Persistence and Dissipation Kinetics of Spiromesifen in Chili and Cotton

In a field study carried out at three different locations, the dissipation of spiromesifen on cotton and chili was studied and its DT₅₀, and DT₉₉ were estimated at each location. Spiromesifen was sprayed on chili at 96 and 192 g a.i. ha⁻¹ and cotton at 120 and 240 g a.i. ha⁻¹. Samples of chili fruits were drawn at 0, 1, 3, 5, 7, 10, 15, 21, 30 days after treatment and that of cotton seed and lint at first picking and harvest. Soil samples were drawn 30 days after treatment from 0 to 15 and 15 to 30 cm layer. Quantification of residues was done on GC–MS in Selected Ion Monitoring (SIM) mode in mass range 271–274 m/z. The LOQ of this method was found 0.033 μg g⁻¹, LOD being 0.01 μg g⁻¹. The DT₅₀ of spiromesifen when applied at recommended doses in chili fruits was found to be 2.18–2.40 days. Ninety-nine percent degradation was found to occur within 14.5–16.3 days after application. Residues of spiromesifen were not detected in cotton seed and lint samples at the first picking. In soil, no residues of spiromesifen were detectable 15 days after treatment.     

Assessment of flubendiamide residues in pigeon pea in different agro-climatic zones of India

Supervised field trials were conducted at the research farms of four agricultural universities located at different agro-climatic zones of India to find out the harvest time residues of flubendiamide and its des-iodo metabolite on pigeon pea (Cajanus cajan) during the year 2006-2007. Two spray applications of flubendiamide 20 WDG at 50 g (T(1)) and 100 g (T(2)) a.i./ha were given to the crop at 15-days interval. The foliage samples at different time intervals were drawn at only one location, however, the harvest time samples of pigeon pea grain, shell, and straw were drawn at all the four locations. The residues were estimated by HPLC coupled with UV-VIS variable detector. No residues of flubendiamide and its des-iodo metabolite were found at harvest of the crop at or above the LOQ level of 0.05 μg/g. On the basis of the data generated, a pre-harvest interval (PHI) of 28 days has been recommended and the flubendiamide 20 WDG has been registered for use on pigeon pea by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India and the MRL has been fixed by Ministry of Health and Family Welfare, Government of India under Prevention of Food and Adulteration as 0.05 μg/g on pigeon pea grains.     

GC–ECD analysis of S-metolachlor (Dual Gold) in cotton plant and soil in trial field

The analytical method of S-metolachlor residue and its degradation in cotton and soil in trial field were investigated. S-metolachlor EC (96% w/w) was applied as pre-emergence at dosages of 1,500 and 2,250 ml ha(-1) 3 days after sowing of the cottonseeds in the field. The soil and the plant samples were collected at different intervals and the residues of S-metolachlor were analyzed by GC-ECD. The results showed that the degradation of S-metolachlor in cotton leaves in Beijing and Nanjing coincides with C = 0.1113e(-0.1050t) and C = 0.1177e(-0.1580t), respectively; the half-lives were about 6.6 and 4.4 days. The degradation of S-metolachlor in soil in Beijing and Nanjing coincides with C = 1.0621e(-0.0475) (t), and C = 0.9212e(-0.0548) (t), respectively; the half-lives were about 14.6 and 12.6 days,. At harvest time, the S-metolachlor in cotton seeds and soil samples were detected by GC-ECD and confirmed by GC/MS. The results showed that the residues in cottonseeds were lower than the USA EPA's maximum residue limit of 0.1 mg kg(-1) in cottonseed. It could be considered as safe to human beings and environment.     

Assessment of carcinogenic heavy metal levels in Brazilian cigarettes

Total mercury (Hg(T)) and bioavailability Hg (Hg(HCl)) concentrations in soil were determined in five districts in Wuhu urban area. Spatial pattern of soil Hg concentration was generated through kriging technology. Results showed that Hg concentration in soil ranged from 0.024 to 2.844 mg kg(?-1) with an average of 0.207 mg kg(?-1). Hg concentration in soil appeared to have a block distribution and decreased from downtown to surrounding district. And Hg concentrations appeared to have a medium scale spatial auto correlation, strongly affected by human activity. The maximal Hg average concentration (0.332 mg kg(?-1)) in soil appeared in Jinghu district, where the high intensity of human activities is. Second highest Hg average concentration (0.263 mg kg(?-1)) in soil appeared in development district, where the intensive industrial activities are. Bioavailability Hg concentration in soil ranged from 2.6 to 4.9 μg kg(?-1) with an average of 3.8 μg kg(?-1), which had a ratio of 0.28~6.44% to total Hg. The ratios of bioavailability Hg to total Hg in vegetable soil were bigger than those of park soil. Correlation analysis showed that total Hg, organic matter, total phosphorus, and bioavailability Hg concentrations in soil were significantly positively correlated. Hg concentration in vegetable ranged from 2.7 to 15.2 μg kg(?-1) with an average of 6.5 μg kg(?-1). Hg concentration in vegetable was positively correlated with Hg(HCl) concentration in soil. According to the calculation on hazard quotient (HQ) for children, inhalation of Hg vapor from soil is the main exposure pathway, in which HQ is 2.517 × 10(?-2), accounting for 80.3% of the four exposure pathways. Hazard index (HI) of the four exposure pathways is lower than the "safe" level of HI = 1; therefore, exposure of soil Hg exhibited little potential health risk to children in Wuhu urban area.     

Pesticide residue analysis of soil,water, and grain of IPM basmati rice

The main aim of the present investigations was to compare the pesticide load in integrated pest management (IPM) with non-IPM crops of rice fields. The harvest samples of Basmati rice grain, soil, and irrigation water, from IPM and non-IPM field trials, at villages in northern India, were analyzed using multi-pesticide residue method. The field experiments were conducted for three consecutive years (2008–2011) for the successful validation of the modules, synthesized for Basmati rice, at these locations. Residues of tricyclazole, propiconazole, hexconazole, lambda cyhalothrin, pretilachlor chlorpyrifos, DDVP, carbendazim, and imidacloprid were analyzed from two locations, Dudhli village of Dehradun, Uttrakhand and Saboli and Aterna village of Sonepat, Haryana. The pesticide residues were observed below detectable limit (BDL) (<0.001–0.05 μg/g) in all 24 samples of rice grains and soil under IPM and non-IPM trials. Residues were below detection level (<0.001–0.05 μg/L) in irrigation water samples (2008–09). Residues of tricyclazole and carbendazim, analyzed from same locations, revealed pesticide residues as BDL (<0.001–0.05 μg/g) in all 40 samples of Basmati rice grains and soil. It was also observed as BDL (<0.001–0.05 μg/L) for 12 water samples (2009–2010). The residues of tricyclazole, propioconazole, chlorpyrifos, hexaconazole, pretilachlor, and λ-cyhalothrin were also found as BDL (<0.001–0.05 μg/g) in 40 samples of Basmati rice grains and soil and 12 water samples (<0.001–0.05 μg/L) (2010–2011).     

Dynamics of pesticide residues in nectar and pollen of mustard (Brassica juncea (L.) Czern.) grown in Himachal Pradesh (India)

Residues dynamics of Endosulfan (525.00 g a.i. ha(-1)), Imidacloprid seed treatment (21 g a.i. kg(-1)), Lambdacyhalothrin (75.00 g a.i. ha(-1)) and Spiromesifen (225.00 g a.i. ha(-1)) in nectar and pollen of mustard, Brassica juncea (L.) Czern. grown in Himachal Pradesh (India) were determined through bioassay (using Drosophila melanogaster Meig. as test organism) and GC (Gas chromatographic) and HPLC (High performance liquid chromatographic) methods. In general chromatographic methods were more sensitive for the determination of above given pesticides compared to bioassay method. Average recoveries in nectar samples varied between 82.85 and 88.90% by bioassay and 91.20 and 93.55% by chromatographic techniques. In pollen samples, recoveries varied between 81.44 and 86.44% by bioassay and 88.50 and 91.30% by chromatographic methods. Imidacloprid residues were neither found in nectar nor in pollen samples at the time of sampling i.e. 50% of flowering. The order of average half life of residues was: Lambdacyhalothrin (12.45 h) < Spiromesifen (19.99 h) < Endosulfan (27.49 h) for nectar and Spiromesifen (9.69 h) < Lambdacyhalothrin (12.44 h) < Endosulfan (17.84 h) for pollen samples. It was found that Imidcloprid seed treatment was practically harmless to honey bees, whereas a waiting period of 5 days must be observed on crops sprayed with these chemicals during blooms to avoid any accidental hazards to honey bees.     

Dissipation pattern of flubendiamide in/on brinjal (Solanum melongena L.)

Residues of flubendiamide and desiodo flubendiamide were studied following three applications of flubendiamide 480 SC at 7 days interval at 90 and 180 g a.i. ha(-1) in/on brinjal fruits. An average initial deposit of 0.33 and 0.61 mg kg(-1) of flubendiamide was observed respectively after application at single and double dosages. The residues of flubendiamide dissipated quickly at both the dosages, and after 3 days, the extent of dissipation was found to be about 76% and 79% at the single and double dosages, respectively. Brinjal fruit samples analysed at different time intervals did not show the presence of desiodo flubendiamide. The half-life of flubendiamide was observed to be 0.62 and 0.54 days at single and double dosages, respectively. The limit of determination of flubendiamide and desiodo flubendiamide was observed to be 0.05 mg kg(-1). Soil samples analysed after 15 days of the last application did not reveal the presence of flubendiamide and desiodo flubendiamide at their determination limit of 0.05 mg kg(-1). An assessment of the total intake of flubendiamide resulting through the consumption of brinjal fruits and its comparison with acceptable daily intake seems to be quite safe from consumer point of view.     

Dissipation and residues of bispyribac-sodium in rice and environment

The dissipation and residues of bispyribac-sodium in rice cropping system were studied. Bispyribac-sodium residues were extracted by a simple analytical method based on QuEChERs and detected by LC-MS/MS. The limit of detection for bispyribac-sodium of this method was 0.375?×?10^?3 ng. The limit of quantification (LOQ) was 5.0 μg/kg for rice plant samples, 2.0 μg/kg for rice hull, 0.2 μg/kg for water, and 0.1 μg/kg for soil and husked rice samples. The average recoveries of bispyribac-sodium ranged from 74.7 to 108 %, with relative standard deviations less than 13 %. The half-lives of bispyribac-sodium in rice plant, water, and soil were in the range of 1.4–5.6 days. More than 90 % of bispyribac-sodium residue dissipated within 5 days. The final residues of bispyribac-sodium in rice were all below LOQ at harvest time.     

Dissipation of flubendiamide in/on Brinjal (Solanum melongena) fruits

A field experiment was conducted at Anand Agricultural University, Anand during Sept-Dec, 2009 to study the rate of degradation of flubendiamide in/on brinjal fruits following foliar application of Fame 480 SC at 90 (standard dose) and 180 (double dose) g a.i. ha(?-1). The residues estimated using HPLC revealed persistence of flubendiamide in/on brinjal till 3rd and 7th day after the last spray at standard and double dose, respectively. The residues of flubendiamamde were reported as parent compound, and no desiodo metabolite was detected. The initial deposits of 0.17 and 0.42 μg g(?-1) in/on brinjal fruits reached below determination level of 0.05 μg g(?-1) on the 5th and 10th day at standard and double dose, respectively. The half life of flubendiamide on brinjal fruits ranged from 2.68 to 2.55 days. Soil samples analyzed on the 15th day after the last spray revealed residues at below determination level (0.05 μg g(?-1)) at either dose of application.     

Determination of imazosulfuron persistence in rice crop and soil

Imazosulfuron is a new post-emergence sulfonylurea herbicide. It is highly active at low application rates to control annual and perennial broad-leaf weeds and sedges in rice. There is increasing concerned about the persistence of pesticide residues in soils, crop produce and subsequent contamination of groundwater. Thus persistence of imazosulfuron residues under field condition was evaluated. Imazosulfuron was applied at 30, 40, 50 and 60 a. i. g ha ⁻¹ rates, 4 days after transplanting of rice as post-emergence herbicide. Soil and plant samples treated with imazosulfuron were collected at 60, 90 and 120 days after herbicide application and analyzed for residues. Rice grains and straw samples were sampled at harvest (120 days). Residues of imazosulfuron in soil were not found after 90 and 120 DAS (days after spraying). Rice grains contained 0.006, 0.009 μg g⁻¹ residues at 50 and 60 g ha ⁻¹ application rates. 0.009 and 0.039 μg g⁻¹ residues of imazosulfuron were detected at 50 and 60 g/ha rates respectively in rice straw. Residues of imazosulfuron were not detected applied at 30 and 40 g ha⁻¹ in rice grains and straw, respectively and can be safely applied to the transplanted rice.     

Dissipation behavior and risk assessment of butralin in soybean and soil under field conditions

Dissipation behavior, final residue, and risk assessment of butralin in soybean, green soybean, plant, and soil were investigated. Butralin residues were extracted with acetonitrile and then soybean samples were detected with gas chromatography-mass spectrometer (GC-MS) and soil samples were determined with GC with nitrogen phosphorous detector (GC-NPD). The limit of quantification (LOQ) of the method was 0.01 mg/kg for soybean, green soybean, plant, and soil. Average recoveries ranged from 90.4 ~ 98.2% for green soybean, 86.2 ~ 86.6% for soybean, 86.0 ~ 98.8% for plant, and 85.0 ~ 106.8% for soil. The relative standard deviations (RSDs) were 2.0 ~ 7.2% for green soybean, 2.0 ~ 3.0% for soybean, 3.1 ~ 8.1% for plant, and 1.8 ~ 6.6% for soil. Half-lives of butralin in soil samples varied in the range of 11–22 days. At harvest time, final residues of butralin in soybean and green soybean were lower than LOQ. Risk assessment demonstrated that, at recommended dosage and frequency, butralin would not induce significant harm on humans. The study could be used as a quantitative basis for application of butralin on soybean.     

A regional inventory and monitoring setup to evaluate bark peeling damage by red deer (Cervus elaphus) in coniferous plantations in Southern Belgium

Sediment phosphorus (P) fractions and sorption characteristics and P release from intact sediment cores of Baiyangdian Lake in North China in spring 2009 were investigated. Results of chemical fractionation showed that total P (TP) content in sediment ranged from 443 to 611 mg kg(?-1). Of the P fractions including inorganic P (IP) and organic P (OP), IP was a dominant component of TP and present in the form of P bounded to calcium (Ca-P) while the bioavailable P content bounded to Al, Fe, and Mn oxides and hydroxides (Fe/Al-P) varied from 14 to 102 mg kg(?-1). The batch experiments showed that the sediments had appreciable maximum P adsorption capacity from 141.86 to 377.37 mg kg(?-1). However, the zero P equilibrium concentration (C?(eq))in most sampling sites was larger than the P concentration in water column. Accordingly, the sediments from those sampling sites would release P into the overlying water at the positive P flux rates as a P release source. Significant positive correlation between P flux rates and Fe/Al-P revealed that the sediment P release would mainly originate from the bioavailable P fraction. It is evident that the inherent phosphorus present in lake sediments would be a major threat to the water quality and ecosystem reservation in Baiyangdian lake.     

Residues of endosulfan in the livers of wild catfish from a cotton growing area

Residues of endosulfan insecticide (-and -isomers, and endosulfan sulphate) were determined in the livers of catfish from a cotton growing area during the summer and winter of 1988. The concentration of total endosulfan residues found in the fish was up to 0.31 mg kg^-1 wet wt. It decreased in winter with a maximum 0.02 mg kg^-1 wet wt. The difference in endosulfan residues between seasons was statistically significant (ANOVA,p<0.01).     

Dissipation studies of fentrazamide (YRC-2388) in soil under anaerobic condition

Dissipation of fentrazamide in soil and water under flooded (anaerobic) conditions was studied. Fentrazamide was applied to soil at 100 g ha(-1). Soil was extracted with 0.1 N HCl?:?acetone (1?:?1 v/v) followed by partition and cleanup with silica SPE. Separation was achieved in an ODS-II column with a mobile phase of acetonitrile?:?water (70?:?30 v/v) and detection at 214 nm. Recovery of fentrazamide varied from 75.2-90.4% and 89.9-97.8% in soil and water, respectively. Fentrazamide dissipated rapidly and fentrazamide residues were not detected after 100 and 35 days of application in soil and water, respectively. Half life in soil and water was 9.06 and 3.66 days, respectively. Dissipation followed monophasic first order kinetics pattern. No fentrazamide was detected in soil, rice grain and rice straw at harvest of crop. Calibration curves for quantification were linear and relative standard deviation (RSD) was 1.78%. LOD for instrument was 0.002 μg mL(-1) and LOQ for methods were 0.005 μg g(-1) for soil and water.     

Comprehensive re-analysis of archived herring gull eggs reconstructs historical temporal trends in chlorinated hydrocarbon contamination in Lake Ontario and Green Bay, Lake Michigan, 1971-1982

Herring gull egg homogenates collected between 1971 and 1982 from a colony in central Lake Ontario (Scotch Bonnet Island) and from a colony in central Green Bay, Lake Michigan (Big Sister Island) were archived in the Canadian Wildlife Service Specimen Bank. Pooled samples (N = 10) were exhaustively analyzed in 1993 for a wide range of individual chlorinated hydrocarbon contaminant (CHC) compounds: DDT, mirex and chlordane compounds and metabolites, chlorobenzenes (CBzs), dieldrin, chlorostyrenes (CSs), hexachlorocyclohexanes (HCHs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), and 87 PCB congeners, including the TCDD-like non-ortho and mono-ortho congeners. PCBs and DDTs were the dominant residues in eggs from both Lake Ontario (31-242 mg kg(-1) and 9-64 mg kg(-1)) and Green Bay (34-133 mg kg(-1) and 14-91 mg kg(-1)). SigmaPCBs declined by a factor of 4-5 and DDTs a factor of 4-7 at both colonies between 1971 and 1982. Lake Ontario eggs had significantly higher residues of 2,3,7,8-TCDD (0.2-2.0 microg kg(-1)), HCBz (0.1-4.7 mg kg(-1)), OCS (0.03-0.45 mg kg(-1)), three HpCSs (0.13-0.97 mg kg(-1)), mirex and mirex photodegradation products (2.1-9.2 mg kg(-1)) than Green Bay eggs. HCBz levels in Lake Ontario eggs declined a factor of 40, TCDD and chlorostyrenes a factor of 8-10, and mirex a factor of 4 between 1971-1978. Green Bay eggs had slightly higher levels of chlordane-related compounds, dieldrin and beta-HCH than Lake Ontario eggs. There were no consistent or strong trends in residue levels of these pesticides, PCDDs (except TCDD) and PCDFs in either lake, indicating that rates of input and removal of these CHCs in the lakes were much closer in the early 1970s than was the case for the other compounds.     

Dissipation of flubendiamide residues in/on cabbage (Brassica oleracea L.)

Residues of fubendiamide and its metabolite desiodo flubendiamide were estimated in cabbage and soil using high-performance liquid chromatography with UV–vis detector. The initial deposits of flubendiamide residues on cabbage were found to be 0.16 and 0.31 μg g^?1 following two applications of flubendiamide 20 WG at 12.5 (standard dose) and 25 (double dose) g a.i. ha^?1 respectively at 10-days interval. The half-life values (t _1/2) of flubendiamide on cabbage ranged from 3.4 to 3.6 days. When flubendiamide applied at both the standard and double dose, no detectable residues were found in cabbage and soil at harvest. Thus, a waiting period of 1.63 days was suggested for the safe consumption of flubendiamide-treated cabbage. These data could provide guidance for the proper and safe use of this pesticide on cabbage crops in India.     

Multiresidue analysis of neonicotinoids by solid-phase extraction technique using high-performance liquid chromatography

For routine monitoring of pesticides, a multiresidue analysis through solid-phase extraction technique and using high-performance liquid chromatography (HPLC) in cotton seed cake (CSC) has been developed. Extraction of fortified samples was carried out with aqueous acetone under vacuum. The concentrated extract was loaded onto the solid-phase extraction units, preconditioned with acetonitrile. The extraction units were then washed with hexane and finally eluted with acetonitrile. The pesticide residues were determined using a multiresidue method by reversed-phase HPLC. The average percentage recoveries were found to range between 65.47% and 110% at spiking levels of 10 to 40 mg/kg. The method developed shows a healthy rate of recovery and can successfully be utilized for the extraction and screening of neonicotinoid residues in CSC. The detection limits for imidacloprid, acetamiprid, and thiacloprid using this method were found to be 5, 10, and 20 mg/kg, respectively.     

Phosphate adsorption characteristics at the sediment–water interface and phosphorus fractions in Nansi Lake, China, and its main inflow rivers

Phosphorus fractions and phosphate adsorption characteristics of 16 sediments from a shallow freshwater lake (Nansi Lake, China) and its inflow estuaries were investigated. In the present study, the sediment phosphorus is fractionated into exchangeable P (exch-P), Al-P, Fe-P, Ca-P, organic P (OP), inorganic P (IP) and total P (TP). The results show that the total phosphorus (TP) content in the sediments ranges from 571.67 to 1,113.55 mg kg(-1), and calcium bound phosphorus (Ca-P) is the main fraction of IP. The biologically available phosphorus (BAP) ranges from 32.02 to 229.67 mg kg(-1) in the Nansi Lake sediments. Phosphate adsorption on the sediments mainly occurs within 10 h and is completed within 48 h. The content of native adsorbed phosphorus (omega(NAP)) varies greatly from 6.05 to 194.37 mg kg(-1), showing a significant correlation with the total maximal amount of phosphorus adsorbed (TQ(max)). Adsorption efficiency (m) ranges from 574.79 to 3,220.68 l kg(-1) and zero equilibrium phosphorus concentration (C(EPC)) ranges from 0.010 to 0.157 mg l(-1). After the South-to-North Water Diversion Project, the inherent phosphorus present in sediments will be a major threat to the diverted water quality and be a predominant factor determining the trophic status of the lake even if the external load is reduced.     

Persistence of metsulfuron-methyl in wheat crop and soil

Possible bioaccumulation of pesticides in crop produce may cause ailing effect on animal and human. Thus there is a need to evaluate these chemicals in the soil and crop produce at harvest. Metsulfuron-methyl is a post-emergence herbicide. It is highly active to control broad-leaf weeds in cererals, pasture and plantation crops. Metsulfuron-methyl was applied at 3, 4, 5, and 8 g a.i. ha(-1) rates, after 30 days of sowing in wheat as post-emergence herbicide. Soil samples treated with metsulfuron-methyl were collected after 30 and 60 days along with control and at harvest after herbicide application and analyzed for residues by High Performance Liquid Chromatography (HPLC) using photo diode array detector at 220 nm. Wheat grains and straw samples were sampled at harvest. At harvest the residue level of metsulfuron-methyl in soil was found below the detection limit at 3-5 g a.i. ha(-1) application rates and 0.002 microg g(-1) at 8 g a.i. ha(-1), respectively. No residues of metsulfuron-methyl were detected in wheat grains at 3-4 g a.i. ha(-1) rates. However 0.002 microg g(-1) residues were detected in wheat straw at 5 and 8 g a.i. ha(-1) application rates. It can be concluded that metsulfuron-methyl application at 3-4 g a.i. ha(-1) can be safely applied to the wheat crop as post-emergence herbicide.     

Determination and study on dissipation and residue determination of cyhalofop-butyl and its metabolite using HPLC-MS/MS in a rice ecosystem

Cyhalofop-butyl is an aryloxyphenoxypropionate postemergence herbicide with good control of barnyard grass in rice paddies. In this study, method for the determination of cyhalofop-butyl and its metabolite was developed with high-performance liquid chromatography tandem mass spectrometry. Dissipation and residue levels of cyhalofop-butyl and its metabolite in rice ecosystems were also investigated. Recoveries and relative standard deviations of cyhalofop-butyl and cyhalofop acid in six matrices at three spiking levels ranged from 76.1 to 107.5 % and 1.1 to 8.2 %, respectively. The limit of quantitation (LOQ) of cyhalofop-butyl and cyhalofop acid was 0.01 mg/kg in paddy water, paddy soil, rice plant, rice straw, rice hulls, and husked rice. For field experiments, the results showed that cyhalofop-butyl degraded to cyhalofop acid quickly, and the half-lives of cyhalofop acid in paddy water, paddy soil, and rice plant were 1.01–1.53, 0.88–0.97, and 2.09–2.42 days, respectively. Ultimate residues of cyhalofop-butyl and its metabolite in the rice samples were not detectable or below 0.01 mg/kg at harvest.