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.     

Study of the toxicity of diuron and its metabolites formed in aqueous medium during application of the electrochemical advanced oxidation process "electro-Fenton"

Diuron (N'-[3,4-dichlorophenyl]-N,N-dimethylurea) is a herbicide belonging to the phenylurea family, widely used to destroy weeds on uncultivated surfaces. Because of its toxicity for aquatic organisms and suspicion of being carcinogenic for humans, diuron is the object of growing environmental concern. Therefore, we have developed the electro-Fenton method, an electrochemical advanced oxidation process (EAOP), to degrade diuron in aqueous medium, and we have studied the evolution of the toxicity of treated solution during the process. Indeed, the EAOPs catalytically generate hydroxyl radicals that oxidize the persistent organic pollutants, and can ultimately destroy and mineralize them. But, sometimes, relatively toxic organic metabolites are formed during the oxidation reaction. In this work, the evolution of toxicity of diuron aqueous solutions was studied at different initial concentrations, during treatment by the electro-Fenton method. Samples were collected at various electrolysis times and mineralization degrees during the treatment. The toxicity of the samples was measured using the bacteria Vibrio fischeri (Microtox) and the green alga Scenedesmus obliquus. Our results demonstrated that the toxicity of diuron aqueous solutions (concentrations=3.0-27.6 mg L(-1)) varied considerably with time. The formation and disappearance of several metabolites, having toxicity often stronger than that of the initial herbicide, were observed. To improve the efficiency of water decontamination, the electro-Fenton method should be applied during a time long enough (several hours) and at relatively high electrolysis current (I=250 mA) to reach a nearly complete mineralization of the herbicide in the aqueous medium.     

Effective elution of RDX and TNT from particles of Comp B in surface soil

During live fire training exercises, large amounts of explosives are consumed. Low order detonations of high explosive payloads result in the patchy dispersal of particles of high explosive formulations over large areas of firing range soils. Dissolution of explosives from explosive formulation particles into soil pore water is a controlling factor for transport, fate, and effects of explosive compounds. We developed an empirical method to evaluate soils based on functionally defined effective dissolution rates. An automated Accelerated Solvent Extractor was used to determine the effective elution rates under controlled conditions of RDX and TNT from soil columns containing particles of Comp B. Contrived soils containing selected soil geosorbants and reactive surfaces were used to quantitatively determine the importance of these materials. Natural soils from training ranges of various soil types were also evaluated. The effects of geosorbants on effective elution rates were compound- and sorbent-specific. TNT elution was less than that of RDX and was greatly slowed by humic acid. Iron and iron-bearing clays reduced the effective elution rates of both RDX and TNT. This empirical method is a useful tool for directly generating data on the potential for explosives to leach from firing range soils, to identify general bulk soil characteristics that can be used to predict the potential, and to identify means to engineer soil treatments to mitigate potential transport.     

Pliocene large-mammal assemblages from northern Chad: sampling and ecological structure

Numerous Pliocene large-mammal assemblages have been discovered in Chad over the last decade. They offer a unique opportunity to understand the settings in which important chapters of Hominid evolution took place in Central Africa. However, it is crucial to first investigate both sampling and taxonomic homogeneity for these Chadian assemblages because they occur over large sectors in a sandy desert that offers virtually no stratigraphic section. Using cluster analysis and ordination techniques, we show that the three Pliocene sectors from Chad are homogeneous and adequate sampling units. Previous stable isotope analyses on these assemblages have indicated that the environment became richer in C(4) plants between approximately 5.3 and 3.5-3 Ma. To test whether this environmental change has affected the structure of palaeo-communities, we assigned body mass, trophic and locomotor eco-variables to mammal species from the three sectors. Statistical analysis shows that the overall ecological structure of the assemblages is not linked with the opening of the plant cover, and eco-variables show no temporal trend from the oldest sector to the youngest. For example, there is no significant change in the relative diversity of grazing and browsing taxa, although mixed feeders are less diversified in the youngest sector than in the preceding one. This pattern apparently does not result from potential biases such as methodological artefacts or taphonomic imprint. Instead, it seems that local heterogeneous environmental factors have played a major role in shaping the ecological spectrum of Chadian mammal palaeo-communities during the Pliocene.     

Physiology of the digestive tract of the sedentary polychaete Terebellides stroemi

The digestive tract of the sedentary polychaete Terebellides stroemi, collected from 88 m depth on the French Catalan Coast, was studied using histological, biochemical, cytological and spectrographic techniques. The ciliated oesophagus possesses a ventral pharyngeal pouch with a muscle bulb. The stomach is divided into two parts, the fore stomach is ciliated, but the hind stomach takes the place of a gizzard with a thick peritrophic membrane and a thick muscle mantle. The digestive gland enters the digestive tract at the boundary of the two stomachal areas; it is comprised of epithelial lamellae with a glandular epithelium. The gland cells contain a spherocrystal secretion with a high calcium and phosphorus content. The cells are also absorbant due to their microvillar brush border and to the storage of glycogen and lipids in the basal epithelium. A biochemical study using the Apizym System confirmed the secretion of enzymes such as phosphatases, esterases and various carbohydrases. Tryptic and chymotryptic enzymes were visualized by biochemical hydrolysis of synthetic substrates. The epithelium of the fore intestine is similar in appearance to the epithelium of the digestive gland, but consists of a single epithelial layer. Hind intestine and rectum are only excretory systems. The presence of this digestive gland does not seem to have been described elsewhere in polychaetes but is similar to the Morren's gland of some oligochaetes. The study was carried out during 1982 and 1983.     

Effect of metals on the adsorption and extractability of 14C-phenanthrene in soils

The fate of polycyclic aromatic hydrocarbons (PAHs) in contaminated soils may be affected by several environmental factors including the presence of co-contaminants. This study was conducted in order to assess the effect of metals on (i) the adsorption of 14C-phenanthrene in soils and (ii) its extractability and ability to form non-extractable residues. The first objective was accomplished using batch adsorption experiments with an uncontaminated agricultural soil spiked with the metals Cd, Cu, Pb, and Zn. Adsorption of phenanthrene was significantly higher after the addition of the metals (Kf = 21.48 vs. 8.55) and the desorption less readily reversible when compared to the unspiked soil. The extractability of phenanthrene was assessed with incubation (4 months, laboratory conditions) and microlysimeter experiments (6 months, natural climatic conditions) on three soils spiked with metals. All the soils were labelled with 14C-phenanthrene. The amount of extractable phenanthrene residues was significantly higher when the metals had been added to the soils. Nevertheless, the quantity of non-extractable residues was non-significantly different between the spiked and unspiked soils. The mechanism leading to increased adsorption and extractability of phenanthrene in the presence of metals is still unknown. In perspective, it would be interesting to assess the bioavailability of PAHs in the presence of metals in further experiments.     

Metallothionein induction, antioxidative responses, glycogen and growth changes in Tubifex tubifex (Oligochaete) exposed to the fungicide, fenhexamid

Laboratory studies were conducted to determine the effects of different concentrations of fenhexamid (0.1, 1, and 10 mg L(-1)) on growth, oxidative stress, protein, glycogen, and metallothionein (MT) contents in Tubifex tubifex after an exposure of 2, 4, and 7 days. In addition, residues of the fungicide were followed in water and in the worms. In water, fenhexamid concentration decreased slowly (maximum -2 +/- 0.03% after 2 days for 1 mg L(-1)). In the worms, it increased after 4 days and decreased thereafter, confirming that the worms were exposed to the fungicide and not to a degradation product. LC50 values were between 95.22 +/- 5.36 and 32.11 +/- 1.8 mg L(-1) depending on exposure time. Exposure to fenhexamid had a negative effect on T. tubifex growth (maximum effect -12.2 +/- 0.8% after 7 days with 10 mg L(-1)) demonstrating the toxic effect of the pesticide. This growth rate decrease was accompanied by a reduction in protein and glycogen contents. The activity of catalase (CAT), and glutathione reductase (GR) increased in response to the fungicide demonstrating an oxidative stress in the worms. In contrast glutathion-S-transferase activity (GST) decreased. Exposure to fenhexamid also induced synthesis of MT (maximum +78 +/- 8% after 2 days for 10 mg L(-1)). The specificity of MT concentration increase in response to metals is discussed.     

Environmental impact of two successive chemical treatments in a small shallow eutrophied lake: Part I. Case of aluminium sulphate

This paper deals with the efficiency and effects of addition of aluminium sulphate on soft water quality of a shallow eutrophic lake. Almost all the controlled variables improved with treatment, especially nutrient concentrations such as soluble reactive phosphorus (SRP) and transparency. However, aluminium sulphate was not added in sufficient quantity to reduce the total phosphorus content. SRP concentration was significantly reduced in the short term. Moreover, external loading of phosphorus was high and not taken into account by the in-lake treatments. Finally, resuspension of sediment (polymictic lake) removed the alum hydroxide layer on the sediment surface, which reduced treatment effectiveness. No significant pH decrease was noted following alum addition. According to bibliographical toxicological data, monomeric aluminium content does not show any toxic effect on aquatic fauna and flora. In spite of low SRP in the water column, the treatment did not prevent appearance of Microcystis sp. colony (> 10 colony per ml) approximately 30 days after alum application.