Importance of considering pesticide stereoisomerism--proposal of a scheme to apply Directive 91/414/EEC framework to pesticide active substances manufactured as isomeric mixtures

An important gap has been detected in the application of the European framework for the evaluation of pesticide active substances constituted by enantiomeric and other kind of stereoisomeric mixtures. Up to date, little attention has been paid to the different biological properties of these compounds. Considering efficacy, toxicity, environmental fate and behaviour and ecotoxicity of separated isomers is necessary to fulfil Directive 91/414/EEC objectives of health and environment protection. Here, a critical review of this question for pesticide active substances is presented. An evaluative scheme for considering this question in the framework of Directive 91/414/EEC is also proposed.     

Empty nests in the great tit (Parus major) and the pied flycatcher (Ficedula hypoleuca) in a polluted area

Great tits (Parus major) are sometimes found to incubate in their nests even though the nests contain no eggs. This phenomenon has been observed in different parts of Europe (Sweden, Finland, UK, Netherlands, Germany) and it has become more common during the 1980s. We analysed the occurrence of empty nests in P. major and in pied flycatcher (Ficedula hypoleuca) in SW Finland from 6-year data collected in a polluted area around a copper smelter which emits large quantities of sulphuric oxides and heavy metals. Among first broods 3.3% of P. major females incubated in empty nests. Incubation on empty nests was not observed in F. hypoleuca, but in this species 2.4% of the nests remained without eggs. In both species empty nests were more common close to the pollution source than farther away. Histopathological analyses in P. major suggest that there are diverse reasons for the incapability of a female to lay. One out of five P. major females captured from incubating in an empty nest had dark cysts in her oviduct. Two P. major females had very scanty medullary bone tissue in their tibiotarsus and tarsometatarsus and one female showed exceptionally high concentrations of lead in her bone tissue. We conclude that air pollutants enhance the number of empty nests especially in F. hypoleuca, but cannot wholly explain the phenomenon in P. major.     

Isolation and identification of intermediates from biodegradation of low chlorinated biphenyls (Delor-103)

Microorganism Pseudomonas species P2 metabolizes polychlorinated biphenyls (PCBs) and biphenyl, producing the whole spectrum of intermediates, among them coloured intermediates, which are suitable for the monitoring of PCBs degradation by optical sensors. Knowledge of chemical structures and conditions of development of colour metabolites is necessary for application of optical analytical methods. The main goal of this work was the isolation and identification of intermediates from the biodegradation of the mixture of low chlorinated biphenyls (Delor-103), which is based on the solid phase extraction (SPE) of the whole mixture using LiChrolut EN cartridges, then silylation of the extract as one way to the identification of one part of intermediates by GC-MS, and acetylation of the extract as a way for the further concentration and analysis of more polar chlorobiphenylols and chlorobiphenyldiols. The combination of SPE and following acetylation allows to obtain chlorobiphenylols and chlorobiphenyldiols as an almost pure fraction. The acetylation method could be also used instead SPE procedure with the same final concentration effect. Using the simulation mass spectrometry program, two new compounds, dihydrodihydroxytrichloro- and tetrahydrodihydroxytrichlorobiphenyl, as silylderivatives, were identified.     

Modelling the absorption and desorption of cadmium on paper pulp using kinetic approaches

The presence of toxic metals on paper pulp and the migration of these metals to food from the food package is receiving significant attention. The final exposure levels for consumers depend on two main processes. First the potential of metals to bind paper pulp during manufacture. Second, the metal potential to migrate from paper to food during storage and use. Binding and unbinding processes are modelled for cadmium kinetics through kinetic approaches. The cadmium concentration in paper pulp is estimated from the cadmium concentration in the water-pulp liquor during manufacture, the temperature, and contact time. Two food simulants have been employed for desorption studies, water and acetic solution (3%, w/w). As expected, under acidic conditions desorption is total and rapid (close to 100% desorption reached in a few minutes). However, the desorption of cadmium into the neutral food simulant depends on the initial cadmium concentration in the paper pulp, temperature and contact time. Surface response curves for each combination are presented. Temperature did not affect cadmium binding, but played a significant role for the desorption processes into the neutral food simulant. The proposed equations offer a good fitting of the experimental values, with p < 0.001 and residuals within a factor of 3 for over 99% of the measured data. These models allow estimations of the expected exposure levels in consumers, on the basis of manufacture and use conditions. Linking the expected exposure with toxicity thresholds, such as the admissible daily intake (ADI), would allow a scientific assessment of the maximum acceptable cadmium levels in water-pulp liquors during manufacture and in the final paper pulp on the basic of the use patterns of each food packaging material.     

Adsorption of atrazine from aqueous solution on heat treated kerolites

The adsorption of 6-chloro-N(2)-ethyl-N(4)-isopropyl-1,3,5-triazine-2,4-diamine (atrazine) on heat treated kerolite samples at 110 degrees C (K-110), 200 degrees C (K-200), 400 degrees C (K-400) and 600 degrees C (K-600) from aqueous solution at 25 degrees C has been studied. The evolution of surface properties of kerolite samples such as specific surface area and porosity after heat treatment was analysed. The clays were characterised by using usual techniques: FTIR spectroscopy, XRD diffraction, TG and DTG analysis, surface analysis and Hg porosimetry. The adsorption experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K(f)) of the samples; K(f) values range from 468 mgkg(-1) for the K-110 sample up to 2291 mgkg(-1) for the K-600 sample. The values obtained for the removal efficiency (R), (percentage of pesticide removed), ranged from 48% for K-110 up to 78% for K-600. The adsorption experiments showed that the stronger heat treatment, the most effective adsorption of atrazine, so, as this type of clay is relatively plentiful, these activated samples might be used in order to remove this pesticide from water.     

Symbiotic efficiency of autochthonous arbuscular mycorrhizal fungus (G. mosseae) and Brevibacillus sp. isolated from cadmium polluted soil under increasing cadmium levels

The effect of inoculation with indigenous naturally occurring microorganisms (an arbuscular mycorrhizal (AM) fungus and rhizosphere bacteria) isolated from a Cd polluted soil was assayed on Trifolium repens growing in soil contaminated with a range of Cd. One of the bacterial isolate showed a marked PGPR effect and was identified as a Brevibacillus sp. Mycorrhizal colonization also enhanced Trifolium growth and N, P, Zn and Ni content and the dually inoculated (AM fungus plus Brevibacillus sp.) plants achieved further growth and nutrition and less Cd concentration, particularly at the highest Cd level. Increasing Cd level in the soil decreased Zn and Pb shoot accumulation. Coinoculation of Brevibacillus sp. and AM fungus increased shoot biomass over single mycorrhizal plants by 18% (at 13.6 mg Cd kg(-1)), 26% (at 33.0 mg Cd kg(-1)) and 35% (at 85.1 mg Cd (kg(1)). In contrast, Cd transfer from soil to plants was substantially reduced and at the highest Cd level Brevibacillus sp. lowered this value by 37.5% in AM plants. Increasing Cd level highly reduced plant mycorrhization and nodulation. Strong positive effect of the bacterium on inocula, are important in plant Cd tolerance and development in Cd polluted soils.     

Activated sludge inhibition by chemical stressors--a comprehensive study.

The effects of shock loads of 1-chloro-2,4-dinitrobenzene (CDNB); cadmium; 1-octanol; 2,4-dinitrophenol (DNP); weakly complexed cyanide; pH 5, 9, and 11; and high ammonia levels on activated sludge biomass growth, respiration rate, flocculation, chemical oxygen demand removal, dewaterability, and settleability were studied. For all chemical shocks, except ammonia and pH, concentrations that caused 15, 25, and 50% respiration inhibition were used to provide a single pulse shock to sequencing batch reactor systems containing a nitrifying or non-nitrifying biomass. Cadmium and pH 11 shocks were most detrimental to all processes, followed by CDNB. The DNP and cyanide primarily affected respiration, while pH 5, pH 9, octanol, and ammonia did not affect the treatment process to a significant extent. A chemical source-process effect matrix is provided, which we believe will aid in the development of methods that prevent and/or attenuate the effects of toxic shock loads on activated sludge systems.     

The three-year monitoring of 18 elements in five edible mushroom species collected from an old orchard

Abstract

The content of Al, As, Be, Cd, Ca, Cr, Co, Cu, Fe, Pb, Li, Mg, Mn, Ni, Rb, Se, Sr, and Zn in fruiting bodies of edible mushrooms Calocybe gambosa, Entoloma clypeatum, Entoloma saepium, Xerocomellus chrysenteron, and Amanita rubescens growing in an orchard planted with fruit trees and situated close to a high-grown forest was studied during years 2016–2018. A. rubescens showed the highest potential of the element accumulation with bioconcentration factors of 48.5, 16.2, 7.80, 6.53, 1.75, and 1.68 obtained for Rb, Cd, Cu, Zn, Sr, and Mg, respectively. Both Entoloma species accumulated the elements similarly with bioconcentration factors >1.0 obtained for Rb, Cu, Cd, and Mg. Bioconcentration factors <0.05 were obtained for Al, Cr, Fe, and Pb in all studied species. The contents of beryllium (<0.1?mg/kg dry matter) were always the lowest among the studied elements. The contents of some elements of studied mushroom species significantly fluctuated over the years. Despite the fact that some studied elements (As, Be, Cd, Pb, Ni) are considerably toxic for humans, the pronounced effect on health is not expected if the studied mushroom species are consumed occasionally and do not represent the main component of the diet.     

Study on the formation and transport of ozone in relation to the air quality management and vegetation protection in Tenerife (Canary Islands)

An experimental study on the formation and transport of ozone in ambient air was performed in Tenerife (Canary Islands) in order to investigate the processes affecting ozone levels and air quality. The special features of Tenerife (prevalence of the trade wind pattern (NE), orography and the specific location of the local ozone sources) permit to quantify the role of the ‘long-range transport from northern latitudes' versus the ‘formation and transport of ozone downwind of the main urban areas' of Tenerife. Levels of O₃, NO₂ and O_X were monitored in different types of environments to achieve this purpose. The results showed that: (1) upwind of the urban areas ozone is mainly transported from the ocean by trade winds, (2) local ozone titration (by NO) and ozone replenishment from the ocean are the main causes of ozone variations in urban and suburban areas, and (3) photochemical ozone production occurs downwind of the urban areas. Photochemical production causes daylight O₃ and O_X levels downwind of urban areas to be frequently (60% and 35% days/year, respectively) higher than upwind of the urban sites (O₃ and O_X excess frequently in the range 5–20 ppbv). Due to the above processes, different daily ozone cycles occur in short distances (<30 km), with maximum O₃ levels during daylight or night depending on the site. Ozone phytotoxicity was assessed by calculating the AOT40 index upwind and downwind of the main urban areas. The critical value for the 5-day-AOT40 index was simultaneously exceeded at the two sites (few times/year) during long-range transport events. During the additional exceedances of the critical value downwind of the urban area, relatively high 5-day-AOT40 values were recorded upwind of the urban site. Thus, long-range transport from northern latitudes may produce relatively high 5-days-AOT40 levels in the oceanic boundary layer. These results are important for the protection of the large number of endemic plants in the Canaries. The conceptual model discussed in this study may be qualitatively applied to other islands which possess features similar to those of Tenerife.     

Photocatalytic degradation of formaldehyde containing wastewater from veterinarian laboratories

The photocatalytic destruction of methanol, formaline (mixture of formaldehyde, methanol and water) and formaline wastes from the preservation of vertinarian physiologic samples has been attempted by two different processes, at high concentrations of reagents and by dossification of reagents, varying pH in both. Experiment evolution has been monitored by measuring the organic matter such as TOC and formaldehyde concentrations [H2CO]. Also, methanol and methanol-formaldehyde interactions with the TiO2 surface have been analysed by FTIR spectroscopy. Results indicate that at high concentrations the catalyst surfacial alterations given by methoxy, formates or carbonates, according to the pH of the sample can profoundly affect catalyst behaviour. It has been established that reagent dossification is advantageous for enhancing photonic efficiency as it minimizes the adsorbate presence that hampers the photocatalytic process.