Toxicity of fipronil and its enantiomers to marine and freshwater non-targets

Fipronil is a phenylpyrazole insecticide used in agricultural and domestic settings for controlling various insect pests in crops, lawns, and residential structures. Fipronil is chiral; however, it is released into the environment as a racemic mixture of two enantiomers. In this study, the acute toxicity of the (S,+) and (R,-) enantiomers and the racemic mixture of fipronil were assessed using Simulium vittatum IS-7 (black fly), Xenopus laevis (African clawed frog), Procambarus clarkii (crayfish), Palaemonetes pugio (grass shrimp), Mercenaria mercenaria (hardshell clam), and Dunaliella tertiolecta (phytoplankton). Results showed that S. vittatum IS-7 was the most sensitive freshwater species to the racemic mixture of fipronil (LC50 = 0.65 microg/L) while P. pugio was the most sensitive marine species (LC50 = 0.32 microg/L). Procambarus clarkii were significantly more sensitive to the (S,+) enantiomer while larval P. pugio were significantly more sensitive to the (R,-) enantiomer. Enantioselective toxicity was not observed in the other organisms tested. Increased mortality and minimal recovery was observed in all species tested for recovery from fipronil exposure. These results indicate that the most toxic isomer of fipronil is organism-specific and that enantioselective toxicity may be more common in crustaceans than in other aquatic organisms.     

Sorption of fipronil and its metabolites on soils from South Australia

This paper reports on the sorption of fipronil [(+/-)-5-amino-1-(2,6-dichloro-alpha,alpha,alpha-trifluoro-p-tolyl)-4-trifluoromethyl-sulfinylpyrazole-3-carbonitrile] and its two main metabolites, desulfynil and sulfide derivatives on a range of soils from South Australia. The Freundlich sorption coefficient (Kf) values for fipronil on the soils ranged from 1.94 to 4.84 using a 5% acetonitrile/water mixture as the soil solution. Its two metabolites had a higher sorption affinity for soils, with Kf values ranging from 11.09 to 23.49 for the sulfide derivative and from 4.70 to 11.77 for the desulfynil derivative. Their sorption coefficients were found to be better related to the soil organic carbon than clay content. The presence of cosolvents in soil solutions had a significant influence on the sorption of fipronil. The Freundlich sorption coefficients showed a log linear relationship with the fractions of both acetonitrile and methanol in solutions. The sorption coefficient of fipronil on Turretfield soil in the aqueous solution was estimated to be from 13.80 to 19.19. Methanol had less effect on the sorption of fipronil than acetonitrile. The Kd values for fipronil on the eight soils using a 5% methanol/water mixture were from 5.34 to 13.85, which reflect more closely the sorption in the aqueous solution. The average Koc value for fipronil on the eight South Australian soils was calculated to be 825+/-214.     

Influence of fipronil compounds and rice-cultivation land-use intensity on macroinvertebrate communities in streams of southwestern Louisiana, USA

Laboratory tests of fipronil and its degradation products have revealed acute lethal toxicity at very low concentrations (LC50) of <0.5 microg/L to selected aquatic macroinvertebrates. In streams draining basins with intensive rice cultivation in southwestern Louisiana, USA, concentrations of fipronil compounds were an order of magnitude larger than the LC50. The abundance (rho=-0.64; p=0.015) and taxa richness (r2=0.515, p<0.005) of macroinvertebrate communities declined significantly with increases in concentrations of fipronil compounds and rice-cultivation land-use intensity. Macroinvertebrate community tolerance scores increased linearly (r2=0.442, p<0.005) with increases in the percentage of rice cultivation in the basins, indicating increasingly degraded stream conditions. Similarly, macroinvertebrate community-tolerance scores increased rapidly as fipronil concentrations approached about 1 microg/L. Pesticide toxicity index determinations indicated that aquatic macroinvertebrates respond to a gradient of fipronil compounds in water although stream size and habitat cannot be ruled out as contributing influences.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco, Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-alpha,alpha,alpha -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g(-1); short-term experiment) to 200 days (initial concentration = 689 ng g(-1); long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

Degradation of fipronil under laboratory conditions in a tropical soil from sirinhaém pernambuco,Brazil

The objective of this research was to assess the degradation of fipronil [5-amino-1-(2,6-dichloro-α,α,α -trifluoro-p-tolyl)-4-trifluoromethylsulfinylpyrazole-3-carbonitrile] in soils from sugar cane fields in Northeastern Brazil. Degradation experiments were carried out under laboratory conditions (controlled temperature and in the dark), where sterile and non-sterile soils (Ustoxs) were incubated [under moisture content of 55% of the water holding capacity (WHC)] and analyzed for fipronil disappearance and metabolite formation. Microbial communities present in the soil degrade fipronil. However, biodegradation seems to be dependent on the bioavailability of the fipronil and the half-life according to the zero-order model. Fipronil degradation rate appeared to be biphasic. Degradation fipronil ranged from 83 days (initial concentration = 978 ng g^{? 1}; short-term experiment) to 200 days (initial concentration = 689 ng g^{? 1}; long-term experiment). This an initial slower rate followed by a faster rate after 90 days of incubation may lead to shorter half-life than that calculated with the zero-order model. The sulfone derivative (an oxidation product) was the predominant metabolite, but the sulfide (a reduction product) and amide (a hydrolysis product) derivatives were also formed under non-sterile conditions after 120 days of incubation. The metabolites underwent further biodegradation, particularly the sulfone derivative. Bioavailability appears to affect fipronil degradation in soils with an effective capacity to adsorb fipronil (such as Ustoxs), while redox potential was important for the formation of metabolites. Despite the fine texture, more aerobic sites were present, thus favoring the formation of the sulfone metabolite over that of the sulfide metabolite. Therefore, microaggregation of Ustoxs, with high clay content, played a very important role in determining the types of metabolites formed.     

The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day(-1), less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0-1 cm layer of soils. Only 5-7% of each pesticide was recovered from the 1-2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2-10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5-10% of the applied thiobencarb and between 10-20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.     

Residues of phosphamidon in rice fields

Thirty-day-old seedlings of rice plants (IR-20 variety) from the nursery were transplanted into experimental plots and after 52 days were sprayed with phosphamidon (Dimecron 85% EC) at two dose-rates (0.38 kg a.i. ha(-1) and 0.76 kg a.i. ha(-1)). Residues of phosphamidon in the plant, soil and water were analysed by GLC, at various time intervals, and were found to decrease steadily up to 15 days. A second application of the pesticide was made on day 113 and grains harvested on day 138. The residue level in the plants was 0.12 microg g(-1) and in the grains 0.04 microg g(-1) with the high dose. This is slightly below the EPA prescribed tolerance level of 0.05 microg g(-1). The residues in both soil and water were very low, 24 h after spraying.     

Effect of metal tolerant plant growth promoting Bradyrhizobium sp. (vigna) on growth, symbiosis, seed yield and metal uptake by greengram plants

The nickel and zinc tolerant plant growth promoting Bradyrhizobium sp. (vigna) RM8 was isolated from nodules of greengram, grown in metal contaminated Indian soils. The plant growth promoting (PGP) potentials of strain RM8 was assessed both in the presence and absence of nickel and zinc under in vitro conditions. Strain RM8 tolerated a high level of nickel (300 microg ml(-1)) and zinc (1400 microg ml(-1)) on yeast extract mannitol agar medium. Bradyrhizobium sp. (vigna) strain RM8 produced 13.3 microg ml(-1) of indole acetic acid in Luria Bertani broth at 100 microg ml(-1) of tryptophan which increased to 13.6 microg ml(-1) at 50 microg Ni ml(-1) and 13.5 microg ml(-1) at 300 microg Zn ml(-1). Strain RM8 was positive for siderophore, HCN and ammonia both in the absence and presence of nickel and zinc. The PGP activity of this strain was further evaluated with increasing concentrations of nickel and zinc using greengram as a test crop. The bioinoculant enhanced the nodule numbers by 82%, leghaemoglobin by 120%, seed yield by 34%, grain protein by 13%, root N by 41% and shoot N by 37% at 290 mg Ni kg(-1) soil. At 4890 mg Zn kg(-1) soil, the bioinoculant increased the nodule numbers by 50%, leghaemoglobin by 100%, seed yield by 36%, grain protein by 13%, root N by 47% and shoot N by 42%. The bioinoculant strain RM8 reduced the uptake of nickel and zinc by plant organs compared to plants grown in the absence of bioinoculant. This study suggested that the bioinoculant due to its intrinsic abilities of growth promotion and attenuation of the toxic effects of nickel and zinc could be exploited for remediation of metal from nickel and zinc contaminated sites.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

Fate in soil of 14C-sulfadiazine residues contained in the manure of young pigs treated with a veterinary antibiotic

The fate of (14)C-labeled sulfadiazine ((14)C-SDZ) residues was studied in time-course experiments for 218 days of incubation using two soils (A(p) horizon of loamy sand, orthic luvisol; A(p) horizon of silt loam, cambisol) amended with fresh and aged (6 months) (14)C-manure [40 g kg(-1) of soil; 6.36 mg of sulfadiazine (SDZ) equivalents per kg of soil], which was derived from two shoats treated with (14)C-SDZ. Mineralization of (14)C-SDZ residues was below 2% after 218 days depending little on soil type. Portions of extractable (14)C (ethanol-water, 9:1, v/v) decreased with time to 4-13% after 218 days of incubation with fresh and aged (14)C-manure and both soils. Non-extractable residues were the main route of the fate of the (14)C-SDZ residues (above 90% of total recovered (14)C after 218 days). These residues were high immediately after amendment depending on soil type and aging of the (14)C-manure, and were stable and not remobilized throughout 218 days of incubation. Bioavailable portions (extraction using CaCl(2) solution) also decreased with increasing incubation period (5-7% after 218 days). Due to thin-layer chromatography (TLC), 500 microg of (14)C-SDZ per kg soil were found in the ethanol-water extracts immediately after amendment with fresh (14)C-manure, and about 50 microg kg(-1) after 218 days. Bioavailable (14)C-SDZ portions present in the CaCl(2) extracts were about 350 microg kg(-1) with amendment. Higher concentrations were initially detected with aged (14)C-manure (ethanol-water extracts: 1,920 microg kg(-1); CaCl(2) extracts: 1,020 microg kg(-1)), probably due to release of (14)C-SDZ from bound forms during storage. Consistent results were obtained by extraction of the (14)C-manure-soil samples with ethyl acetate; portions of N-acetylated SDZ were additionally determined. All soluble (14)C-SDZ residues contained in (14)C-manure contributed to the formation of non-extractable residues; a tendency for persistence or accumulation was not observed. SDZ's non-extractable soil residues were associated with the soluble HCl, fulvic acids and humic acids fractions, and the insoluble humin fraction. The majority of the non-extractable residues appeared to be due to stable covalent binding to soil organic matter.     

Spatial variability of arsenic and chromium in the soil water at a former wood preserving site

Contamination of industrial sites by wood preservatives such as chromated copper arsenate (CCA) may pose a serious threat to groundwater quality. The objective of this study was to characterise the spatial variability of As and Cr concentrations in the solid phase and in the soil water at a former wood impregnation plant and to reveal the fundamental transport processes. The soil was sampled down to a depth of 2m. The soil water was extracted in situ from the vadose zone over a period of 10 months at depths of 1 and 1.5m, using large horizontally installed suction tubes. Groundwater was sampled from a depth of 4.5m. Results showed that arsenic and chromium had accumulated in the upper region of the profile and exhibited a high spatial variability (As: 21-621 mg kg(-1); Cr: 74-2872 mg kg(-1)). Concentrations in the soil water were high (mean As 167 microg L(-1); Cr: 62 microg L(-1)) and also showed a distinct spatial variability, covering concentration ranges up to three orders of magnitude. The variability was caused by the severe water-repellency of the surface soil, induced by the concurrent application of creosote wood preservatives, which leads to strong preferential flow as evident from a dye experiment. In contrast to soil water concentrations, only low As concentrations (<12 microg L(-1)) were detected in the groundwater. High Cr concentrations in the groundwater (approx. 300 microg L(-1)), however, illustrated the pronounced mobility of chromium. Our study shows that at sites with a heterogeneous flow system in the vadose zone a disparity between flux-averaged and volume-averaged concentrations may occur, and sampling of soil water might not be adequate for assessing groundwater concentrations. In these cases long-term monitoring of the groundwater appears to be the best strategy for a groundwater risk assessment.     

Effects of scrubber by-product-stabilized dairy lagoon sludge on growth and physiological responses of sunflower (Helianthus annuus L.)

Brick manufacturing industries are challenged to comply with clean air mandates. Dry air scrubbers have been used to remove acid gases from the exhaust air from brick manufacturing plants. The use of dry air scrubbers results in the production of large quantities of an alkaline powder by-product. A greenhouse experiment was conducted to evaluate the potential of using dairy lagoon sludge stabilized with the scrubber by-product as a soil amendment. Lagoon sludge was stabilized with scrubber by-product at an application rate of 20 gl(-1). The sludge-scrubber by-product mixture was applied to a sandy loam soil to provide amendments ranging between 28 and 168 kg of plant available nitrogen (PAN)/ha for the growth of Helianthus annuus (sunflower). Use of the sludge-scrubber by-product mixture as a nitrogen fertilizer did not adversely affect sunflower seedling emergence; however, significantly higher (p<0.05) plant volume indices, leaf area, dry shoot and root masses, and seed yields were obtained for mature plants grown in sludge-treated soil relative to the control or fertilizer treatment. The sludge amendment did not severely impact gas exchange or chlorophyll a fluorescence of the plants and nutrient content of the sunflower tissues was generally within a sufficient range. The increased growth and yield of sunflower plants indicated the potential of the sludge-scrubber by-product mixture as a soil amendment in agricultural crop production.     

Use of oxytetracycline and tylosin in intensive calf farming: evaluation of transfer to manure and soil

Antibiotics may enter soils with manure from treated animals. Because of their biological effects, antibiotics are regarded as potential micropollutants. The levels of oxytetracycline and tylosin over time were followed in faeces, bedding and manure, and then in the soil of a manured field and surrounding drainage courses, after oral treatment of calves. Fifty Simmental calves were treated for 5 days with 60 mg/kg/day of oxytetracycline. After 15 days the animals were treated for 5 days with 20 mg/kg/day of tylosin. Tylosin degraded rapidly, and was no longer detected in manure 45 days after cessation of treatment and no trace of the compound was detected in soil or surrounding water (detection limits 10 microg/l). The half-life of oxytetracycline in manure was 30 days and the compound was still detectable in this matrix (820 microg/kg) after 5 months maturation. In the manured soil oxytetracycline was detected at concentrations at least 10 times lower than the European Agency for the Evaluation of Medicinal Products threshold (100 microg/kg) requiring phase II environmental risk assessment. Oxytetracycline was not detected in the water courses (detection limit 1 microg/l). These results demonstrate that the processes occurring between faeces production and application of manure to the soil are very effective in reducing the load of TYL and OTC in the environment. For both drugs a toxicity test was performed using the alga Selenastrum capricornutum. The EC50 was 4.18 mg/l for oxytetracycline and 0.95 mg/l for tylosin. A worst-case hazard assessment for the aquatic environment was performed comparing the ratio between the measured concentrations (LOD) and effect data from previous work (OTC) or from this work (TYL). This showed ratio between toxicity levels (bacteria) (EC50=0.14 mg/l) and measured concentrations (LOD=1 microg/l) for OTC to be 140. The corresponding value for TYL (LOD=10 microg/l) was 95.     

High levels of heavy metals in rice (Oryza sativa L.) from a typical E-waste recycling area in southeast China and its potential risk to human health

Very few studies have investigated the heavy metal contents in rice samples from a typical E-waste recycling area. In this study, 10 heavy metals (As, Ba, Cd, Co, Cr, Cu, Hg, Mn, Ni and Pb) in 13 polished rice and relevant hull samples, six relevant paddy soil samples were investigated. The geometric mean concentrations of Cd, Cu and Hg in soil samples were 1.19, 9.98 and 0.32 microg g(-1), respectively, which were 4.0, 2.0 and 1.1-folds of the maximum allowable concentration (MAC) (0.30, 50.00, 0.30 microg g(-1), respectively) for Chinese agricultural soils. The analyzed metal concentrations were significantly different between rice and relevant hull except for As, Cd and Hg (p<0.05). All metal concentrations, except for Co, in rice hull were higher than those in polished rice. The geometric mean of Pb in polished rice reached 0.69 microg g(-1), which was 3.5-folds higher than the MAC (0.20 microg g(-1)) by the safety criteria for milled rice. Cd contents in 31% of the rice samples exceeded the national MAC (0.20 microg g(-1)), and the arithmetic mean also slightly exceeded national MAC. In addition, Cd and Pb contents in local rice were much higher than commercial rice samples examined in this work and previous studies. Comparing the tolerable daily intakes given by FAO/WHO with the mean estimated daily intakes; Pb daily intake through rice consumption in this area was 3.7 microg day(-1)kg(-1) body weight (bw), which already exceeded the FAO tolerable daily intake, and the Cd daily intake (0.7 microg day(-1)kg(-1) bw) through rice had already taken up 70% of the total tolerable daily intake (1 microg day(-1)kg(-1) bw). The daily intake of Hg and As through rice was much lower than the tolerable daily intakes, but bioaccumulation of Hg through the food chain and intake of As from other food stuff should also be of concern.     

Thallium in French agrosystems-II. Concentration of thallium in field-grown rape and some other plant species

The aim of this study was to assess thallium (Tl) uptake into the aerial parts of selected crop species grown on French soils with high Tl content of pedogeochemical origin (0.3-40 mg Tl kg(-1) on a dry wt (DW) basis). Husked wheat and maize grains contained less than 4 microg Tl kg(-1) DW, but rape shoots accumulated Tl with a shoot-soil partition coefficient (PC) > 1, and rape seeds had PC > 3. Tl content of rape seed reached 33 mg Tl kg(-1) DW and higher concentrations in soil corresponded to increased concentrations in rape seeds. It is argued that parent material of the soil and pedogenesis have a considerable effect on Tl accumulation in rape seeds. These results show enhanced phytoavailability of Tl of pedogeochemical origin and prompt questions on the potential for food chain contamination by Tl in rape cattle cakes.     

Distribution of polycyclic aromatic hydrocarbons in thirty typical soil profiles in the Yangtze River Delta region, east China

Polycyclic aromatic hydrocarbons (PAHs) were quantified in 30 soil profiles from the Yangtze River Delta Region, in east China. Relative concentrations of PAH compounds with different benzene rings and ratios of fluoranthene to fluoranthene plus pyrene and benz(a)anthracene to benz(a)anthracene plus chrysene were used to identify the possible sources of soil PAHs. Total concentrations of 15 PAHs in topsoils ranged from 8.6 to 3881 microg kg(-1) with an average of 397 microg kg(-1). Half of the soil samples were considered to be contaminated with PAHs (>200 microg kg(-1)) and two sampling sites were heavily polluted by PAHs with concentrations >1000 microg kg(-1). Phenanthrene was found in soils below a depth of 100 cm in half of the sampling sites, but the detectable ratio of benzo(a)pyrene decreased sharply from 100% in topsoil to 0 in the 4th horizon.     

Effects of butachlor on microbial populations and enzyme activities in paddy soil

This paper reports the influences of the herbicide butachlor (n-butoxymethlchloro -2', 6'-diethylacetnilide) on microbial populations, respiration, nitrogen fixation and nitrification, and on the activities of dehydrogenase and hydrogen peroxidase in paddy soil. The results showed that the number of actinomycetes declined significantly after the application of butachlor at different concentrations ranging from 5.5 microg g(-1) to 22.0 microg g(-1) dried soil, while that of bacteria and fungi increased. Fungi were easily affected by butachlor compared to the bacteria. The growth of fungi was retarded by butachlor at higher concentrations. Butachlor however, stimulated the growth of anaerobic hydrolytic fermentative bacteria, sulfate-reducing bacteria (SRB) and denitrifying bacteria. The increased concentration of butachlor applied resulted in the higher number of SRB. Butachlor inhibited the growth of hydrogen-producing acetogenic bacteria. The effect of butachlor varied on methane-producing bacteria (MPB) at different concentrations. Butachlor at the concentration of 1.0 microg g(-1) dried soil or less than this concentration accelerated the growth of MPB, while at 22.0 microg g(-1) dried soil showed an inhibition. Butachlor enhanced the activity of dehydrogenase at increasing concentrations. The soil dehydrogenase showed the highest activity on the 16th day after application of 22.0 microg g(-1) dried soil of butachlor. The hydrogen peroxidase could be stimulated by butachlor. The soil respiration was depressed during the period from several days to more than 20 days, depending on concentrations of butachlor applied. Both the nitrogen fixation and nitrification were stimulated in the beginning but reduced greatly afterwards in paddy soil.     

Dynamics of fipronil residue in vegetable-field ecosystem

Fipronil insecticide has been widely used to control vegetable pests in China recently. The research was conducted to evaluate the fate of fipronil in vegetable-field ecosystem and provide the scientific basis of using this insecticide. Developed on the analytical methods of fipronil residue and its four metabolisms, the degradation dynamics of their residue in a vegetable and the soil of the vegetable fields was studied. The results showed that (1) degradation of fipronil was faster in pakchoi (half-life 2.6 days) than in soil (half-life 7.3 days); (2) degradation reaction occurred in soil was governed mainly by photodegradation and oxidization accompanying with production of the metabolites, MB46513 and MB46136. Reduction and hydrolyzation played little role in the degradation process. In pakchoi, degradation was mainly contributed by reduction though oxidization and hydrolyzation occurred simultaneously. The metabolite products were MB45950, MB46136 and RPA200766; (3) the final residue in pakchoi was at a level of 0.003 mg kg⁻¹, which was much lower than the USA’s upper limit of 0.04 mg kg⁻¹ in rice. Therefore, a dosage of 24 g hm⁻² was suggested and considered as safe to human beings and animals.     

Metolachlor persistence in laboratory and field soils under Indian tropical conditions

Metolachlor [2-chloro-N-(2-methoxy-1-methylethyl)-2'-ethyl-6'- methyl acetanilide] dissipation under both field and laboratory conditions were studied during summer season in an Indian soil. Metolachlor was found to have moderate persistence with a half-life of 27 days in field. The herbicide got leached down to 15-30 cm soil layer and residues were found up to harvest day of the sunflower crop in both 0-15 cm and 15-30 cm soil layers. Metolachlor was found to be more persistent in laboratory studies conducted for 190 days. The rate of degradation was faster in soil under flooded partial anaerobic conditions as compared to aerobic soil with a half-life of 44.3 days. In aerobic soil, metolachlor was very stable with only 49% dissipation in 130 days. Residues remained in both the soils up to the end of the experimental period of 190 days.     

The mobility of thiobencarb and fipronil in two flooded rice-growing soils

The mobility of the rice pesticides thiobencarb (S-[(4-chlorophenyl) methyl] diethylcarbamothioate) and fipronil ([5-amino-3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]pyrazole) were investigated in the glasshouse under flooded conditions using two Australian rice-growing soils. When using leakage rates of 10 mm day^?1, less than 20% of applied thiobencarb and fipronil remained in the water column after 10 days due to rapid transfer to the soil phase. Up to 70% and 65% of the applied thiobencarb and fipronil, respectively, were recovered from the 0–1 cm layer of soils. Only 5–7% of each pesticide was recovered from the 1–2 cm layer, and less than 2% was recovered from each 1 cm layer in the 2–10 cm region of the soils. Analysis of the water leaking from the base of the soil cores showed between 5–10% of the applied thiobencarb and between 10–20% of the applied fipronil leaching from the soil cores. The high levels of pesticide in the effluent was attributed to preferential flow of pesticide-laden water via soil macropores resulting from the wetting and drying process, worm holes and root channels.