Gas phase reactions of unsaturated esters with Cl atoms

Background, aim, and scope  

Acrylate and methacrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon (CH₂=CHCOO– and CH₂=CCH₃COO–, respectively) and are widely used in the polymer plastic and resin production. Rate coefficients for Cl reactions for most of the unsaturated esters have not been previously determined, and a good understanding is needed of all the atmospheric oxidation processes of these compounds in order to determine lifetimes in the atmosphere and to evaluate the impact of these reactions on the formation of photo-oxidants and therefore on health and environment.     

Temporal and spatial changes of PAH concentrations in Mytilus galloprovincialis from Ria de Vigo (NW Spain)

The aim of this study was to establish the temporal trends and spatial distribution of Polycyclic Aromatic Hydrocarbons (PAHs) in Ria de Vigo by means of studying the PAH burden in wild mussels. The samples were collected in eight sites along the margins of the Ria de Vigo during November from 1998 to 2008 and Polycyclic Aromatic Hydrocarbon contents were determined using high performance liquid chromatography–fluorescence derivatization (HPLC–FLD). Quality of chemical analysis was guaranteed by participation in QUASIMEME intercalibration exercises carried out during the period of analysis. The concentrations for the sum of 13 PAHs were in the range 24–480 μg/kg dw, typical of an urban and industrialized area (50–500 μg/kg dw) except for a punctual input in La Guía in 1998 that led to a concentration above 1,000 μg/kg dw. In general, the sites in the outermost section of the estuary (ría) showed the lowest values, with an increasing gradient in the medium and inner parts of the ría. Temporal patterns show, in general, a downward trend. The relative proportion of 3 and 4 ring PAHs also varies with the site, the former being predominant in the outermost area and the latter in the medium and inner parts of the ría. This is consistently related with the sources and processes taking place in different areas of the estuary.     

Pyrethroid use-malaria control and individual applications by households for other pests and home garden use

Presence of pyrethroid insecticides in human breast milk and in thatch wall material of dwellings from Southern Africa subtropical area (Manhiça, Mozambique) was investigated to assess potential pyrethroid route of human exposure. Human breast milk samples were collected during 2002 when pyrethroids were widely used as insecticides for mosquito bed nets in Mozambique for malaria control. The median concentration value of total pyrethroids ranged between 87 and 1200 ng/g lw, with λ-cyhalothrin being the most predominant pyrethroid in human breast milk contributing for 35% of the total amount. Moreover, and for the first time, an isomer-specific enrichment was found in human breast milk, showing a selective isomeric accumulation or metabolism in the human body. Based on the calculated pyrethroid concentrations in human breast milk, the daily ingestion rate of pyrethroid was estimated. The nursing infant dietary intake ranged from 0.67 to 9.0 μg (kg of body weight)^− 1 day^− 1. In addition, thatch materials collected after the reintegration of dichlorodiphenyltrichloroethene (DDT) as insecticide residual spraying (IRS) in Mozambique, showed the presence of pyrethroids with concentration values ranging between 6.9 and 700 ng/g dw. In thatch material as well as in human breast milk, pyrethroid contamination was mainly attributed to the agriculture usage of this insecticide knowing that agriculture represent the 80% of the economy in Mozambique. However, a possible usage of this insecticide as IRS in Mozambique cannot be excluded despite their low efficiency for malaria control. The continued use of these compounds (both for agriculture and malaria prevention) and the ingestion rates calculated from the breast milk concentrations indicate that these insecticides cannot be overlooked for the assessment of the lactation risks of breastfeeding infants from the Manhiça region.     

Studies on atmospheric degradation of diazinon in the EUPHORE simulation chamber

The gas phase atmospheric degradation of diazinon has been investigated at the large outdoor European Photoreactor (EUPHORE) in Valencia, Spain. The rate constant for reaction of diazinon with OH radicals was measured using a conventional relative rate method with di-n-buthylether as reference compound being k = (3.5 ± 1.2) × 10⁻¹¹ cm³ molecule⁻¹ s⁻¹ at 302 ± 10 K and atmospheric pressure. The available evidence indicates that tropospheric degradation of diazinon is mainly controlled by reaction with OH radicals, and that the tropospheric lifetime with respect to the OH reaction is estimated to be around 4 h whereas its lifetime with respect to the photolysis is higher than 1 d under our conditions. Significant aerosol formation was observed following the reaction of diazinon with OH radicals, and the main carbon-containing products detected in the particle phase were hydroxydiazinon, hydroxydiazoxon and 2-isopropyl-6-methyl-pyrimidinyl-4-ol.     

Geographic and trophic patterns of OCs in pelagic seabirds from the NE Atlantic and the Mediterranean: a multi-species/multi-locality approach

Trophic ecology and geographic location are crucial factors explaining OC levels in marine vertebrates, but these factors are often difficult to disentangle. To examine their relative influence, we analyzed PCBs, DDTs and stable-nitrogen isotope signatures (δ15N) in the blood of 10 pelagic seabird species across 7 breeding localities from the northeast Atlantic and western Mediterranean. Large scale geographic patterns emerged due to the confined character and greater historical OC inputs in the Mediterranean compared to the Atlantic basin. Spatial patterns also emerged at the regional scale within the Atlantic basin, probably associated with long-range pollutant transport. Trophic ecology, however, was also a major factor explaining OC levels. We found clear and consistent OC differences among species regardless of the sampled locality. However, species δ15N and blood OC levels were not correlated within most breeding localities. Petrel species showed significantly greater OC burdens than most shearwater species but similar trophic positions, as indicated by their similar δ15N signatures. This pattern probably results from Petrel species feeding on mesopelagic fish and squid that migrate close to the sea surface at night, whereas shearwater species mainly feed on epipelagic diurnal prey. In sum, this study illustrates the lasting and unequal influence of past human activities such as PCB and DDT usage across different marine regions. In addition, our results suggest that multi-species designs are powerful tools to monitor geographic patterns of OCs and potentially useful to assess their vertical dynamics in the marine environment.     

Phenol tolerance, changes of antioxidative enzymes and cellular damage in transgenic tobacco hairy roots colonized by arbuscular mycorrhizal fungi

Phytoremediation has been recognized as a cheap and eco-friendly technology which could be used for the remediation of organic pollutants, such as phenolic compounds. Besides, the extent to which plants react to environmental pollution might depend on rhizosphere processes such as mycorrhizal symbiosis. In the present work, phenol tolerance of transgenic tobacco hairy roots (HR), namely TPX1, colonized with an arbuscular mycorrhizal fungus (AMF) was studied. However, the question is whether AMF symbiosis can moderate adverse effects of phenol to the plant tissues. Thus, the antioxidative response as well as parameters of oxidative damage, like malondialdehyde (MDA) content, were determined. Antioxidative enzymes such as peroxidase, superoxide dismutase, ascorbate peroxidase were higher in TPX1 HR colonized with AMF, compared to wild type HR colonized by AMF, in the presence of increasing concentrations of the pollutant. Besides, MDA levels remained unaltered in TPX1 HR associated with AMF treated with the xenobiotic. These results, suggested that this culture could tolerate phenol and moreover, it has an efficient protective mechanism against phenol-induced oxidative damage, which is of great importance in the selection of species with remediation capacities. Thus, transgenic HR colonized with AMF could be considered as an interesting model system to study different processes which play a key role in the phytoremediation of organic pollutants.     

The microbiota of an unpolluted calcareous soil faces up chlorophenols: Evidences of resistant strains with potential for bioremediation

To highlight the effects of a variety of chlorophenols (CP) in relation to the response of an indigenous bacterial community, an agricultural Mediterranean calcareous soil has been studied in microcosms incubated under controlled laboratory conditions. Soil samples were artificially polluted with 2-monochlorophenol (MCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP), at concentrations ranging from 0.1 up to 5000 mg kg⁻¹. Both activity and composition of the microbial community were assessed during several weeks, respectively, by respirometric methods and PCR-DGGE analysis of extracted DNA and RNA. Significant decreases in soil respirometric values and changes in the bacterial community composition were observed at concentrations above 1000 mg kg⁻¹ MCP and TCP, and above 100 mg kg⁻¹ PCP. However, the persistence of several active bacterial populations in soil microcosms contaminated with high concentration of CP, as indicated by DGGE fingerprints, suggested the capacity of these native bacteria to survive in the presence of the pollutants, even without a previous adaptation or contact with them.The isolation of potential CP degraders was attempted by culture plating from microcosms incubated with high CP concentrations. Twenty-three different isolates were screened for their resistance to TCP and PCP. The most resistant isolates were identified as Kocuria palustris, Lysobacter gummosus, Bacillus sp. and Pseudomonas putida, according to 16S rRNA gene homology. In addition, these four isolates also showed the capacity to reduce the concentration of TCP and PCP from 15% to 30% after 5 d of incubation in laboratory assays (initial pollutant concentration of 50 mg L⁻¹). Isolate ITP29, which could be a novel species of Bacillus, has been revealed as the first known member in this bacterial group with potential for CP bioremediation applications, usually wide-spread in the soil natural communities, which has not been reported to date as a CP degrader.     

Intercomparison exercise for gases emitted by a cement industry in Spain: a functional data approach

This paper describes the results of an intercomparison exercise referring to the measurement of atmospheric pollutants emitted by cement plants. The research was conducted in 2008 in Catalonia, Spain. Thirteen Spanish companies accredited to make pollutant measurements and with suitably approved equipment and trained staff participated in the research. The aim of the research was to evaluate the technical competence of the accredited companies in conducting tests in situ. The results obtained from the application of the methodology described in international standards--on the basis of conventional statistical analyses--were compared with those obtained using functional data analysis. On comparing the two methods, it was concluded that the functional method, although more complex, has advantages over the conventional statistical method. This is because the functional approach compares curves rather than mean values. Furthermore, it does not presuppose a normal distribution of the data.     

Determinants of efficiency in the provision of municipal street-cleaning and refuse collection services

Effective waste management systems can make critical contributions to public health, environmental sustainability and economic development. The challenge affects every person and institution in society, and measures cannot be undertaken without data collection and a quantitative analysis approach. In this paper, the two-stage double bootstrap procedure of Simar and Wilson (2007) is used to estimate the efficiency determinants of Spanish local entities in the provision of public street-cleaning and refuse collection services. The purpose is to identify factors that influence efficiency. The final sample comprised 1072 municipalities. In the first stage, robust efficiency estimates are obtained with Data Envelopment Analysis (DEA). We apply the second stage, based on a truncated-regression, to estimate the effect of a group of environmental factors on DEA estimates. The results show the existence of a significant relation between efficiency and all the variables analysed (per capita income, urban population density, the comparative index of the importance of tourism and that of the whole economic activity). We have also considered the influence of a dummy categorical variable - the political sign of the governing party - on the efficient provision of the services under study. The results from the methodology proposed show that municipalities governed by progressive parties are more efficient.