Oxidation of MCPA and 2,4-D by UV radiation, ozone, and the combinations UV/H2O2 and O3/H2O2

The phenoxyalkyl acid derivative herbicides MCPA (4-chloro 2-methylphenoxyacetic acid) and 2,4-D (2,4-dichlorophenoxyacetic acid) were oxidized in ultrapure water by means of a monochromatic UV irradiation and by ozone, as well as by the combinations UV/H2O2 and O3/H2O2. In the direct photolysis of MCPA, the quantum yield at 20 degrees C was directly evaluated and a value of 0.150 mol Eins(-1) was obtained in the pH range 5-9, while a lower value of 0.41 x 10(-2) mol Eins(-1) was determined at pH=3. Similarly, for 2,4-D a value of 0.81 x 10(-2) mol Eins(-1) was deduced, independent of the pH of work. The influence of the additional presence of hydrogen peroxide was established in the combined process UV/H2O2, and the specific contribution of the radical pathway to the global photo-degradation was evaluated. The oxidation by ozone and by the combination O3/H2O2 was also studied, with the determination of the rate constants for the reactions of both herbicides with ozone and hydroxyl radicals at 20 degrees C. These rate constants for the direct reactions with ozone were 47.7 and 21.9 M(-1) s(-1) for MCPA and 2,4-D respectively, while the found values for the rate constants corresponding to the radical reactions were 6.6 x 10(9) and 5.1 x 10(9) M(-1) s(-1).     

(M)VOC and composting facilities. Part 2: (M)VOC dispersal in the environment

BACKGROUND, AIMS AND SCOPE: Composting facilities are known to release odorous volatiles due to biodegradation of municipal waste and plant residues. Although odour perception and its grading is influenced by experience, attitude and adaptation, these emissions have created a lack of acceptance for residents in the vicinity of composting facilities. Enclosure of compost pile halls, ventilation systems and biofilters are often insufficient to minimise the burden of compost-derived compounds in the air. Moreover, economic considerations forced smaller communities to establish less sophisticated facilities with open storage areas and other relevant sources for wind-borne dispersal of bioaerosols. Aim of the present study was to characterise the immission and dispersal of microbial volatiles (MVOC) and, besides, to find coincidences between MVOC and compost odour. METHODS: In the course of this study, the surroundings of two composting facilities, differing in their type of process engineering, were investigated for emission of volatiles in the environment. Both microbially and plant-derived substances were assessed, several of which have low odour thresholds. Air samples were taken in distances ranging from 50 to 800 m in a downwind direction from each facility. RESULTS AND DISCUSSION: Compost-derived and microbial volatile organic compounds (MVOC) were found at distances of up to 800 m from the composting facilities. Terpenes like alpha-pinene, camphene and camphor were the dominant compounds and coincided with typical compost odour, whereas several typical MVOC were not found at greater distances. The terpenes in combination with certain MVOC may play an important role in the perception of compost odour. Exposure concentrations were not of toxicological relevance, but sensory irritation and psychohygienic effects due to an annoyance potential of such compounds should not be dismissed. RECOMMENDATIONS AND OUTLOOK: Although terpenes are generally associated with pleasant odour characteristics, they seemed to contribute to malodours in a mixture with other VOC, in this context of volatile waste from compost facilities. Malodorous emissions from biowaste have to be considered as sources of health complaints and the investigation of mixtures of compost-derived volatiles is still inevitable. Exposure levels have to be discussed taking VOC mixtures into account. Within composting facilities, technical devices have to be improved to minimise dispersal of volatiles to prevent residents from immissions eventually causing health complaints.     

Enhanced experimental flexibility and control in ecotoxicological mesocosm experiments--a new outdoor and indoor pond and stream system

Scope The German Federal Environmental Agency has put into operation a new modular mesocosm system consisting of eight outdoor and eight indoor ponds and streams in order to investigate fate and effects of chemicals and municipal wastewater in aquatic ecosystems. General design and special characteristics are given to demonstrate the wide range of possibilities for experimental research. - General design. Each of the 16 streams with riffle and pool sections can be varied in length up to 106 m. The streams can be run as circular or flow-through systems at a flow velocity of 0.02 to 0.6 m/s. Physico-chemical standard parameters are measured on-line. The 16 ponds, which can be connected to the stream systems, are equipped with drainage and pore water-sampling devices for simulating processes in the littoral zone including influent and effluent ground water flow. Perspectives Since the highly flexible and controllable construction also allows treating a wide range of hydrological and ecological experiments external institutions are invited to submit proposals.     

Cytoprotective and anti-apoptotic action of HSP70 stress protein in Oreochromis niloticus exposed to residual dilutions of insecticides with fipronil and ethiprole

Abstract

The objective of this research was to investigate the potential damage caused by the residual concentrations of the insecticides Regent^® WS 800 and Curbix^® SC 200, containing fipronil and ethiprole, respectively as active ingredients, on the liver of Oreochromis niloticus. The analyses of HSP70 shock protein labelling and cell death process by TUNEL method were performed in order to measure the effects of the exposure of cell repair system of fish to both insecticides. Statistical analyses showed no significant molecular damage to the hepatic tissue of animals. Nevertheless, variations in HSP70 and DNA fragmentation levels, endpoint of cell repair system response and cellular death, respectively, were observed in several groups. These results indicate that the cell repair machinery was efficient when in contact with residual concentrations of insecticides. However, the DNA fragmentation detected by the TUNEL method suggests that even in face of the cytoprotective action of the HSP70 protein, there are damages that become irreparable. To finish, it is worth mentioning that given the results obtained from residual concentrations, use in the field should be with caution.     

One-year study of the elemental composition and source apportionment of PM10 aerosols in Florence, Italy

An extensive investigation was carried out for the characterisation of the air particulate composition in Florence. The aim was to determine the aerosol elemental concentrations, as well as to identify pollution sources. For our investigation, the external Particle-Induced X-Ray Emission-Particle-Induced gamma-Ray Emission beam facility of the Istituto Nazionale di Fisica Nucleare, Van de Graaff accelerator at the Physics Department of the Florence University was used. We report the results of the analysis of a long temporal series (approximately 1 yr) of PM10 particulate samples, collected on Millipore filters on a daily basis in three different sites (characterised by different urban settings). Daily concentrations of more than 20 elements were detected. The long sampling period (approximately 1 yr) allowed a comparison with the air quality recommended values and the identification of seasonal variations. Four main sources (traffic, oil-combustion, soil-dust, and wind transported sea-salt) were extracted with the help of Principal Component Analysis (PCA). An absolute PCA showed traffic to be the major source both in the high traffic site and in the urban background site.     

Biochemical composition of a meso-bathyal lobster

To characterise some traits of the life strategies of Polycheles typhlops, a deep-sea small lobster usually encountered as by-catch within deep trawls in the Southern Tyrrhenian Sea (Mediterranean Sea), we analysed the biochemical composition of the caudal muscles of 49 specimens collected in March and April 2007. Differences in the biochemical composition between females and males were weak, but relevant differences in protein (>90% of the organic C) and lipid (4–6%) contents were observed between developmental stages both in females and males. These differences are likely to be related to different food items and/or to the metabolic shifts associated with their reproduction. We argue that this deep-sea lobster could cover a relevant role in the meso-pelagic food webs and attract future commercial interest.     

Phototransformation of <Emphasis Type="SmallCaps">l</Emphasis>-tryptophan and formation of humic substances in water

Humic substances are poorly known, though they represent a major pool of non-biotic organic carbon on earth. In particular, there is little knowledge on the formation of humic substances by irradiation of organic matter dissolved in waters. Specifically, it is known that humic substances can be formed from proteins by photochemical processes in surface waters, but the role of single amino acids and their transformation pathways are not yet known. Therefore, here we studied the phototransformation of aqueous l-tryptophan under simulated sunlight. Irradiated l-tryptophan solutions were analyzed by absorption, fluorescence, nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies, chromatography, potentiometry and mass spectrometry (MS). The solutions appeared turbid after irradiation; therefore, nephelometry and dynamic laser light scattering were used to characterize the suspended particles. Results show that about 95% of l-tryptophan was degraded in 8-h irradiation, undergoing deamination and decarboxylation of the amino acidic moieties to release ammonium and formate. The MS signal at m/z 146 suggests the formation of 3-ethylindole, while pH-metric and NMR data revealed the presence of hydroxylated compounds. The phototransformation intermediates of l-tryptophan had fluorescence and absorption spectra similar to those of humic substances, they were able to produce ^·OH upon irradiation and tended to aggregate by both ionic and hydrophobic interactions. Overall, our findings reveal for the first time the nature of products formed upon phototransformation of l-tryptophan. Interestingly, the transformation of l-tryptophan is quite different from that of the previously studied l-tyrosine, although both compounds produce humic-like materials under irradiation.     

Molecular insight into the population structure of common and spotted dolphins inhabiting the pelagic waters of the Northeast Atlantic

Several cetacean species exhibit fine-scale population structure despite their high dispersal capacities and the apparent continuity of the marine environment. In dolphins, most studies have focused on coastal areas and continental margins, and they revealed differentiated populations within relatively small geographic areas, sometimes in conjunction with a specialisation for different habitats (ecotypes). We analysed the population genetic structure of short-beaked common dolphins (Delphinus delphis) and Atlantic spotted dolphins (Stenella frontalis) in the Azores and Madeira, the two most isolated archipelagos of the North Atlantic. The archipelago of the Azores is divided into three groups of islands and stands 900 km away from Madeira. It is not known whether individuals migrate between groups of islands and archipelagos, nor whether distinct ecotypes are present. These questions were investigated by genetic analyses of 343 biopsy samples collected on free-ranging dolphins. The analyses consisted in sequencing part of the mitochondrial hyper-variable region, screening up to 14 microsatellite loci, and molecular sexing. Results did not unravel any population structure at the scale of the study area. Lack of differentiation matches expectations for spotted dolphins, which are transient in both archipelagos, but not for common dolphins, which are present year-round in the Azores and potentially resident. Absence of genetic structure over hundreds and even thousands of kilometres implies the existence of gene flow over much larger distances than usually documented in small delphinids, which could be achieved through individual movements. This finding indicates that population structure in oceanic habitat differs from that observed in coastal habitat.     

Modis reflectance and active fire data for burn mapping and assessment at regional level

This paper presents an algorithm for rapid and accurate burn mapping that is applied here to the forest fires occurred in Galicia (northwest Spain) in August 2006, when nearly 930 km² were almost entirely burned over the course of eight days. The algorithm synergistically combines remotely-sensed reflectance and active fire data as measured by the MODIS (MODerate resolution Imaging Spectrometer) sensor on board Terra and Aqua NASA (National Aeronautics and Space Administration) satellites. Burned area data collected from this work was compared to official fires statistics from the Spanish Ministry of Environment and to perimeters that were derived using a high spatial resolution satellite image. In a later step, burn patches area analyzed using information from the National Forest Map (1:50,000) and some Geographical Information Systems (GIS) tools.