Residue determination and dissipation of ioxynil octanoate in maize and soil

A simple and efficient residue analysis method for direct determination of ioxynil octanoate in maize and soil was developed and validated with High Performance Liquid Chromatography-Ultra Violet (HPLC-UV). The samples were extracted with mixtures of acetonitrile and deionized water followed by Solid Phase Extraction (SPE) to remove co-extractives prior to analysis by HPLC-UV. The recoveries of ioxynil octanoate extracted from maize and soil samples ranged from 86 %–104 % and 84 %–96 %, respectively, with relative standard deviation (RSD) less than 7.84% and sensitivity of 0.01 mg kg^?1. The method was applied to determine the residue of ioxynil octanoate in maize and soil samples from experimental field. Data had shown that the dissipation rate in soil was described as pseudo-first-order kinetics and the half-life (t_1/2) was less than 1.78 days. No ioxynil octanoate residue (<0.01 mg kg^?1) was detected in maize at harvest time withholding period of 60 days after treatments of the pesticide. Direct confirmation of the analytes in field trial samples was realized by Liquid Chromatography-Mass Spectrometry (LC-MS).     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

丙溴磷在稻田环境中的残留动态研究

确立了气相色谱法测定丙溴磷残留量的检测方法.采用该方法,丙溴磷在土壤、植株、糙米、稻壳和田水中的平均添加回收率为87.2％～103.6％,变异系数为3.20％～11.50％,最低检测质量浓度:田水为0.005 mg/kg;土壤、植株、糙米和稻壳为0.050 mg/kg.残留动态研究表明,丙溴磷在田水、植株和土壤中的半衰...     

Distribution of pesticide residues in soil and uncertainty of sampling

Pesticide residues were determined in about 120 soil cores taken randomly from the top 15 cm layer of two sunflower fields about 30 days after preemergence herbicide treatments. Samples were extracted with acetone-ethyl acetate mixture and the residues were determined with GC-TSD. Residues of dimethenamid, pendimethalin, and prometryn ranged from 0.005 to 2.97 mg/kg. Their relative standard deviations (CV) were between 0.66 and 1.13. The relative frequency distributions of residues in soil cores were very similar to those observed in root and tuber vegetables grown in pesticide treated soils. Based on all available information, a typical CV of 1.00 was estimated for pesticide residues in primary soil samples (soil cores). The corresponding expectable relative uncertainty of sampling is 20% when composite samples of size 25 are taken. To obtain a reliable estimate of the average residues in the top 15 cm layer of soil of a field up to 8 independent replicate random samples should be taken. To obtain better estimate of the actual residue level of the sampled filed would be marginal if larger number of samples were taken.     

Preliminary study on persistence in soil and residues in maize of imidacloprid

The aim of this work was to study the distribution of imidacloprid in soil and its translocation to roots and aerial parts of maize plant. The main objective was to assess imidacloprid residues in field environment, in order to provide data on honeybees exposure level to such an active substance. Imidacloprid has been detected and quantified by Triple Quadrupole HPLC-MS-MS. Pesticide persistence in the soil and its residues in pollen and in maize plants have been evaluated during the growing of maize plants developed from seeds dressed with Gaucho 350 FS (imidacloprid: 1.0 mg/seed). The sowing has been performed by means of a pneumatic precision drill. Samples have been collected at 30, 45, 60, 80, 130 days after the sowing, as pollen samples have been collected at the tasseling. Imidacloprid presence in aerial part of maize plant declined to 2-3 μg/kg 80 days after the sowing, while concentration in kernel at harvest was <1 μg/kg. Maize pollen represents an important part of protein supply of beehives, and it is of critical importance to bee foraging. The values detected (imidacloprid residues <1 μg/kg) showed that maize pollen source should not be relevant for acute toxicity impact on honey bees.     

Occurrence and distribution of hexachlorocyclohexane isomers in vegetation samples from a contaminated area

The occurrence and distribution of four major hexachlorocyclohexane (HCH) isomers (alpha-, beta-, gamma- and delta-) were studied in vegetation samples of a highly contaminated area close to a small-scale industrial belt in Lucknow (North India). Eight species of plants were collected at different points of the contaminated area and different parts of the plants were separated in order to study the difference in uptake and accumulation. The samples were extracted by matrix solid-phase dispersion (MSPD) extraction and finally determined by a gas-chromatograph equipped with (63)Ni electron capture detector (ECD). HCH isomers were present in almost all samples and the concentration of total HCH in the plant sample analyzed varied between 13 and 44 mg kg(-1), being the main isomer of beta-HCH (8-22 mg kg(-1)). Lindane (gamma-HCH) was present in all samples (1-9 mg kg(-1)). Solanum torvum Sw., and Erianthus munja shows the highest and lowest capacity for accumulation of HCH, respectively with a significant difference at p<0.01 level. The highest concentration of HCH residue in root samples indicates the most likely mechanism of HCH accumulation in these plants was sorption of soil HCH on roots. Solanum torvum Sw., and Withania somnifera (L.) Dunal could accumulate considerable levels of HCH isomers (44 and 34 mg kg(-1), respectively). The results reflect the importance of plants in monitoring purposes and their potential for phytoremediation of HCH contaminated soils.     

Analysis of herbicide Krovar I by liquid chromatography with atmospheric pressure chemical ionization mass spectrometry

A simple, very efficient method is presented for routine analysis of herbicide Krovar I (active components bromacil and diuron) in water and soil samples. Water samples were extracted by liquid-liquid extraction with dichloromethane (DCM) as extraction solvent. For soil samples two different extraction techniques were compared: microwave-assisted solvent extraction and a shaking technique using a platform shaker. Extracts were analyzed by high performance liquid chromatography using a water:methanol gradient. Liquid chromatography was coupled with atmospheric pressure chemical ionization mass spectrometry (LC-APCI-MS) for quantification of bromacil and diuron. Optimization of the APCI-MS was done by using standards in the flow injection analysis mode (FIA). Method detection limit for liquid samples for bromacil is 0.04 microg L(-1) and for diuron 0.03 microg L(-1). Method detection limit for soil samples is 0.01 microg g(-1) dry weight for both compounds. Results of analysis of field samples of water and soil are also presented.     

Biodegradation of alpha and beta endosulfan in soil as influenced by application of different organic materials

A laboratory pot experiment was conducted to study the effect of amending soil with four different sources of organic matter on the degradation rate of alpha and beta endosulfan isomers. Poultry by-product meal, poultry manure, dairy manure, and municipal solid waste compost were cured, dried, ground (<1 mm) and thoroughly mixed with a calcareous soil at a rate of 2% and placed in plastic pots. Endosulfan was added at the rate of 20 mg kg(-1). The moisture level was kept near field capacity and the pots were kept at room temperature. Soil sub-samples, 100 g each, were collected from every pot at days 1, 8, 15, 22, 29, 43, and 57 for the measurement of endosulfan isomers. Endosulfan residues were extracted from the soil samples with acetone. The supernatant was filtered through anhydrous sodium sulphate, 5 mL aliquot was diluted to 25 mL with hexane, mixed well, and then two sub-samples from the filtrates were analyzed for alpha and beta endosulfan isomers by gas chromatography. The results indicated that the half-life (T(1/2)) of alpha-endosulfan in the poultry by-product meal treatment was 15 days compared to about 22 days in the other treatments. The T(1/2) of beta-endosulfan was 22 days in the poultry by-product meal treatment and followed a bi-phasic pattern, 57 days in the municipal solid waste compost treatment and the extrapolated T(1/2) was about 115 days for the other three treatments.     

Determination of acibenzolar-S-methyl and its acidic metabolite in soils by HPLC-diode array detection

A simple and accurate method for the analysis of acibenzolar-S-methyl (benzo[1,2,3]thiadiazole-7-carbothioic acid-S-methyl ester; CGA 245 704; ASM) and its major conversion product, benzo[1,2,3]thiadiazole-7-carboxylic acid (CGA 210 007; BTC), in soils is presented. ASM extraction from soil samples was performed using acetonitrile and BTC was extracted with a mixture of potassium phosphate buffer (0.5 M, pH 3) and acetonitrile (70:30 %, v/v). Both extracts were directly analyzed in a high-performance liquid chromatography-diode array detection (HPLC-DAD) system. Pesticide separation was achieved on a C18 (4.6 mm × 150 mm, 5 μm) analytical column with a isocratic elution of acetonitrile:water 40:60 % (v/v) with 0.6 mL L?1 acetic acid at a flow rate of 1 mL min?1. Linear regression coefficients (r (2)) of the external calibration curves were always above 0.9997. The limits of detection (LOD) and quantification (LOQ) of the method were 0.005 and 0.02 mg kg?1 for ASM, and 0.01 and 0.05 mg kg?1 for BTC, respectively. Recoveries were investigated at six fortification levels and were in the range of 90-120 % for ASM and 74-96 % for BTC with relative standard deviations (RSDs) below 11 % in all cases. The method was also validated by analyzing freshly spiked soil samples with 2.7% organic matter content at 0.5 mg kg?1 level, with slightly lower recovery values only for ASM. Moreover, recoveries for intermediate aged residues of the analytes were similar to fresh residues. This method was also applied to determine ASM half-life (t(?) = 8.7 h) and the rate of the acidic metabolite formation.     

Aged and bound herbicide residues in soil and their bioavailability. Part 2: Uptake of aged and non-extractable (bound) [carbonyl-14C]methabenzthiazuron residues by maize

[Carbonyl-14C]methabenzthiazuron (MBT) was applied to growing winter wheat in an outdoor lysimeter. The amount applied corresponded to 4 kg Tribunil/ha. 140 days after application the 0-2.5 cm soil layer was removed from the lysimeter. This soil contained about 40% of the applied radioactivity. Using 0,01 M CaCl2 solution or organic solvents, the extractable residues were removed from the soil. The bioavailability of the non-extractable as well as aged residues remaining in the soil was investigated in standardized microecosystems containing 1.5 kg of dry soil. During a 4 weeks period the total uptake (4 maize plants/pot) amounted up to 3.6; 2.2; and 0.9% of the radioactivity from soils containing aged MBT residues, MBT residues non-extractable with 0.01 M CaCl2 or MBT residues non-extractable with organic solvents, respectively. About 20% of the radioactivity found in maize leaves represented chromatographically characterized parent compound. At the end of the plant experiment the soil was extracted again with 0.01 M CaCl2 and with organic solvents. The soil extracts and also the organic phases obtained from the aqueous fulvic acid solution contained unchanged parent compound.     

Variability of pesticide residues in cauliflower units collected from a field trial and market places in Greece

To estimate the variability of pesticide residue levels present in cauliflower units, a total of 142 samples were collected from a field trial of a cooperative farmer, and 120 samples were collected from different market places in Thessaloniki, Greece. The collected samples were extracted using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction technique, and the residues were determined by liquid chromatography–tandem mass spectrometry. The developed method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD), and limit of quantification (LOQ). The average recoveries for all the analytes, derived from the data of control samples fortified at 0.01, 0.05, 0.1, and 0.2 mg/kg, ranged from 74 to 110% with a relative standard deviation of ≤8%. The correlation coefficient (R²) was ≥0.997 for all the analytes using matrix-matched calibration standards. The LOD values ranged from 0.001 to 0.003 mg/kg, and the LOQ was determined at 0.01 mg/kg for all the sought analytes. The matrix effect was found to be at a considerable level, especially for cypermethrin and deltamethrin, amounting to +90% and +145%, respectively. For the field samples, the unit-to-unit variability factors (VFs) calculated for cypermethrin and deltamethrin were 2.38 and 2.32, respectively, while the average VF for the market basket samples was 5.11. In the market basket samples, residues of cypermethrin, deltamethrin, chlorpyrifos, and indoxacarb were found at levels ≥LOQ and their respective VFs were 7.12, 5.67, 5.28, and 2.40.     

Development of an analytical method for analysis of flubendiamide, des-iodo flubendiamide and study of their residue persistence in tomato and soil

Flubendiamide is a new insecticide that has been found to give excellent control of lepidopterous pests of tomato. This study has been undertaken to develop an improved method for analysis of flubendiamide and its metabolite des-iodo flubendiamide and determine residue retention in tomato and soil. The analytical method developed involved extraction of flubendiamide and its metabolite des-iodo flubendiamide with acetonitrile, liquid-liquid partitioning into hexane-ethyl acetate mixture (6:4, v v?1) and cleanup with activated neutral alumina. Finally the residues were dissolved in gradient high pressure liquid chromatography (HPLC) grade acetonitrile for analysis by HPLC. The mobile phase, acetonitrile-water at 60:40 (v v?1) proportion and the wavelength of 235 nm gave maximum peak resolution. Using the above method and HPLC parameters described, nearly 100 % recovery of both insecticides were obtained. There was no matrix interference and the limit of quantification (LOQ) of the method was 0.01 mg kg?1. Initial residue deposits of flubendiamide on field-treated tomato from treatments @ 48 and 96 g active ingredient hectare?1 were 0.83 and 1.68 mg kg?1, respectively. The residues of flubendiamide dissipated at the half-life of 3.9 and 4.4 days from treatments @ 48 and 96 g a.i. ha?1, respectively and persisted for 15 days from both the treatments. Des-iodo flubendiamide was not detected in tomato fruits at any time during the study period. Residues of flubendiamide and des-iodo flubendiamide in soil from treatment @ 48 and 96 g a.i. ha?1 were below detectable level (BDL, < 0.01 mg kg?1) after 20 days. Flubendiamide completely dissipated from tomato within 20 days when the 480 SC formulation was applied at doses recommended for protection against lepidopterous pests.     

Determination of fungicide kresoxim-methyl residues in cucumber and soil by capillary gas chromatography with nitrogen-phosphorus detection

The method of residue analysis of kresoxim-methyl and its dissipation rate in cucumber and soil in a greenhouse were studied. Residues of kresoxim-methyl were extracted from cucumber and soil matrices with acetone, purified by liquid-liquid extraction and Florisil cartridges, and then determined by GC with NP-detector. The limit of detection was estimated to be 9 x 10-12 g, and the minimum determination concentration of kresoxim-methyl in the samples was 0.005 mg kg-1. The average recoveries ranged from 89.4 to 100.2% with a coefficient variation between 2.4 and 8.9%. Dissipation study showed that the half-lives of kresoxim-methyl in cucumber were approximately 6.5 days at both the recommended and double the recommended dosage. Half-lives for both the treatments were approximately 8 days in soil. The present study revealed that the residues in cucumber were below the MRL (0.05 mg kg-1, fixed by EU) after 7 days for both treatments.     

Residues of chlorantraniliprole in rice field ecosystem

The fate of chlorantraniliprole was studied in rice field ecosystem, and a simple and reliable analytical method was developed for determination of chlorantraniliprole in soil, rice straw, paddy water and brown rice. Chlorantraniliprole residues were extracted from samples with acetonitrile. The extract was cleaned up with QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method, and determined by high-performance liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The average recoveries were 76.9-82.4% from soil, 83.6-89.3% from rice straw, 95.2-103.1% from paddy water and 84.9-87.7% from brown rice. The relative standard deviation was less than 15%. The limits of detection (LODs) of chlorantraniliprole calculated as a sample concentration (S/N ratio of 3) were 0.012 μg L(-1) for paddy water, 0.15 μg kg(-1) for soil, brown rice and rice straw. The results of the kinetics study of chlorantraniliprole residue showed that chlorantraniliprole degradation in soil, water and rice straw coincided with C=0.01939e(-0.0434t), C=0.01425e(-0.8111t), and C=1.171e(-0.198t), respectively; the half-lives were about 16.0 d, 0.85 d and 3.50 d, respectively. The degradation rate of chlorantraniliprole in water was the fastest, followed by rice straw. The final residues of chlorantraniliprole on brown rice were lower than maximum residue limit (MRL) of 0.02 mg kg(-1) after 14 d Pre-Harvest Interval (PHI). Therefore, a dosage of 150 mL a.i.hm(-2) was recommended, which could be considered as safe to human beings and animals.     

Effects of fungicides triadimefon and propiconazole on soil bacterial communities

The impact of fungicides triadimefon and propiconazole on soil bacterial populations from a strawberry field was investigated. Two fungicides were applied to the soil at concentrations of 10 mg/kg or 100 mg/kg with soil water contents 20.2% (fresh soil water content) or 26.0% (field capacity). Changes in bacterial communities were assessed using DNA extraction, polymerase chain reaction (PCR) amplification of the 16S rDNA and denaturing gradient gel electrophoresis (DGGE). High performance liquid chromatography (HPLC) was utilized to detect the residue of fungicides in soils. The results showed that propiconazole was more persistent than triadimefon in soils, and the two soil water contents did not cause significant differences in dissipation rates between the two fungicides. A high concentration of propiconazole could inhibit the existence of soil microbes while one of triadimefon might induce the microbial population in the first stage. From unweighted pair-group method using arithmetic averages (UPGMA) dendrograms, the effect of triadimefon and propiconazole at the two applied concentrations on a soil bacterial community could be long term. After triadimefon was applied for 60 days and propiconazole for 75 days, the compositions of microbial communities were not recovered. From the viewpoint of environmental protection, it was of significant importance to pay more attention not only to the residues of pesticide but also to the change in soil microbial communities.     

Inorganic arsenic and trace elements in Ghanaian grain staples

A total of 549 samples of rice, maize, wheat, sorghum and millet were obtained from markets in Ghana, the EU, US and Asia. Analysis of the samples, originating from 21 countries in 5 continents, helped to establish global mean trace element concentrations in grains; thus placing the Ghanaian data within a global context. Ghanaian rice was generally low in potentially toxic elements, but high in essential nutrient elements. Arsenic concentrations in rice from US (0.22 mg/kg) and Thailand (0.15 mg/kg) were higher than in Ghanaian rice (0.11 mg/kg). Percentage inorganic arsenic content of the latter (83%) was, however, higher than for US (42%) and Thai rice (67%). Total arsenic concentration in Ghanaian maize, sorghum and millet samples (0.01 mg/kg) was an order of magnitude lower than in Ghanaian rice, indicating that a shift from rice-centric to multigrain diets could help reduce health risks posed by dietary exposure to inorganic As.     

液相色谱测定土壤中氟磺胺草醚残留量方法研究

采用甲醇／浓盐酸浸渍振荡提取，二氯甲烷萃取，经弗罗里硅土柱层析净化，用液相色谱法测定。方法的最低检出含量为０．０２ｍｇ／ｋｇ，添加回收率在９５．８％￣９６．６％之间。     

Bioavailability of PCDD/F from contaminated soil in young Goettingen minipigs

For the general population the intake of food of animal origin is the main route of human exposure to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F). Besides this the ingestion of contaminated soil might be an important exposure path for small children. For risk assessment the knowledge of the bioavailable fraction of soil bound contaminants is important. In a balance study with young Goettingen minipigs the oral bioavailability of PCDD/F from contaminated soil was estimated by determination of the retention of PCDD/F from soil in different organs and tissues. Relative bioavailability was estimated by comparing the retention from soil to the retention of PCDD/F in organs and tissues after oral administration of a PCDD/F mixture extracted from the same soil by solvent. The soil had a PCDD/F-contamination of 5.3 microg I-TEq/kg and originated from a former arable land that had been treated with sludge from the port of Hamburg some years ago. Two groups of each four animals were exposed daily for 28 days via their diet either to 0.5 g soil per kg body weight and day (2.63 ng I-TEq/(kg(bw).d)) or to a daily dose of 1.58 ng I-TEq/(kg(bw).d) given to the diet by solvent. Five unexposed animals were used as a control group. Liver, adipose tissue, muscle, brain and blood were analyzed for their PCDD/F content. Accumulation of PCDD/F from soil or solvent in comparison to control animals was only observed for congeners with 2378-chlorosubstitution and predominantly took place in the liver. Bioavailability of 2378-chlorosubstituted congeners was in the range of 0.64%-21.9% (mean: 10.1%) from soil and 2.8%-59.8% (mean: 31.5%) when administered by solvent. The soil matrix reduced the bioavailability by about 70%. Expressed as I-TEq only 13.8% of the PCDD/F contamination were bioavailable from soil. The relative bioavailability of 2378-chlorosubstituted congeners from soil in relation to administration by solvent was in the range of 2%-42.2% (mean: 28.4%). When not considering the bioavailability, the risk by oral uptake of PCDD/F contaminated soil might be overestimated.     

Simultaneous determination of imidacloprid, thiacloprid, and thiamethoxam in soil and water by high-performance liquid chromatography with diode-array detection

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C18 cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 +/- 4.2% for thiamethoxam, 99 +/- 4.2% for imidacloprid and 94 +/- 1.4% for thiacloprid. The recoveries for water samples ranged from 87 +/- 3.4% for thiamethoxam to 97 +/- 3.9% for imidacloprid and 97 +/- 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5g), and 2, 2, 0.5, micro/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively.     

Cu accumulation in the earthworm Dendrobaena veneta in a heavy metal (Cu, Pb, Zn) contaminated site compared to Cu accumulation in laboratory experiments

Earthworms (Dendrobaena veneta) were exposed to heavy metal contaminated soil from a field site under both laboratory and field conditions. In the laboratory study, D. veneta were analysed for Cu after 2 weeks' exposure. The tissue Cu concentration (Cu(W)) increased proportionally with the total extractable soil Cu content (Cu(T)) in soils that contained less than 150 mg Cu kg(-1). In D. veneta exposed to soils containing more than Cu(T) = 150 mg kg(-1), however, we observed no further increase in Cu(W). In a 64-m(2) field plot at a contaminated site, 81 soil samples were taken and analysed for Cu, Pb, Zn and pH. In June 1994, 1000 D. veneta were homogeneously distributed in the plot and sampled after 1, 2 and 5 weeks to analyse for Cu. Additionally, 2000 D. veneta were introduced in September 1994 and sampled after 1, 2 and 4 weeks. At locations where earthworms were removed, the soil Cu content was estimated by disjunctive kriging. Cu concentration factors (ratio of Cu(W) to Cu(T)) in the field experiment were in excellent agreement with those of the laboratory experiment. This indicates that, with a sufficiently high sampling density, it may be feasible to predict earthworm Cu accumulation in the field using a concentration factor determined in the laboratory.