Residues and dissipation of the pesticide emamectin benzoate under Egyptian field condition: a case study

A simple, rapid analytical procedure for the quantification of emamectin benzoate in tomato was developed using high performance liquid chromatography with fluorescence detector (HPLC-FLD). Emamectin benzoate residues were extracted from tomato samples with n-hexane:ethyl acetate (1:1, v/v). The method involved derivatization using trifluoroacetic anhydride and 1-methylimidazole, prior to analysis by HPLC-FLD. Limit of quantification of this method was found to be 0.01 mg/kg, while limit of detection was 0.005 mg/kg. The dissipation of emamectin benzoate on tomato was studied, and half-life (t_1/2) was estimated in a field study carried out at three different locations. Emamectin benzoate was sprayed on tomato at recommended dosage. Samples of tomato were collected at 0, 1, 3, 7, 10, and 15 days after treatment. The t_1/2 of emamectin benzoate when applied at the recommended doses in tomato was approximately 2.5 days. The residue of emamectin benzoate reached below the maximal residue limit (MRL) 10 days after spraying at the tested dosage. Hence, a safe pre-harvest interval of 10 days is suggested before harvesting of tomato. This study would also be helpful for the Egypt government to establish the MRL of emamectin benzoate in tomatoes and provide guidance on the proper and safe use of this insecticide.     

Effect of pH on the fate of fenazaquin in soil and water under laboratory-simulated condition

The persistence of fenazaquin (4-t-butylphenylethyl quinazolin-4-yl ether) was studied in three different soils, namely, Gangetic alluvial (pH 6.9), laterite (pH 5.3), and terai (pH 5.1) soil and in water at three different pH values (4.0, 7.0, and 9.2) under laboratory-simulated condition and samples were analyzed upto 60 days at regular intervals. Fenazaquin was applied at 5 and 10 µg g^?1 for each soil and at 0.2 and 0.4 µg mL^?1 to each water sample. Dissipation of fenazaquin in soil and water followed first-order kinetics irrespective of any treatments. The half-life of fenazaquin was found in the range of 47–64 days in soils and 3.49–37.6 days in water irrespective of dose. The persistence of fenazaquin in soil significantly increased in the order of Gangetic alluvial soil (pH 6.9) > laterite soil (pH 5.3) > terai soil (pH 5.1), whereas in water the trend of persistence was pH 9.2 ≥ pH 7.0 > pH 4.0. The dissipation of fenazaquin in soil and water was found to be dependent on pH irrespective of doses.     

Persistence of chlorpyriphos in okra (Abelmoschus Esculentus) fruits and soil

Persistence of cypermethrin and chlorpyriphos in okra and soil were studied following the application of pre-mix formulation of insecticides Action 505EC (chlorpyriphos 50%?+?cypermethrin 5%) at single (275?g a.i.?ha^?1) and double dose (550?g a.i.?ha^?1). The average initial deposits of chlorpyriphos in okra were observed to be 0.07 and 0.15?mg?kg^?1 in single and double dose, respectively, which dissipated to 92% after 10 days for both the dosages. Residues of soil under okra crop were found to be 0.15?mg?kg^?1 at the single and 0.36?mg?kg^?1 at the double doses. These residues persisted up to 3 days at single and 5 days at double dose. The half-life (t _1/2) periods of chlorpyriphos on okra and soil were observed to be 0.6 days and 1.9 days for single and double dose, respectively. Residues of chlorpyriphos reached below detectable level (BDL) of 0.01?mg?kg^?1 in okra fruits after 7 days at single dose and in 15 days in double dose. In soil, residues of chlopyriphos persisted up to 5 and 7 days in single and double dose, respectively. Following foliar applications of a insecticide formulation (Action 505EC, (chlorpyriphos 50%?+?cypermethrin 5%) on okra at @ 275 and 550?g active ingredient (a.i.)?ha^?1 resulting in active applications of chlorpyriphos at the rate of 250 and 500?g a.i.?ha^?1 the average initial deposits of chlorpyriphos in okra were observed to be 0.07 and 0.15?mg?kg^?1, respectively. These residue levels dissipated to 92% after 10 days at both the dosages. Residues of soil under the okra crop were found to be 15?mg?kg^?1 at the single and 36?mg?kg^?1 at the double dose. The residues persisted up to 3 days at the single and 5 days at the double dose. The half-life (t _1/2) periods of chlorpyriphos on okra were observed to be 0.6 days for application rates, and 1.9 days for soil. Okra fruits and soil samples collected on the 7th and 15th day after application did not show any chlorpyriphos residues above their determination limits of 0.01 and 0.005?mg?kg^?1, respectively.     

Chloride and atrazine transport through saturated soil columns

A possible contamination of water resources by the application of pesticides is a problem confronting many irrigated areas in arid and semi-arid areas. The best management practices have to be adopted to minimize pesticide transport and leaching under irrigated conditions. Atrazine dissipation in loam and sandy loam soils has been tested in the laboratory using disturbed soil columns under saturated flooding conditions. All the experiments were performed in replicates. The chloride transport was also studied to test its behavior as an inert tracer in both the soils. Atrazine and chloride breakthrough curves were analyzed with the parameter optimization program CXTFIT to determine transport parameters including pore-water velocity (v), retardation coefficient (R), hydrodynamic dispersion coefficient (D), and pulse duration (t _o ). The pore-water velocity and pulse duration of the solute were estimated from the experimental conditions and kept constant during the optimization procedure. The results indicated that the R of chloride was not significantly different from 1, indicating that chloride is an inert tracer for the types of soil tested in this study. The average R of atrazine was 4.56 and 3.15 for sandy loam and loam soils, respectively. Results also showed that the hydrodynamic dispersion coefficient was much higher in the case of sandy loam soil compared to the loam soil for the two solutes, thus indicating non-equilibrium transport conditions. In the case of chloride, D increased from 0.4 for the loam soil to 16.2?cm²/min for the sandy loam soil. Similar results were observed in the case of atrazine in which D for the sandy loam soil was 60% higher than that for the loam soil. More atrazine leaching is expected under field conditions due to the presence of soil cracks and macropores.     

Photodegradation of Benthiocarb

The photodegradation of ¹⁴C-benthiocarb in water, on a glass surface, on soil and silica gel TLC plates was studied. the study was designed to obtain some information of its dissipation and photodegradation under various laboratory conditions. Benthiocarb degrades readily when exposed to either sunlight or UV light (254 nm). However, it is degraded much faster by UV light than by sunlight. Also, benthiocarb decomposes faster in water or on a glass surface or silica gel surface than on a soil surface. the half-life of benthiocarb exposed to UV light was: 1 hr on glass surface; 1.5 hrs in water; 2 hrs on silica gel TLC plate; 20 hrs on soil TLC plate. Benthiocarb in water, and exposed to sunlight, had a half-life of approximately 3 days. the following major photodegradation products were identified: 4-chlorobenzyl alcohol; 4-chlorobenzaldehyde; 4-chlorobenzoic acid.     

Effectiveness of emergent and submergent aquatic plants in mitigating a nitrogen–permethrin mixture

Hydraulically connected wetland microcosms (～50?L) in series were used to test the effectiveness of varying combinations of two common aquatic vascular plants, parrot feather (Myriophyllum aquaticum) and cattail (Typha latifolia), for mitigating contamination from a mixture of nitrogen (ammonium nitrate) and permethrin. The upstream series included Myriophyllum only (M) and Typha only (T) while the combination upstream effluent into downstream series included Myriophyllum into Myriophyllum (M?+?M) and Typha into Myriophyllum (T?+?M). During flow, M into M?+?M more efficiently mitigated nitrogen than T into T?+?M. Post-flow, nitrogen removal efficiency was greater for T versus M and M?+?M versus T?+?M. Mean aqueous dissipation half-lives (t_1/2) of NH₄-N and NO₃-N were more rapid in T than M treatments. Ammonium and nitrate t_1/2 was highly correlated with aquatic plant above-ground shoot biomass. Permethrin mitigation efficiencies and t_1/2 were not significantly affected by plant species either singly or in combination. Trans-permethrin t_1/2 was moderately correlated with plant biomass, but not cis-permethrin t_1/2. Results of this study indicate differences in aquatic plant species and flow path influence nitrogen removal but not permethrin. However, plant species appears less important than overall plant biomass in ascertaining aquatic plant effectiveness in mitigating a nitrogen–permethrin mixture.     

Persistence and dissipation of synthetic pyrethroid pesticides in red soils from the Yangtze River Delta area

Laboratory incubation trials were conducted to investigate the effects of several factors on the persistence as well as the dissipation of three synthetic pyrethroid pesticides in red soils obtained from the Yangtze River Delta region in China. The pyrethroids selected for investigation were cypermethrin, fenvalerate, and deltamethrin, which continue to be used extensively to control pests on farmland in the region despite the concern that they are highly toxic to certain vertebrate and mammalian species. Data from this exploratory study showed that the dissipation half-lives (T _1/2) tended to correlate with soil pH and soil organic matter contents, but not with soil cation-exchange capacity. The T _1/2 values were seen to be shorter in soil samples fertilized with glucose than without. The rates of pyrethroid dissipation also tended to increase with increasing initial soil concentration, but were largely unaffected by whether the pesticides were present in the soil separately or as a mixture. Another noteworthy observation is that microbial activity appeared to dominate the degradation process. Findings of this type could offer valuable clues for future research directions in reducing pesticide persistence in soil, which in turn could lead to the ultimate reduction of environmental pollution caused by pyrethroid application to farmland in the region. Project supported by Chinese Academy of Sciences (Project No. KSCX2-YW-N-038) and the National Key Basic Research Support Foundation (973), China (No. 2002CB4108010).     

Degradation profile of azoxystrobin in Andisol soil: laboratory incubation

The fate of azoxystrobin in soil under the effect of different temperature is of interest because application directions specify soil-surface treatments for number of agricultural pests. Temperature is an important factor governing the rate of degradation in soil pore. The purpose of this investigation was to understand better the effect of temperature on the degradation of azoxystrobin in Japanese Andisol soil. This was done through laboratory incubation of soil at three different temperatures (5 °C, 20 °C, 35 °C). First-order kinetics could be used to describe degradation of azoxystrobin under controlled condition of temperature (r² ? 94). The results showed that, during the 120-day incubation period for azoxystrobin, 64%, 70%, and 78% of applied azoxystrobin were degraded at 5 °C, 20 °C, and 35 °C, respectively. By using the Arrhenius equation, the activation energy of degradation of azoxystrobin fungicide was calculated (7.48 ± 1.74 kJ mol^?1) in soils, which confirm that temperature had a significant influence on the degradation rate. Q₁₀ value of 1.11, for azoxystrobin, indicated that the response of fungicide dissipation to temperature was large. For azoxystrobin, there was a much larger difference in dissipation rates at 5 °C and 35 °C, indicating that biological and/or chemical degradation of azoxystrobin may have nearly reached its optimum at 35 °C.     

Photosynthesis, respiration and calcification of a zooxanthellate scleractinian coral under submerged and exposed conditions

An experimental set-up was designed to investigate photosynthesis, respiration and calcification of zooxanthellate scleractinian corals under submerged and exposed conditions. The results of experiments to determine the effect of exposure to air on the metabolism of Stylophora pistillata (Esper, 1797) revealed that: (1) maximum gross photosynthesis ( p _{g max}) is 3.6 times higher in water than in air; (2) an indicator of photoadaptation (I _k ) does not reveal any difference between water and air; (3) the difference between submerged and aerial respiration is not statistically significant; (4) aerial photosynthesis–irradiance (P–I) curves display lower initial slopes (α) than aquatic P–I curves; (5) there is no calcification in air. Received: 7 February 1997 / Accepted: 4 March 1997     

Behaviour of pendimethalin and oxyfluorfen in peanut field soil: effects on soil biological and biochemical activities

A field experiment was conducted to study the dissipation kinetics of herbicides pendimethalin and oxyfluorfen in black soil of peanut field at half recommended rate (HRE), recommended rate and double recommended rate as well as to assess their effects on soil microbial parameters and enzymatic activities. In addition, their role in the transformations and availability of some plant nutrients like nitrogen transformation (through ammonification and nitrification processes) and availability of phosphorous were also studied. Incorporation of these herbicides was found to stimulate the activity of soil microbial biomass carbon, fluorescein diacetate hydrolysing activity, alkaline phosphatase and ammonification rates, while dehydrogenase activity, acid phosphatase, nitrification rate and available phosphorous was adversely affected. However, urease remains almost unchanged except for little stimulation at later stages. Dissipation of pendimethalin and oxy?uorfen followed first-order reaction kinetics with half-life (T_1/2) of 13.7–20.1 and 21.5–27.4 days, respectively. Residues of both herbicides persisted up to 60 days in the soil at all the doses except 45 days for pendimethalin at HRE.     

Single and multiple daily dose toxicokinetics of fluoride after oral administration of sodium fluoride along with aluminum sulfate in goats

Our previous study suggested that toxicokinetic parameters of fluoride were significantly changed on the 30th day as compared with 1st day, after repeated oral administration of sodium fluoride alone for 30 days in goats. The purpose of this study was to investigate whether aluminum sulfate has ameliorative effect on the toxicokinetics of fluoride. For this, sodium fluoride (20 mg kg^?1 b. wt.) along with aluminum sulfate (150 mg kg^?1 b. wt.) was administered in goats for 30 days to investigate its effect on toxicokinetics of fluoride on days 1 and 30. The fluoride levels against time were adequately described by one compartment open model. The peak plasma level of fluoride was observed at 2 h. The toxicokinetics data revealed a nonsignificant decrease in β (elimination rate constant) and C _max (the maximum plasma concentration) and increase in t _1/2 K _a (absorption half-lives), t _1/2 β (elimination half-lives), area under the plasma (AUC) concentration versus time curve and mean residence time (MRT) was observed for the last dose from their respective first dose values. On the basis of changes in the toxicokinetic parameters, it was concluded that repeated oral administration has cumulative effect on plasma fluoride level and concurrent oral administration of aluminum sulfate has ameliorative action on the toxicokinetics of fluoride in goats.     

Persistence of gemfibrozil, naproxen and mefenamic acid in natural waters

The occurrence of pharmaceuticals in natural waters is a potential threat to human nutrition and ecosystem quality. The persistence of the acidic pharmaceuticals gemfibrozil, naproxen and mefenamic acid was studied in surface waters of Maracaibo Lake and Tule reservoir (Venezuela) under laboratory conditions. A quick and easy analytical method was developed for the determination of the acidic drugs at microgram per liter levels using aqueous derivatization, liquid–liquid extraction and gas chromatography–mass spectrometry. Pharmaceuticals degradation followed a pseudo first-order kinetic and their half-lives were calculated for every experimental condition. Under sunlight, naproxen and mefenamic acid were degraded at moderate rates with half-lives from 9.6 ± 0.5 to 27.0 ± 6.6 days, while gemfibrozil had a higher persistence (t _1/2 = 119.5 ± 15.6 − 288.8 ± 61.3 days).     

Effects of changing climate on water and nitrogen availability with implications on the productivity of Norway spruce stands in Southern Finland

An integrated process-based model was used to study how the changing climate affects the availability of water and nitrogen, and consequently the dynamics of productivity of Norway spruce (Picea abies) on sites with different initial soil water conditions in southern Finland over a 100-year period. The sensitivity of the total stem volume growth in relation to short-term availability of water and nitrogen was also analyzed. We found that a high proportion (about 88–92%) of the total precipitation was lost in total evapotranspiration (incl. canopy evaporation (E_c), transpiration (E_t) and ground surface evaporation (E_g)), under both current and changing climate. Furthermore, under the changing climate the cumulative amount of E_c and E_g were significantly higher, while E_t was largely lower than under the current climate. Additionally, the elevated temperature and increased expansion of needle area index (L) enhanced E_c. Under the changing climate, the increasing soil water deficit (W_d) reduced the canopy stomatal conductance (g_cs), the E_t, humus yield (H, available nitrogen source) and nitrogen uptake (N_up) of the trees. During the latter phases of the simulation period, the canopy net photosynthesis (P_nc) was lower due to the reduced N_up and soil water availability. This also reduced the total stem volume production (V_s) on the site with the lower initial soil moisture content. The growth was slightly more sensitive to the change in precipitation than to the change in nitrogen content of the needles, when the elevated temperature was assumed. According to our findings, drought stress episodes may become more frequent under the changing climate. Thus, adaptive management strategies should be developed to sustain the productivity of Norway spruce in these conditions, and thus, to mitigate the adverse impacts of climate change.     

Release of Cd immobilized by soil constituents and its bioavailability

Release of Cd immobilized by soil constituents (clay, humic acids, bacterial cells) in vitro and under soil conditions and its bioavailability to lettuce were studied. The most resistant to extraction with 0.02 M EDTA in vitro as well as under soil conditions was cadmium immobilized by humic acids during decomposition of contaminated plant residues but Cd‐dead cells when 0.1 M NaNO₃ was the extractant.

Cadmium addition (3 mg kg^‐1) to soil and its form were without effect on plant growth and amount of metal accumulated in roots. Tops of plants grown in soil supplemented with Cd‐resting cells contained significantly less metal then other ones.     

Hydrodynamics and bed stability of open channel flows with submerged foliaged plants

In this work we investigate experimentally and numerically the flow structure around foliaged plants deployed in a channel with gravels on the bed under submerged and barely submerged conditions. Velocity and Reynolds stress were measured by using a NORTEK Vectrino profiler. Visual observation shows that the initial motion of gravels is easier to be triggered under the condition of flow with barely submerged vegetation. This is confirmed by the measured velocity, Reynolds stress and total kinetic energy (TKE) profiles. The velocity exhibits a speed up in the near-bed region, and the associated Reynolds stress and TKE increase there. A 3D numerical model is then verified against the experiments and used to investigate systematically the effect of degree of submergence of foliaged plants on the channel bed shear stress. The results show that the maximum bed shear stress occurs when the foliage is situated slightly below the water surface, which can enhance channel bed instability.     

Geochemistry of soil around a fluoride contaminated area in Nayagarh District,Orissa, India: Factor analytical appraisal

Fluoride contamination in soil was studied in the vicinity of a hot spring in Nayagarh district of Orissa. Both bulk soil from 0 to 30 cm depth and profile soils from 0 to 90 cm depth were analyzed for total fluoride (F_t) and 0.01 M CaCl₂ extractable fluoride (F_ca), major elements, pH, EC and Organic Carbon (OC). High concentrations of both F_t and F_ca were observed in the area surrounding the hot spring and the village of Singhpur. Principal factor analysis (PFA) on the parameters of the bulk soils suggests that two major chemical processes due to three factors, control the soil geochemistry of the area. Factor-1 contributes 37.11% of the total variance and is strongly loaded with Al, Si, Fe, F_tand F_ca, and explains the fluoride enrichment of the soil, whereas the second and the third factors contribute 16.6 and 12.2%, respectively and explain the controlling process of carbonate precipitation and soil alkalinity. Multiple regression analysis of the scores of the factors was performed to derive a fluoride contamination index in soil. The magnitude of the factor effect on the contamination index follows the order of Factor-1 > Factor-2 > Factor-3. The spatial distribution of the contamination index is used to classify the area into highly contaminated, moderately contaminated and uncontaminated zones.     

Photodegradation of Benthiocarb

The photodegradation of ¹⁴C-benthiocarb in water, on a glass surface, on soil and silica gel TLC plates was studied. the study was designed to obtain some information of its dissipation and photodegradation under various laboratory conditions. Benthiocarb degrades readily when exposed to either sunlight or UV light (254 nm). However, it is degraded much faster by UV light than by sunlight. Also, benthiocarb decomposes faster in water or on a glass surface or silica gel surface than on a soil surface. the half-life of benthiocarb exposed to UV light was: 1 hr on glass surface; 1.5 hrs in water; 2 hrs on silica gel TLC plate; 20 hrs on soil TLC plate. Benthiocarb in water, and exposed to sunlight, had a half-life of approximately 3 days. the following major photodegradation products were identified: 4-chlorobenzyl alcohol; 4-chlorobenzaldehyde; 4-chlorobenzoic acid.     

Spatial variations in the N2O emissions and denitrification potential of riparian buffer strips in a contaminated urban river

Spatial variations in the N₂O emissions and denitrification potential of riparian buffer strips (RBS) in a polluted river were examined. The river received large pollutant inputs from urban runoff and wastewater discharge, resulting in impaired water quality in the river and downstream reservoir. The potential for nitrogen removal by RBS was evaluated by measuring in situ N₂O emission fluxes in static closed chambers and sediment denitrification potentials with acetylene inhibition techniques. The results showed that N₂O emission fluxes decreased from the upstream (16.39 μg/(m²·h)) to downstream (0.30 μg/(m²·h)) sites and from the water body to upland sites. The trend in decreasing N₂O emission fluxes in the downstream direction was mainly associated with sediment/soil textures (clay loam→sandy soil) and sediment/soil water contents and was also related to the vegetation along the RBS and nutrients in the sediments/soils. The correlation coefficient was highest (r=0.769) between the N₂O emission flux and sediment/soil water content. Sediment/soil denitrification potentials under N-amended and ambient conditions were higher (highest 32.86 mg/(kg·h)) for the upstream sites, which were consistent with in situ N₂O flux rates.     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

多效唑在番茄和土壤中的残留与降解动态研究

研究了多效唑（paclobutrazol）在番茄（Lycopersicon eseulentum）和土壤中的残留分析方法及残留动态。建立番茄和土壤样品中多效唑残留的固相萃取-高效液相色谱（SPE-HPLC）检测方法,样品用乙腈提取,再用φ（甲醇-二氯甲烷）=5∶95混合溶剂经LC-NH2固相萃取柱净化,以φ（乙腈-水）=55∶45作流动相,Shiseido C18色谱柱（4.6 mm×250 mm,5μm）于222 nm波长检测,外标法定量。在0.1~5.0 mg·L-1范围内,多效唑峰面积与其质量浓度之间呈良好线性关系,相关系数为0.9995。采用田间试验方法,在番茄幼苗期施用不同多效唑质量分数50、100、200、600 mg·kg-1,研究在不同处理时间1、6 h,1、2、3、7、14、21、30、45、60 d,多效唑在番茄以及土壤中的残留动态变化。添加质量分数水平为0.05、0.1、0.5 mg·kg-1时,多效唑在果实、植株和土壤中的添加回收率分别为92.45%~103.70%、94.52%~98.85%和94.30%~102.10%,变异系数分别为3.69%~5.00%、1.58%~4.53%和1.28%~3.35%。结果表明：多效唑在番茄植株和土壤中的降解规律均符合一级动力学方程C=Coe-kt。当施用质量分数为600 mg·kg-1时,其在番茄植株中的残留半衰期为1.66 d,在土壤中的半衰期为2.78 d;在植株中的降解速率大于在土壤中的降解速率。按照推荐使用的施用浓度,采收时多效唑在番茄和土壤中无残留,证明推荐施用浓度是合理的。