Metal exposure in cows grazing pasture contaminated by iron industry: Insights from magnetic particles used as tracers.

Magnetic particles (MP) emitted by an iron smelter were used to investigate the exposure of cows grazing on a grassland polluted by these MP and by large amounts of potentially toxic elements (PTE). The morphology as well as the chemical composition of the MP separated from cow dung were studied. Large amounts of typical MP were found (1.1 g kg(-1) dry weight) in the cow dung sampled from the exposed site, whereas these particles were absent from the reference unpolluted site. The ingested MP were mainly technogenic magnetic particles (TMP) emitted by the smelter. Considering the MP concentration in the grazed grass on the exposed site, it was concluded that cows absorb the MP not only from the grass but also from the soil surface. The results of a mild acidic leaching of the MP suggested that the particles were possibly submitted to a superficial dissolution in the abomasum, pointing at a potential route of transfer of the PTE originating from the TMP and leading into food chains. TMP were only a small part of the anthropogenic contamination having affected the soil and the dung. However, due to their unequivocal signature, TMP are a powerful tracer of the distribution of PTE in the different compartments constituting the food chains and the ecosystems. Furthermore, the measurement of the particle sizes gave evidence that a noticeable proportion of the MP could enter the respiratory tract.

Isolation of technogenic magnetic particles.

Technogenic magnetic particles (TMPs) emitted by various industrial sources, such as smelting plants, end up after atmospheric transfer on the soil surface. In the present study, we characterised the origin and composition of such particles emitted by a large iron smelting plant and deposited on particular substrates, namely tombstones, which act as a very interesting and appropriate matrix when compared to soil, tree bark, lichens or attic dust. The isolation and subsequent description of TMPs require a critical step of separation between different components of the sample and the magnetic particles; here, we described an efficient protocol that fulfils such a requirement: it resorts to water suspension, sonication, repeated magnetic extraction, sedimentation, sieving and organic matter destruction at 550 °C in some instances. The isolated TMPs displayed a noticeable crystalline shape with variable compositions: a) pure iron oxides, b) iron+Cr, Ni or Zn, and c) a complex structure containing Ca, Si, Mg, and Mn. Using Scanning Electron Microscope Energy Dispersive X-ray (SEM-EDX), we obtained profiles of various and distinct magnetic particles, which allowed us to identify the source of the TMPs.

The inclusion of atmospheric particles into the bark suber of ash trees.

A slow deposition of atmospheric components occurs on tree barks. One part of them can be incorporated into bark tissues. This work demonstrates that mineral particles are present inside the suber tissue in four-year-old ash tree stems. Most of these particles are smaller than 2 microm. Scanning electronic microscope studies - using energy dispersive X-ray spectroscopy (SEM-EDX) - on stem cuttings show that they are located either inside the dead suber cells or between these cells. Numerous particles are composed of clay, quartz, feldspar or mica. Others, clearly of anthropogenic origin, are metallic fragments composed of Fe, Ni, Cr, Pb, etc. Spherical fly ashes were found, composed of Si, Al or Fe, and demonstrating an anthropogenic formation. Such particles were isolated and purified from suber ashes obtained at 550 degrees C, after aqueous and acidic treatments, and their composition was established through SEM-EDX. These results reinforce the idea that the suber of tree barks alone can be considered as archives for atmospheric deposition.

How can the fipronil insecticide access phloem?

Seeds of sunflower plants coated with the fipronil (14)C-insecticide were allowed to grow in the greenhouse. The distribution of the (14)C-compounds was studied in each part of the plant after three months. After 83 days of culture small amounts of (14)C-compounds were found in the inflorescence (0.6 per thousand of the seed deposit) which were fipronil itself or its lipophilic or hydrophilic metabolites. The (14)C-compounds were found in each part of the inflorescence (bracts, ray and disk florets containing pollen, akenes). The (14)C-concentration in the xylem sap evaluated at this stage was much too low to explain the accumulated amount in the inflorescence. Under controlled conditions in a culture chamber, it was then demonstrated that a net phloem transfer of (14)C-fipronil occurred from developed leaves to growing organs. This allowed us to suppose that a similar (14)C-fipronil phloem transfer could occur toward the inflorescence during its formation. A quantitative evaluation suggests that most of the labeled compounds at this stage were not coming from the leaves but from the roots and stem where storage compounds were hydrolyzed for sustaining inflorescence development.

A PIXE and ICP-MS analysis of metallic atmospheric contaminants in tree bark tissues, a basis for biomonitoring uses.

The qualitative and quantitative metallic content of tree barks of Argania spinosa (L.) Skeels were studied. Argania spinosa is an endemic species in Morocco. This tree is adapted to semi-arid climates and exposed to specific conditions of relative humidity, temperature, wind, and particle transport. Three sites were sampled in Morocco: the large town of Rabat, the harbor of Agadir, and Aït Baha, a countryside location exposed to continuous desert wind. The methodologies included (1) in situ microanalysis with proton-induced X-ray emission (PIXE) and (2) trace element determinations by mass spectrometry with inductively coupled plasma (ICP-MS) associated with extraction procedures. Both methods allowed detection of elements coming from different bark compartments. The profile of airborne contaminants in the barks was typical of the sampling sites. The level of lead in barks sampled in Rabat reached 100 ng cm(-2), or higher, while it varied between 3 and 35 ng cm(-2) in Aït Baha. The in situ study of the microscopic structure of the bark provided the location of major and minor elements at various depths inside the bark. A differential between free deposit on the bark surface and penetrated content was found for the major and trace elements. The free deposit on the bark surface was suspected to be mostly the result of recent contamination. Part of the contaminants spread out on the surface penetrated the superficial suber. This long-term accumulation affected mostly Pb. In deeper levels, airborne elements at low concentrations and elements resulting from root uptake were concurrently present and resulted in a complex situation, as noted for zinc.

Soil distribution of fipronil and its metabolites originating from a seed-coated formulation.

Seed-coating with the insecticide fipronil has been intensively used in sunflower cultivation to control soil pests such as wireworms. A research project was undertaken to determine the soil distribution of fipronil and of its main phenylpyrazole metabolites. Under agronomic conditions, the quantity of fipronil in the seed-coat (437 microg/seed) decreased continuously during the cultivation period (3.9 microg day(-1) during the first two months; 0.3 microg day(-1) during the next four months). At the end of the cultivation period, 42% of all phenylpyrazole compounds remained in the seed-coat. Fipro nil was poorly mobile in soil, and at the end of the cultivation period it was mostly concentrated in the soil layer close to the seed (3240 microg kg(-1) soil). Starting from the seed-coating, a fipronil concentration gradient was measured in the soil, up to a distance of 11 cm from the seed. Degradation in the soil occurred at a moderate rate, probably due to the fact that water solubilization of the solid active ingredient present in the seed coating was rate limiting. Indeed, after 6 months of cultivation, only 51% of the fipronil seed-coating was found in the soil, about 7% having been absorbed by the sunflower plant, and 42% remaining in the seed coat. The predominant metabolites produced in the soil were sulfone-fipronil, sulfide-fipronil and amide-fipronil, which were produced at average rates of 5 microg kg(-1) soil day(-1), 3 microg kg(-1) soil day(-1), and 0.4 microg kg(-1) soil day(-1), respectively. In contrast, the photoproduct, desulfinyl-fipronil, was barely detected. All phenylpyrazole compounds were poorly mobile, except for the amide derivative, which is devoid of insecticidal activity in marked contrast to the other metabolites. Furthermore, detectable soil contamination was limited to a zone of about 11 cm around the seed.

Uptake and xylem transport of fipronil in sunflower.

The phenylpyrazole insecticide, fipronil, is used in seed coating against Agriotes larvae, which infest mainly corn and sunflower. Coating the seeds of the cultivated plants with fipronil has proven its effectiveness against Agriotes populations. In the case of sunflower or even corn, the possible root uptake of this insecticide may lead to a toxic effect against pollinators such as honeybees. In the present report, the uptake and transport of fipronil inside the sunflower seedling was studied in the laboratory. In a first study, sunflower was cultivated on an aqueous medium containing fipronil. An intense root uptake of fipronil occurred, leading to a transport into leaves depending upon transpiration. In a second study, plants were cultivated on a soil in which fipronil was uniformly distributed. Under our soil conditions (20% organic carbon), the partition coefficient between soil and water (K(d)) was found to be equal to 386 +/- 30. The average rate of fipronil transfer from soil water to seedlings was from 2 to 2.6 times lower than water transfer. During the 3 week experiment, 55% of recovered labeled compounds was in the parent form and 35% had been converted to lipophilic metabolites, with either a 4-CF(3)-SO(2) or 4-CF(3)-S substituant, which are also very potent lipophilic insecticides. This paper suggests that the possible uptake of fipronil by sunflower seedlings under agronomic conditions is mainly controlled by the physicochemical characteristics of the seed-coating mixture.

Phototransformation of the insecticide fipronil: identification of novel photoproducts and evidence for an alternative pathway of photodegradation.

Fipronil is a recently discovered insecticide of the phenylpyrazole series. It has a highly selective biochemical mode of action, which has led to its use in a large number of important agronomical, household, and veterinary applications. Previous studies have shown that, during exposure to light, fipronil is converted into a desulfurated derivative (desulfinyl-fipronil), which has slightly reduced insecticidal activity. In this study, the photodegradation of fipronil was studied in solution at low light intensities (sunlight or UV lamp). In addition to desulfinyl-fipronil, a large number of minor photoproducts were observed, including diversely substituted phenylpyrazole derivatives and aniline derivatives that had lost the pyrazole ring. Desulfinylfipronil itself was shown to be relatively stable under both UV light and sunlight, with only limited changes occurring in the substitution of the aromatic ring. Since this compound accumulated to levels corresponding to only 30-55% of the amount of fipronil degraded, it was concluded that one or more alternative pathways of photodegradation must be operating. On the basis of the structurally identified photoproducts, it is proposed that fipronil photodegradation occurs via at least two distinct pathways, one of which involves desulfuration at the 4-position of the pyrazole ring giving the desulfinyl derivative and the other of which involves a different modification of the 4-substituent, leading to cleavage of the pyrazole ring and the formation of aniline derivatives. The latter compounds do not accumulate to high levels and may, therefore, be degraded further. The ecological significance of these results is discussed, particularly with regard to the insecticidal activity of the photoproducts.

Fipronil metabolism and dissipation in a simplified aquatic ecosystem.

Several phenylpyrazole derivatives are selective inhibitors of chloride channel activities in insects. In this chemical family, fipronil is a powerful insecticide now widely used for several purposes. The dissipation of this molecule in a simplified aquatic ecosystem has been studied for 3 months, using (14)C-labeled fipronil. The main features of the complex process leading to fipronil transformation in this system were the following. The fipronil aqueous solution was submitted to two chemical transformations: the photodependent desulfuration of the side chain bound to the 4-position of the heterocyclic ring and the chemical hydrolysis of the nitrile function bound to the 3-position. Fipronil, rapidly transferred from the water solution to the organic matter, was protected from the previously mentioned chemical transformations but evolved to give two main metabolites, which were either reduced or oxidized in the side chain on the 4-position. These derivatives were powerful insecticides as shown by LC(50) measurements on Aedes aegypti larvae (LC(50) for CF(3)-S-R and CF(3)-SO(2)-R = 8.8 nM). During the course of this experiment, nitrile hydrolysis took place slowly, originating either from the chemical hydrolysis in the aqueous solution or from enzymatic hydrolysis inside the microbial biomass. The fipronil-amide (3-NH(2)-CO-R') derivative, although much more polar than fipronil itself, was mostly bound to the organic matter. Other more polar derivatives were also detected but in very small amounts. No (14)CO emission was observed during the experiment.

Exploiting plant metabolism for the phytoremediation of persistent herbicides.

Weed control by herbicides has helped us to create the green revolution and to provide food for at least the majority of human beings living today. However, some herbicides remain in the environment and pose an ecological problem. The present review describes the properties and fate of four representative herbicides known to be presistent in ecosystems. Metabolic networks are depicted and it is concluded that removal of these compounds by the ecologically friendly technique of phytoremediation is possible. The largest problem is seen in the uptake of the compounds into suitable plants and the time needed for such an approach.