Determination and study on dissipation and residue of bismerthiazol and its metabolite in Chinese cabbage and soil

A simple and accurate method for the determination of bismerthiazol and its metabolite 2-amino-5-mercapto-1,3,4-thiadiazole was developed in Chinese cabbage and soil by high-performance liquid chromatography-diode array detection in this study. The limits of detection were 0.06 mg/kg for bismerthiazol and 0.03 mg/kg for 2-amino-5-mercapto-1,3,4-thiadiazole, respectively. Recoveries of cabbage and soil were investigated at three spiking levels and were in the range of 84.0–96.0 % for bismerthiazol and 71.0–74.6 % for 2-amino-5-mercapto-1,3,4-thiadiazole, with relative standard deviations below 7.0 %. For field experiments, the half-life of bismerthiazol was 2.4–2.5 days in Chinese cabbage and 2.5–4.8 days in soil at the two experimental locations in China. Dissipation residues of 2-amino-5-mercapto-1,3,4-thiadiazole were lower than 0.72 mg/kg. Terminal residues of bismerthiazol and its metabolite were less than 3.0 and 0.3 mg/kg in Chinese cabbage, respectively. No bismerthiazol or metabolite residues were detected in soil on days 5, 7, 10, and 14 after the last spraying at the two dosage levels.     

Residues and dissipation of trifloxystrobin and its metabolite in tomatoes and soil

A simple residue analytical method using the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure for the determination of trifloxystrobin and its metabolite trifloxystrobin acid (CGA321113) in tomato and soil was developed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of detection were 0.0005 mg/kg for trifloxystrobin and 0.001 mg/kg for trifloxystrobin acid, respectively. The average recoveries in tomato and soil ranged from 73–99 % for trifloxystrobin and 75–109 % for trifloxystrobin acid, with relative standard deviations below 15 %. The method was then used to study the dissipation and residues in tomato and soil. The dissipation half-lives of trifloxystrobin in tomato were 2.9 days (Beijing) and 5.4 days (Shandong), while in soil were 1.9 days (Beijing) and 3.0 days (Shandong), respectively. The final results showed that the major residue compound was trifloxystrobin in tomato whereas it was its metabolite, trifloxystrobin acid, in soil. The final residues of total trifloxystrobin (including trifloxystrobin acid) were below the EU maximum residue limit of 0.5 mg kg^?1 in tomato 3 days after the treatment.     

Dissipation and residue of azoxystrobin in banana under field condition

A method was developed for determining azoxystrobin in banana and cultivation soil using gas chromatography. The dissipation and residue of azoxystrobin in banana fields at GAP conditions were investigated. The average recoveries ranged from 80.3 to 96.0 % with relative standard deviations of 2.9 to 7.2 % at three different spiking levels for each matrix. The results indicated that the half-life of azoxystrobin in bananas and soil ranged from 7.5 to 13.5 days in Guangdong and from 8.7 to 12.7 days in Fujian. The dissipation rates of azoxystrobin in banana and soil were almost the same. Terminal residues in banana and banana flesh (0.01 mg/kg) were all below the maximum residue limit (2 mg/kg by Codex Alimentarius Commission and China). The results demonstrated that the safety of using azoxystrobin at the recommended agriculture dosage to protect bananas from diseases.     

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.     

Occurrence of phthalic acid esters in Gomti River Sediment, India

Cadmium and lead are important environmental pollutants with high toxicity to animals and human. Soils, though have considerable metal immobilizing capability, can contaminate food chain via plants grown upon them when their built-up occurs to a large extent. Present experiment was carried out with the objective of quantifying the limits of Pb and Cd loading in soil for the purpose of preventing food chain contamination beyond background concentration levels. Two separate sets of pot experiment were carried out for these two heavy metals with graded levels of application doses of Pb at 0.4–150 mg/kg and Cd at 0.02–20 mg/kg to an acidic light textured alluvial soil. Spinach crop was grown for 50 days on these treated soils after a stabilization period of 2 months. Upper limit of background concentration levels (C _ul) of these metals were calculated through statistical approach from the heavy metals concentration values in leaves of spinach crop grown in farmers’ fields. Lead and Cd concentration limits in soil were calculated by dividing C _ul with uptake response slope obtained from the pot experiment. Cumulative loading limits (concentration limits in soil minus contents in uncontaminated soil) for the experimental soil were estimated to be 170 kg Pb/ha and 0.8 kg Cd/ha. Based on certain assumptions on application rate and computed cumulative loading limit values, maximum permissible Pb and Cd concentration values in municipal solid waste (MSW) compost were proposed as 170 mg Pb/kg and 0.8 mg Cd/kg, respectively. In view of these limiting values, about 56% and 47% of the MSW compost samples from different cities are found to contain Pb and Cd in the safe range.     

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 dynamic and residue distribution of flusilazole in mandarin

In this paper, dissipation dynamic and terminal residue of flusilazole in mandarin and soil, as well as residue distribution of flusilazole in mandarin, were studied at three sites in China. Mandarin peel, mandarin pulp, whole mandarin, and soil samples were extracted by acetonitrile, cleaned up with dispersive solid-phase extraction, then analyzed by gas chromatography–mass spectrometry. The dissipation half-lives of flusilazole in mandarin and soil at all three experiment sites were 6.3–8.4 days and 5.5–13.4 days, respectively, with the exception of the soil dissipation at the Hunan site, which showed an increase–decrease process. Flusilazole residue levels in whole mandarin were all below 0.1 mg/kg on 14 days after the last application. Terminal residue study showed that flusilazole was mostly distributed in mandarin peel, which indicates minimal risk for eating mandarin pulp. These results could provide guidance for the proper and safe use of flusilazole on citrus fruits, and further our understanding of pesticide distribution in citrus fruits.     

Comparative assessment of pesticide residues in grain, soil, and water from IPM and non-IPM trials of basmati rice

The integrated pest management (IPM) modules of pesticide schedule on Basmati rice were validated at field experiments conducted in Northern India for consecutive 3 years (2005–2008). The pesticide residues were found below the detectable limit (<0.01–0.001 mg/kg) in soil and irrigation water samples of Kaithal region. In Dehra Dun region of Uttrakhand, the residues of carbendazim in rice grains and soil were detected below <0.01 mg/kg level. In second year experiments (2006–2007), only four non-IPM soil samples indicated the presence of chlorpyrifos and endosulfan in the range of ND <0.001 to 0.07 mg/kg, out of 45 samples analyzed. Carbendazim applied as seed treatment at Dehradun and Kaithal field trials was found below detectable limit in both IPM and non-IPM rice grains (<0.01 mg/kg) and irrigation water (0.01 μl/ml). Chlorpyrifos was detected in five water samples from Kaithal and one from Pant Nagar in the range of 0.003–0.006 μl/L, α- and β-isomer of endosulfan in the range of 0.005–0.03, and 0.005–0.02 μl/ml, respectively, in one sample from Pant Nagar and two from Kaithal, out of a total of 22 samples. In the region of Uttrakhand and Uttar Pradesh during 2007–2008, four non-IPM samples of soil indicated trace levels of endosulfan, out of 16 samples analyzed. The residues were detected below detection limit for carbendazim (<0.01 mg/kg) in soil samples of Dehradun IPM fields and for endosulfan and carbendazim (0.001–0.01 μl/L) in water samples each from IPM and non-IPM fields of Uttar Pradesh. The results of 3-year trials of IPM module indicated basmati rice as safe and economical with pesticide residue-free rice grains.     

Dissipation and residue of triforine in strawberry and soil

Two independent field trials were performed in Guangdong and Hubei, China in 2011 to investigate the dissipation and residue levels of triforine in strawberry and soil. A fast and simple method using gas chromatography with electron capture detector was developed and validated to determine triforine levels in strawberry and soil. The average recovery of triforine in strawberry ranged from 87.46 to 104.32 % with a relative standard deviation (RSD) of 0.72 to 4.54 %; that in soil ranged from 83.82 to 103.01 % with an RSD of 3.89 to 4.36 %. The limit of quantification of the proposed method was 0.01 mg/kg for both strawberry and soil. The results suggest that the triforine dissipation curves followed the first-order kinetic. The half-lives of triforine in strawberry from Guangdong and Hubei were 3.58 and 4.42 days, respectively; those in soil were 3.53 and 4.10 days, respectively. The terminal residues of triforine in strawberry ranged from 0.032 to 0.264 mg/kg at preharvest intervals of 0.5, 1, and 3 days. These values are lower than the maximum residue limit of 1 mg/kg in strawberry set by the Codex Alimentarius Commission.     

Dissipation kinetics and residues of triazolopyrimidine herbicides flumetsulam and florasulam in corn ecosystem

The dynamic and residues of florasulam and flumetsulam in corn field ecosystem were investigated using quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The limits of quantification (LOQs) of the proposed method ranged from 0.005 to 0.01 mg/kg. Mean recoveries and relative standard deviations (RSDs) of the two compounds in all samples at three spiking levels ranged 94–110 % and 2.0–9.2 %, respectively. Florasulam and flumetsulam degradation followed first-order kinetics with half-lives 1.7–2.9 and 3.3–8.7 days in soil and 1.3–1.8 and 0.9–1.7 days in plant, respectively. The residues in all the samples were found to be less than the LOQs at preharvest intervals of 53 and 78 days. The results suggest that the combined use of florasulam and flumetsulam on corn is considered to be safe under the recommended conditions and can be utilized for establishing the maximum residue limit (MRL) of florasulam in corn in China.     

Residue and intake risk assessment of prothioconazole and its metabolite prothioconazole-desthio in wheat field

In the environment, plants and animals in vivo, pesticides can be degraded or metabolized to form transformation products (TPs) or metabolites, which are even more toxic than parent pesticides. Hence, it was necessary to evaluate residue and risk of pesticides and their TPs (or metabolites). Here, a rapid, simple, and reliable method using QuEChERS and LC-MS/MS had been developed for simultaneous analysis of prothioconazole and its toxic metabolite, prothioconazole-desthio, in soil, wheat plant, straw, and grain. The average recoveries of prothioconazole and prothioconazole-desthio in four matrices ranged from 86 to 108% with relative standard deviations (RSDs) of 0.53–11.87% at three spiking levels. The method was successfully applied to investigate the dissipation and terminal residues of the two compounds in wheat field. It was shown that prothioconazole was rapidly degraded to prothioconazole-desthio, with half-lives below 5.82 days. Prothioconazole-desthio was slowly dissipated in soil and plant. The terminal residues of prothioconazole in wheat grain with a pre-harvest interval (PHI) of 21 or 28 days were below the maximum residue limits (MRLs) (0.1 mg/kg, Codex Alimentarius Commission (CAC)). We also evaluated the intake risk of prothioconazole-desthio residues in wheat grain in China. For long-term intake assessment, the hazard quotients (HQ) ranged from 1.30 to 5.95%. For short-term intake assessment, the acute hazard indexes (aHI) ranged from 1.94 to 18.2%. It indicated that the intake risk of prothioconazole-desthio in wheat consumption was acceptable. Thus, the prothioconazole application on wheat with the scientific practices would not pose public health risk.     

Assessment of cadmium content of potato grown in Weining County,Guizhou Province,China

A total of 54 soil and 54 potato samples have been collected from Weining County to evaluate the accumulation of cadmium in potatoes. The concentrations of the total Cd and the available Cd in the soil samples have been detected. The total concentrations of Cd were from 0.41 to 10.0 mg/kg with an average value of 2.60 mg/kg in soil. The concentrations of available Cd in the soil were 0.07 to 3.47 mg/kg with an average value of 0.59 mg/kg. The concentration of the available Cd showed a good linear positive correlation with the total Cd content in the soil. For the 54 potato samples, the Cd concentrations were from 0.023 to 0.18 mg/kg with an average value 0.083 mg/kg (fresh weight).The bioconcentration factor (BCF) values of Cd in potatoes, based on dry weight, were from 0.02 to 0.96 with an average value 0.24. The uptake of cadmium by plants is dependent on various soil and environmental factors. A regression model to predict the concentration of cadmium in Weining potatoes based on soil properties and elevation was developed. The results showed the elevation and the soil pH played an important role and had a negative influence on the uptake of Cd by potato in Weining County. The mean intake of Cd by adults through consumption of potato from Weining would be 5.9 μg/day, and it is well below the provisionally tolerable daily intake for Cd (70 μg/day).     

Characteristics and distribution of analyzed metals in soil profiles in the vicinity of a postflotation waste site in the Bukowno region, Poland

The lead–zinc industry in the Bukowno region of southern Poland has polluted the surface layer of the surrounding soils mainly with lead (Pb), cadmium (Cd), zinc (Zn), arsenic (As), and thallium (Tl). Analysis of six soil profiles, taken on the east side of the postflotation waste site of the Mining and Metallurgical Plants ZGH "Boles?aw" in Bukowno, showed that they were podzol soils, taking form of loose sands with neutral pH and reducing conditions. Concentration of organic matter in the horizons ranged from 2 to 80 %. The main components of the mineral soil were quartz, carbonates, K-feldspars, plagioclases, and micas (sericite). The highest total concentrations of metals were found in the O, A, and B horizons. Over 90 % of the Cd content, 80 % of the Pb content, 60 % of the Zn content, ～60 % of the Tl content, and 20 % of the As content occurred as mobile forms. The corresponding total concentrations were 10 mg/kg Cd, 922 mg/kg Pb, 694 mg/kg Zn, <1 mg/kg Tl, and <5 mg/kg As. This can potentially be taken up from the soil and transported in the trophic chain. Comparing the total metal content with the legal limits in Poland, it is observed, that the investigated soils exceeded the permissible levels of Cd, Pb, and Zn for agricultural soils. Arsenic and Tl are not reflected in the chemical quality of soil classifications.     

Investigation on diazinon and oxydemeton-methyl residues in cucumbers grown in Kerman greenhouses

Pesticides are considered as the most polluting substances. The residue of pesticides in agricultural crops, especially in greenhouse harvests, has been reported critical. Cucumber, considered as a vegetable, is an agricultural product which is commonly found in the Iranian food basket. The current study aims to assess the level of diazinon and oxydemeton-methyl existing in cucumbers sampled from Kerman greenhouses. The pesticide residue was extracted by acetone and dichloromethane. The extracts were cleaned up according to the solid-phase extraction method. The pesticide residues were then determined by capillary gas chromatography with nitrogen-phosphorus detection. The recoveries were 83 and 85 %, the limit of detection was 0.028 and 0.034 mg/kg, and the limits of qualification were 0.093 and 0.113 mg/kg for diazinon and oxydemeton-methyl in cucumber samples, respectively. The median of diazinon residue was detected 0.582 mg/kg, which was 11.64 times the national maximum residue limit (MRL) (0.05 mg/kg), and the median for oxydemeton-methyl was 1.910 mg/kg, being 1.91 times the MRL (1 mg/kg).     

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.     

Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Dissipation of S-metolachlor in plant and soil and effect on enzymatic activities

The present study aimed at evaluating the dissipation of S-metolachlor (S-MET) at three doses in maize growing on diverse physico-chemical properties of soil. The effect of herbicide on dehydrogenase (DHA) and acid phosphatase (ACP) activity was estimated. A modified QuEChERS method using LC-MS/MS has been developed. The limit of quantification (0.001 mg kg^?1) and detection (0.0005 mg kg^?1) were very low for soil and maize samples. The mean recoveries and RSDs for the six spiked levels (0.001–0.5 mg kg^?1) were 91.3 and 5.8%. The biggest differences in concentration of S-MET in maize were observed between the 28th and 63rd days. The dissipation of S-MET in the alkaline soil was the slowest between the 2nd and 7th days, and in the acidic soil between the 5th and 11th days. DT₅₀ of S-MET calculated according to the first-order kinetics model was 11.1–14.7 days (soil) and 9.6–13.9 days (maize). The enzymatic activity of soil was higher in the acidic environment. One observed the significant positive correlation of ACP with pH of soil and contents of potassium and magnesium and negative with contents of phosphorus and organic carbon. The results indicated that at harvest time, the residues of S-MET in maize were well below the safety limit for maize. The findings of this study will foster the research on main parameters influencing the dissipation in maize ecosystems.     

Dissipation and residue behavior of mepiquat on wheat and potato field application

A modified LC-MS method for the analysis of mepiquat residue in wheat, potato, and soil was developed and validated. A hydrophilic interaction liquid chromatographic column has been successfully used to retain and separate the mepiquat. Mepiquat residue dynamics and final residues in supervised field trials at Good Agricultural Practice (GAP) conditions in wheat, potato, and soil were studied. The limits of quantification for mepiquat in all samples were all 0.007 mg kg^?1, which were lower than their maximum residue limits. At fortification levels of 0.04, 0.2, and 2 mg kg^?1 in all samples, recoveries ranged from 77.5 to 116.4 % with relative standard deviations of 0.4–7.9 % (n?=?5). The dissipation half-lives (T _1/2) of mepiquat in soil (wheat), wheat plants, soil (potato), and potato plants were 4.5–6.3, 3.0–5.6, 2.2–4.6, and 2.4–3.2 days, respectively. The final residues of mepiquat were below 0.153 mg kg^?1 in soil (wheat), 0.052–1.900 mg kg^?1 in wheat, below 0.072 mg kg^?1 in soil (potato), and below 1.173 mg kg^?1 in potato at harvest time. Moreover, pesticide risk assessment for all the detected residues was conducted. A maximum 0.0012 % of acceptable daily intake (150 mg kg^?1) for national estimated daily intake indicated low dietary risk of these products.     

The decline and residues of hexaconazole in tomato and soil

The decline and terminal residues of hexaconazole in tomato and soil in open field were studied. Hexaconazole residues were determined by gas chromatography coupled with an electron capture detector. Recoveries were between 89% and 110% with RSD of 2.99–5.88% in tomato and 90–119% with RSD of 1.15–5.76% in soil at spiked levels of 0.01, 0.1, and 1 mg/kg, respectively. The limit of detection of hexaconazole was 6.3 × 10⁻¹² g. The decline rates of hexaconazole were described using first-order kinetics and the mean half-lives of hexaconazole in tomato and soil were 4.3 and 18.1 days, respectively. The terminal residues in tomato at interval of 7 days at the dosage of 150 g.a.i./hm² for three or four times were all below 0.1 mg/kg. This work would be the guidance of establishing the maximum residue limit of hexaconazole in tomato in China.     

Accumulation of heavy metals in Spinacia oleracea irrigated with paper mill effluent and sewage

The present study on heavy metal contamination in soil and their accumulation in edible part (leaves) and roots of Spinacia oleracea (Spinach) on irrigation with paper mill effluent (PME)/sewage revealed that there was significant increase in the nickel (Ni, +227.17 %) content of the soil irrigated with PME, whereas in the soil irrigated with sewage chromium (Cr, +274.84 %), iron (Fe, +149.56 %), and cadmium (Cd, +133.39 %), contents were increased appreciably. The value of enrichment factor (EF) for Ni (3.27) indicated moderate enrichment in PME-irrigated soil. The EF of Fe, zinc (Zn), Cd, and Cr were <2 in PME effluent-irrigated soil which showed deficiency of minimal enrichment. In sewage irrigated soil, EF value for Cr, Fe, and Cd indicated moderate enrichment, while the values for Zn and Ni indicated deficiency of minimal enrichment. Among various metallic concentrations, the maximum concentration of Fe was observed in leaves (400.12?±?11.47 mg/kg) and root (301.41?±?13.14 mg/kg) of S. oleracea after irrigation with PME, whereas the maximum concentrations of Fe was found in leaves (400.49?±?5.97 mg/kg) and root (363.94?±?11.37 mg/kg) of S. oleracea after irrigation with sewage for 60 days. The bioaccumulation factor value was found maximum for Cd (2.23) in the plants irrigated with PME while that of Fe (0.90) in the plants irrigated with sewage. The undiluted use of PME/sewage for irrigation increased the concentration of Cr, Cd, Zn, Ni, and Fe metals which were accumulated in S. oleracea, posing a potential threat to human health from this practice of irrigation.