmental pollution, allowing a better understanding of the cause–effect relationship within the investigative monitoring defined in the WFD.     

The effect of macrophytes on retention times in a constructed wetland for wastewater treatment

Retention times of treated water in a constructed wetland (CW) with horizontal subsurface flow were determined both in the vegetative and non-vegetative periods of 2005. Tracer experiments were performed using fluorescein, an organic compound detectable at extremely low concentrations. Nominal and tracer retention times were determined and compared. Winter tracer retention time (TRT 194 h) and nominal retention time (nHRT 190 h) were nearly exactly equal, while summer TRT (335 h) was approximately twofold higher than nHRT (158 h). Residence time distribution function (RTD) was used to compare retention times obtained for the vegetative and non-vegetative periods. The obtained results document a significant influence of dense common reed vegetation on retention characteristics of the studied system. Common reed can convert a significant volume of water from liquid to gas via evapotranspiration (ET) and thus prolong water retention times in the system. This is very important both technically and ecologically. Longer retention times mean a longer time for microbiological decay of wastewater. Water converted from liquid to gas causes cooling of the microclimate, which is very important, especially in intensively cultivated areas with a lack of water.     

The gastropod Osilinus atrata as a bioindicator of Cd,Cu, Pb and Zn contamination in the coastal waters of the Canary Islands

The aim of this study was to assess the use of Osilinus atrata (Gastropoda, Mollusca) as a biomonitor of heavy metals (Cd, Cu, Pb and Zn) within the coastal zone of the Canary Islands. In general, this top-shell snail showed high intraspecific variability in its tissue metal concentrations, which decreased according to the following sequence: Cu≥Zn>Cd≥Pb. In particular, Cd and Zn concentrations were higher in males than in females, whereas Cu concentrations increased slightly with weight, and Pb concentrations decreased. Cd and Cu concentrations showed notable spatial variability; Cd concentrations were higher in the eastern islands (Alegranza, La Graciosa, Lanzarote and Fuerteventura) and La Palma, whereas Cu levels were highest in some western islands (Gran Canaria, La Gomera and El Hierro). The arrival of waters from the African coastal upwelling, the pollution of coastal waters with agricultural fertilisers and the competition for uptake between metals appear to be the likely causes within these patterns of accumulation. In conclusion, O. atrata presents a great potential as a biomonitor of heavy metals, however, more information and further studies are necessary.     

Physicochemical properties of non-living water hyacinth (Eichhornia crassipes) and lesser duckweed (Lemna minor) and their influence on the As(V) adsorption processes

Eichhornia crassipes (Ec) and Lemna minor (Lm) are aquatic plants. They are considered as weeds of the water and approach being a scourge in many parts of the world, choking waterways and hindering transport upon them. At the same time they are known to readily remove heavy metal ions from water. This paper considers the use of non-living plants as novel and inexpensive biosorbent for the removal of As(V) from watersheds. In the first place they were conditioned and characterised to determine their physicochemical and surface properties and in the second place their adsorption properties for As(V) from aqueous solution were evaluated considering the toxicity of this metalloid in the environment. It describes the methodology to prepare the non-living biomasses; the physicochemical characterisation by SEM, XRD, FTIR, TGA analyses and surface characterisation of Ec and Lm by specific surface, hydration kinetic, point of zero charge determination by mass titration, active site density and XPS analysis are described. Both studied biomasses were found to be potential bio-sorbents for arsenic ions from aqueous solution. According to their efficiency to remove arsenic, they can be used in a very low cost metalloid ions removal system.     

Phosphorous cycling and biogeochemistry in a Venezuelan-flooded savanna

In 1970, a programme of land recuperation started in Venezuelan savannas, strongly affected by the seasonality of precipitation; therefore, a network of dykes has been built to alleviate the floods and retain water throughout the dry period. Under the dyked system, the environment has been altered, allowing a change in the herbaceous vegetation towards aquatic species and an increase in primary production. It is assumed that a considerable quantity of nutrients is lost from the ecosystem through the floodgates, a situation that could be worsened with the climate change. This contribution describes the atmospheric input and total output in stream run-off of phosphorous (P) in a flooded savanna. Internal pools of the biogeochemical cycle of P associated with terrestrial compartments are described. In the flooded savanna, a large amount of P is immobilised (29.6?kg?ha^?1) in their above ground biomass by grasses, and in soil microbial biomass. The P budget was nearly balanced, as measured losses were cancelled out by the inputs in rainfall. Soils act as a sink, retaining P coming either from precipitation or from desorption/mineralisation processes. That interruption can be maximised, and losses of P and other nutrients can be minimised with an adequate management of the floodgate.