Inclusion complexes of alpha- and gamma-cyclodextrins and the herbicide norflurazon: I. Preparation and characterisation. II. Enhanced solubilisation and removal from soils

The interaction of norflurazon with alpha- and gamma-cyclodextrins (CDs) yielded the formation of inclusion complexes at a 1:1 stoichiometric ratio in solution and in the solid state. Apparent stability constants of 50.7+/-1.6 and 37+/-1.7 M(-1) and an increase in herbicide solubility by up to five and fourfold for alpha- and gamma-CD, respectively, were determined from the phase solubility diagrams at 25 degrees C in water. Three processing methods (kneading, spray-drying and vacuum evaporation) were used to prepare norflurazon-CD solid inclusion complexes, which were characterised by infrared spectroscopy, differential scanning calorimetry and scanning electron microscopy. A high increase in the norflurazon dissolution rate was obtained with all the solid complexes with gamma-CD, but when alpha-CD was used, only the solid system obtained after the vacuum evaporation process showed a higher dissolution rate. This finding is a first step in the development of new, environmentally sound formulations of norflurazon (NFL), due to the capacity for increasing its dissolution rate and hydrosolubility, and thus diminishing the use of organic solvents. On the other hand, the effect of alpha- and gamma-cyclodextrin on the solubility of norflurazon in solution was also considered as a way of modifying its behaviour in the soil environment. Desorption studies of NFL from soils in the presence of alpha- and gamma-cyclodextrin were carried out using a batch equilibration method. The results obtained showed that alpha- and gamma-cyclodextrin greatly increased the removal of norflurazon previously adsorbed, proving the potential use of these CDs for in situ remediation of pesticide-contaminated soils.     

Residues and dissipation kinetic of abamectin,chlorfenapyr and pyridaben acaricides in green beans (Phaseolus vulgaris L.) under field conditions using QuEChERS method and HPLC

Abstract

The current study estimated the dissipation rates of abamectin, chlorfenapyr and pyridaben acaricides in pods of green beans (Phaseolus vulgaris L.) under field conditions in Egypt. Pesticides were extracted and cleaned-up by QuEChERS method and were analyzed by HPLC. The dissipation of these acaricides followed the first order kinetics model with half-life (t_1/2) values 1.00, 3.50 and 1.50?days for abamectin, chlorfenapyr and pyridaben, respectively. The lowest residues, at different time intervals of field application rate of each pesticide, were observed with abamectin followed by pyridaben and then chlorfenapyr. Pre-harvest intervals (PHIs) were 10.00, 13.50 and 6.00?days for abamectin, chlorfenapyr and pyridaben, respectively and were below the established European maximum residue limits (EU MRLs) 10–14, 14–21 and 7–10?days after application, respectively. If the fresh pods will be consumed after harvest, it is expected that the presence of these pesticides in the food will have a negative impact on human health. Therefore, the elimination of the residues of these harmful pesticides must be carried out.     

Detection of polycyclic aromatic hydrocarbons in skin oil obtained from roofing workers

Twelve polycyclic aromatic hydrocarbons have been analyzed in blood serum and skin oil collected from roofing workers. Although a range of 0.05–36 ng was observed in skin oil samples, none was detected in serum, at detection limits of 1–175 pg/ml.     

Tributyltin contamination around an oil terminal in Sullom Voe (Shetland)

This report provides clear evidence of tributyltin (TBT) contamination of coastal waters close to an oil terminal handling large tankers. Dogwhelk populations from Sullom Voe, Shetland, have been examined for the development by females of certain male sexual characteristics (e.g. a penis and vas deferens). This condition, termed imposex, is a response to exposure to tributylin compounds, and can be quantified by use of the relative penis size index (RPSI). Dogwhelk populations throughout Sullom Voe were strongly affected by TBT (RPSI 34 to 81%), and up to 90% of the females in the oil terminal area were sterile. Queen scallops collected in the Voe contained enhanced concentrations of tin in adductor muscle and gonad tissue (0.02 to 0.23 mg kg(-1) wet weight), but it is considered unlikely that their growth and development is adversely affected. Tin was rarely detected in scallops, queens, or dogwhelks outside the Voe, although the development of a vas deferens in many of the female dogwhelks indicated a degree of contamination of the open waters of Yell Sound. TBT was detectable (2 ng litre(-1) as tin) in only two sea water samples taken from the terminal area.     

Nonlinearities in source receptor relationships for sulfur and nitrogen compounds

The relationship between emissions and deposition of air pollutants, both spatially and in time forms an important focus for science and for policy makers. In practice, this relationship may become nonlinear if the underlying processes change with time, or in space. Nonlinearities may also appear due to errors in emission or deposition data, and careful scrutiny of both data sources and their relationship provides a means of picking up such deficiencies. Nonlinearities in source receptor relationships for sulfur and nitrogen compounds in Europe have been identified in measurement data for the UK. In the case of sulfur, the dry deposition process has been shown to be strongly influenced by ambient concentrations of NH3, leading to substantial increases in deposition rate as SO2 concentrations decline and the ratio SO2/NH3 decreases. The field evidence extends to measurements over three different surfaces in three countries across Europe. A mechanistic understanding of the cause of this nonlinearity has been provided. Apparent nonlinearities also exist in the sulfur deposition field through the influence of shipping emissions. The effect is clear at west coast locations, where during a period in which land-based sulfur emissions declined by 50%, no significant decline in concentrations of SO(2-) in precipitation were observed. The sites affected are primarily the coastal regions of southwestern UK, where shipping sources contribute a substantial fraction of the deposited sulfur, but the effect is not detectable elsewhere. Full quantification of the spatially disaggregated emission and their changes in time will eliminate this apparent nonlinearity in the source-receptor data. For oxidized nitrogen emission and deposition in the UK, there is strong evidence of nonlinearity in the source-receptor relationship. The concentrations and deposition of NO(3-) in precipitation have declined little following a reduction in emissions of 45% during the period 1987 to 2001. The data imply a significant decrease in the average transport distance for oxidized nitrogen and most probably an increase in the average oxidation rate. However, the net effect of changes in aerosol chemistry due to changes in sulfur emissions and less competition for the main oxidants as a consequence of reductions in sulfur emission have not been separated. A quantitative explanation of the cause of this nonlinearity is lacking and the effects are therefore identified as an important uncertainty for the development of further protocols to control acidification, eutrophication and photochemical oxidants in Europe.     

A laboratory exposure procedure for screening pulp and paper mill effluents for the potential of causing increased mixed function oxidase activity in fish

To better understand the relationships between pulp manufacturing processes and mixed function oxidase (MFO) enzyme induction in fish, a practical and standardized exposure procedure is required. This study was undertaken to develop a laboratory-based exposure procedure to quantify the relative MFO induction potencies of different types of pulp and paper mill effluents. One major consideration in developing the procedure was to ensure that the protocol was practical so that tests could be performed in a short time, with small volumes of effluents and using simple experimental conditions. A series of concentration-response and time-course experiments were conducted to find the minimum time and effluent concentration which could distinguish the ability of different effluents to cause significant MFO induction in rainbow trout in the laboratory. Experiments were also conducted to determine the effects of biotic and abiotic factors such as loading density, fish size and feeding regime. This study showed that the exposure of rainbow trout in the laboratory to 10% concentration of secondary-treated effluent for 96 h caused significant increases in hepatic MFO activity. The magnitude of MFO induction was comparable to other field and laboratory observations. While fish size, loading density and feeding regime were found to affect the test results, consistent responses within a laboratory using this protocol are possible, provided that these factors are standardized. Therefore, the short-term exposure approach described in this paper could be a relevant tool for assessing the ability of different types of pulp and paper mill effluents to cause MFO induction in fish.     

Atp-measurements in soil: A combination between the TCA and NRB ® extraction methods

The extraction of ATP from soils with the TCA- and NRB ®-methods shows qualitative and quantitative differences. A combination of both methods results in a higher yield of extracted ATP and in a solution of low optical quenching.     

Plasma ALP activity and blood PCV value changes in chick fetuses due to exposure of the egg to different xenobiotics

The effects of two polycyclic aromatic hydrocarbon (PAH) compounds (benz(k)fluoranthene and fluoranthene) and two heavy metals (cadmium and lead) were studied on the alkaline phosphatase (ALP) enzyme activity and hematocrit (PCV) values in chick fetuses. Eggs were exposed to one of the four compounds before incubation, by applying two exposure methods: injection (into the air cell) or immersion. Fluoranthene, cadmium and lead injection significantly decreased ALP activity compared to the control, while none of the compounds caused significant reduction in ALP activity in the immersion groups; however, a decreasing tendency was seen in these groups as well. Hematocrit values were increased after benz(k)fluoranthene immersion, fluoranthene immersion and cadmium injection. However, the doses in this study are relatively low (compared to other ecotoxicological studies in birds), the alteration in ALP enzyme activity and PCV values was apparent in each treatment group and is indicative of the high sensitivity of chick fetuses.     

Radiocarbon content of synthetic and natural semi-volatile halogenated organic compounds

Some halogenated organic compounds, such as polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and polybrominated diphenyl ethers (PBDEs), have been suggested to have natural sources but separating these compounds from their commercially synthesized counterparts is difficult. Molecular-level 14C analysis may be beneficial since most synthetic compounds are manufactured from petrochemicals (14C-free) and natural compounds should have "modern" or "contemporary" 14C levels. As a baseline study, we measured, for the first time, the 14C abundance in commercial PCB and PBDE mixtures, a number of organochlorine pesticides, as well as one natural product 2-(3',5'-dibromo-2'-methoxyphenoxy)-3,5-dibromoanisole. The latter compound was isolated from a marine sponge and is similar in structure to a PBDE. All of the synthetic compounds were 14C-free except for the pesticide toxaphene. which had a modern 14C abundance, as did the brominated natural compound. The result for toxaphene was not surprising since it was commercially synthesized by the chlorination of camphene derived from pine trees. These results suggest that measuring the 14C content of halogenated organic compounds may be quite useful in establishing whether organic compounds encountered in the environment have natural or synthetic origins (or both) provided that any synthetic counterparts derive from petrochemical feedstock.     

Rückst?nde und Kontaminanten in Lebensmitteln 29. und 30. Oktober 2002, Atrium Hotel, Mainz

Tagungsakündigungen

Rückst?nde und Kontaminanten in Lebensmitteln 29. und 30. Oktober 2002, Atrium Hotel, Mainz