Isoproturon degradation as affected by the growth of two algal species at different concentrations and pH values.

Metabolism of [14C-u-phenyl]isoproturon [3-(4-isopropylphenyl)-1,1-dimethylurea] by two soil and freshwater microorganisms, green alga Chlorella kesslerei and cyanobacterium Anabaena inaequalis, was studied as a function of pH, pesticide concentration, and incubation time. Metabolized isoproturon, in the media, ranged from 0% (Chlorella at pH 5.5 after 1 d) to 22% (Anabaena at pH 5.5 after 10 d). Twenty-five percent faster degradation of isoproturon by Anabaena occurred at pH 5.5 versus pH 7.5, when measured over 10 d. Increased 14C incorporation into tissue, with time and at lower pH, was due mainly to bioaccumulation of [14C]isoproturon and/or its metabolites in the cells. Metabolic degradation resulted in four identifiable (by TLC) metabolites. Based on this, a degradation pathway is proposed, involving mono- and di-N-demethylation, hydroxylation of the isopropyl moiety, and hydrolysis to 4-isopropylaniline. Similarity in the metabolites produced suggests that the enzyme systems responsible for metabolizing isoproturon are almost identical in both photosynthetic micro-algae.     

Isolation and 16S DNA characterization of soil microorganisms from tropical soils capable of utilizing the herbicides hexazinone and tebuthiuron

Six non-fermentative bacteria were isolated from Colombian (South America) and Hawaiian (USA) soils after enrichment with minimal medium supplemented with two herbicides, hexazinone (Hex) and tebuthiuron (Teb). Microscopic examination and physiological tests were followed by partial 16S DNA sequence analysis, using the first 527 bp of the 16S rRNA gene for bacterial identification. The isolated microorganisms (and in brackets, the herbicide that each degraded) were identified as: from Colombia. Methylobacterium organophilum [Teb], Paenibacillus pabuli [Teb], and Micrmbacterium foliorum [Hex]; and from Hawaii, Methylobacterium radiotolerans [Teb], Paenibacillus illinoisensis [Hex], and Rhodococcus equi [Hex]. The findings further explain how these herbicides, which have potential for illicit coca (Erythroxylum sp.) control, dissipate following their application to tropical soils.     

Chlorpyrifos degradation in Turkish soil

Degradation of chlorpyrifos was evaluated in laboratory studies. Surface (0-15 cm) and subsurface (40-60 cm) clay loam soils from a pesticide-untreated field were incubated in biometer flasks for 97 days at 25 degrees C. The treatment was 2 micrograms g-1 [2,6-pyridinyl-14C] chlorpyrifos, with 74 kBq radioactivity per 100 g soil flask. Evolved 14CO2 was monitored in KOH traps throughout the experiment. Periodically, soil subsamples were also methanol-extracted [ambient shaking, then supercritical fluid extraction (SFE)], then analyzed by thin-layer chromatography. Total 14C and unextractable soil-bound 14C residues were determined by combustion. From the surface and subsurface soils, 41 and 43% of the applied radiocarbon was evolved as 14CO2 during 3 months incubation. The time required for 50% loss of the parent insecticide in surface and subsurface soils was about 10 days. By 97 days, chlorpyrifos residues and their relative concentration (in surface/subsurface) as % of applied 14C were: 14CO2 (40.6/42.6), chlorpyrifos (13.1/12.4), soil-bound residues (11.7/11.4), and 3,5,6-trichloropyridinol (TCP) (3.8/4.8). Chlorpyrifos was largely extracted by simple shaking with methanol, whereas TCP was mainly removed only by SFE. The short persistence of chlorpyrifos probably relates to the high soil pH (7.9-8.1).     

In vivo effects of deltamethrin on some biochemical parameters of carp (Cyprinus carpio L.)

Thein vivo effects of deltamethrin (DM) on the blood sugar level, the acetylcholinesterase (AChE, EC 3.1.1.7) activities of the blood serum and various organs (heart, liver and intestine), the lactate dehydrogenase (LDH, EC 1.1.2.3), glutamic-oxaloacetic transaminase (GOT, EC 2.6.1.1), and glutamic-pyruvic transaminase (GPT, EC 2.6.1.2) activities of the blood serum, the adenosine triphosphatases (EC 3.6.1.3; Na⁺/K⁺-ATPase and Mg²⁺-ATPase) activities of the erythrocyte plasma membrane and the catalase (EC 1.11.1.6) activity of the liver were examined throughout 96 h in adult carp (Cyprinus carpio L.) Two sublethal concentrations, 1.0 and 1.5 µg/l of deltamethrin, were used. All fish survived the experiment except one, in an aquarium containing 1.5 ppb of DM, which died after 72 h.The AChE specific activity was significantly inhibited in the heart and intestine after 96 h at both concentrations compared to that in the control animals (P<0.05, Student'st-test), while there was no detectable difference between the two treatment. At the same time there was no detectable change in the liver. In the serum, the AChE activity almost remained unchanged; the only significant decrease could be measured after 96 h at 1.5 µg/l deltamethrin concentration. The blood glucose content exhibited interesting changes: after 24 h fish exposed at 1 µg/l DM seemed to be stressed, although this increase was not significant. When these fish became used to the new conditions (in practice this meant the presence of DM), the glucose level decreased, especially after 72 h. At the same time the control animals kept in similar circumstances showed a small insignificant decrease. Meanwhile fish in aquaria containing 1.5 µg/l DM reacted to the treatment with an increased blood glucose level after 48 h, and this did not change until the end of the treatment. The Na⁺/K⁺-ATPase activity decreased in a dose-dependant manner, while Mg²⁺-ATPase was less affected. A small increase in LDH level was observed, indicating damage of different muscle tissues. However, this phenomenon appeared only with the small dosage after 24 h (P<0.05). It has to be mentioned that the individual values varied to a large extent among of the eight fish.The GOT activities of the serum increased during the treatment. However, significant changes were only expressed after 72 and 96 h at 1 µg/l DM concentrations (P<0.01 andP<0.05), and after a similar long treatment at the high dosage (P<0.05, 72 and 96 h). The GPT did not change significantly in aquaria containing 1 µg/l DM. The only larger increase was measured after 96 h at 1.5 µg/l DM concentration (P<0.05). The catalase activity in the liver of treated carp remained practically at the same level compared to that in control fish.All these changes (concerning the primary effects of this compound) demonstrate the effect of DM on different fish enzymes, at low concentrations under laboratory conditions, which might be useful in practice for biomonitoring using fish.     

Impact of four pesticides on the growth and metabolic activities of two photosynthetic algae

The acute toxicity was determined for soil algae Chlorella kesslerei and Anabaena inaequalis, exposed to pesticides lindane, pentachlorophenol (PCP), isoproturon (IPU), and methyl parathion (MP). Toxicity markers included growth inhibition, chlorophyll biosynthesis, and total carbohydrate content, as a function of dose and time. Concentration response functions (EC50) were estimated by probit data transformation and weighted linear regression analyses. Lindane's toxicity to Chlorella increased sharply with time (EC50 = 7490, 10.3, 0.09 mg L(-1); 24, 48, 72 h), but remained nearly constant through 72 h with Anabaena (8.7-6.7 mg L(-1); 24-72 h). PCP at low concentrations stimulated algal growth and chlorophyll a production, an effect reversed at higher doses. Anabaena was less tolerant of PCP and MP than was Chlorella. The 96-h static EC50 values for Chlorella were: 0.003, 34, 0.05, and 291 mg L(-1) for lindane, PCP, isoproturon, and MP, respectively; for Anabaena, these were 4.2, 0.13, 0.21, and 19 mg L(-1). Carbohydrate production responses were similar to those of cell density (growth) and chlorophyll biosynthesis, with MP having the lowest adverse impact. The overall relative toxicity among the four tested pesticides was: for Chlorella, lindane > IPU > PCP > MP; and for Anabaena, PCP > IPU > lindane > MP. The results confirm that toxicants such as these pesticides may affect individual (though related) species to significantly different degrees.     

Soil-catalyzed oxidation of aniline

Aniline partially degraded in sterile soil to azobenzene, azoxybenzene, phenazine, form=anilide, and acetanilide. Nitrobenzene, $\text{p}$-benzoquinone, and unidentified species were possible products; substantial bound residues may also have formed. Soil-catalyzed conversion of aniline or [$\text{d}$₅]aniline seems evidenced by 6-24X more product recovery in sterile soil than in sterile water alone, a process inhibited by Na₂S₂O₄. Freundlich adsorption constants showed: azobenzene > azoxybenzene > phenazine > aniline.     

Persistence of seven pesticides as influenced by soil moisture1

Abstract

Pesticides are often applied in combination, but less‐often is soil persistence measured this way. The present field and laboratory study determined relative persistence of five herbicides and two insecticides, co‐applied, as a function of three soil water contents. Losses were modeled adequately by first‐order dissipation, with no significant improvement by using a two‐compartment model. The order of persistence in a silt loam, at 25% moisture, was carbofuran < cyanazine < metribuzin = alachlor < atrazine < ethoprop < metolachlor (t_½ ranged from 7–91 days). Carbofuran degradation increased greatly from 12–25% soil moisture; atrazine was unaffected by 12–35%, whereas the remaining compounds showed limited increasing loss in wetter soil. Field‐based persistence was more variable, but generally similar to lab rankings.     

Impact of preferential flow at varying irrigation rates by quantifying mass fluxes

Solute concentration and soluble dye studies inferring that preferential flow accelerates field-scale contaminant transport are common but flux measurements quantifying its impact are essentially nonexistent. A tile-drain facility was used to determine the influence of matrix and preferential flow processes on the flux of mobile tracers subjected to different irrigation regimes (4.4 and 0.89 mm h(-1)) in a silt loam soil. After tile outflow reached steady state either bromide (Br; 280 kg ha(-1)) or pentafluorobenzoic acid (PFBA; 121 kg ha(-1)) was applied through the irrigation system inside a shed (3.5 x 24 m). Bromide fluxes were monitored at an irrigation rate of 4.4 mm h(-1) while PFBA fluxes were monitored at an irrigation rate of 0.89 mm h(-1). At 4.4 mm h(-1) nearly one-third of the surface-applied Br was recovered in the tile line after only 124 mm of irrigation and was poorly fit by the one-dimensional convective-dispersive equation (CDE). On the other hand, the one-dimensional CDE fit the main PFBA breakthrough pattern almost perfectly, suggesting the PFBA transport was dominated by matrix flow. Furthermore, after 225 mm of water had been applied, less than 2% of the applied PFBA had been leached through the soil compared with more than 59% of the applied Br. This study demonstrates that the methodology of applying a narrow strip of chemical to a tile drain facility is appropriate for quantifying chemical fluxes at the small-field scale and also suggests that there may be a critical input flux whereby preferential flow is initiated.