ABSTRACT
BACKGROUND: False detection of pesticides in agricultural produce may raise serious questions regarding both consumer safety and trade. High levels of delta-hexachlorocyclohexane (δ-HCH; 11.7-22.3 mg/kg) were detected in some tobacco samples in a retention time-based GC analysis. Hence, the selection of an appropriate analytical method is an uncompromisable necessity. OBJECTIVES: This research work aimed to elucidate false detection of pesticides along with identification of coeluting tobacco matrix compounds to understand the dynamics of false detection with an increase in the number of analyzed pesticides and to screen suitable analytical methods. METHODS: Initially, retention time-based GC analysis was performed for monitoring of 10 pesticide residues in tobacco leaf matrix, followed by GC-MS/selected-ion monitoring (SIM) analysis. Then, the total number of pesticides to be analyzed was increased to 47, and residue analysis was performed by involving GC-MS/SIM and multidimensional (MD) GC-MS. RESULTS: A false-positive detection of δ-HCH due to a coeluting tobacco aroma compound, neophytadiene, during residue analysis of 10 pesticides in tobacco (Nicotiana tabacum L.) leaf was observed. This problem was resolved by employing the unique quantifier and qualifier ions in SIM mode. However, with 47 pesticides, neophytadiene completely masked the signal of δ-HCH, which resulted in an impure spectrum of δ-HCH (<30% similarity match) even after application of selective quantifier and qualifier ions. Finally, MDGC-MS analysis could resolve it by chromatographic separation of the said analyte from the coeluting matrix compound. CONCLUSIONS: The findings of this work offer the potential to minimize false reporting of target pesticides to comply with consumer safety and trade standards. HIGHLIGHTS: The study identifies various tobacco matrix compounds coeluting with pesticides during multiresidue analysis. Neophytadiene, a tobacco aroma compound, resulted in false-positive detection of δ-HCH. The MDGC-MS could be effectively used as a confirmatory analysis tool for reliable detection of pesticide residue in tobacco leaf matrix.
Subject(s)
Lobelia , Pesticide Residues , Pesticides , Gas Chromatography-Mass Spectrometry , Pesticide Residues/analysis , Pesticides/analysis , NicotianaABSTRACT
The study reports the effect of Inderprastha (IP) and Badarpur (BP) fly ashes on degradation of metolachlor and atrazine in Inceptisol and Alfisol soils. Metolachlor dissipated at faster rate in Alfisol (t1/2 8.2-8.6 days) than in Inceptisol (t1/2 13.2-14.3 days). The fly ashes enhanced the persistence of metolachlor in both the soils; however, the extent of effect was more in Inceptisol (t1/2 16.6-33.8 days) than Alfisol (t1/2 8.4-12 days) and effect increased with fly ash dose. 2-Ethyl-6-methylacetanilide was detected as the only metabolite of metolachlor. Atrazine was more persistent in flooded soils (t1/2 10.8-20.3 days) than nonflooded soils (t1/2 3.7-12.6 days) and fly ash increased its persistence, but effect was more pronounced in the flooded Inceptisol (t1/2 23.7-31 days) and nonflooded Alfisol (t1/2 6.3-10.1 days). Increased herbicide sorption in the fly ash-amended soils might have contributed to the increased pesticide persistence. The IP fly ash inhibited microbial biomass carbon at 5 % amendment levels in both the soils, while BP fly ash slightly increased microbial biomass carbon (MBC) content. Dehydrogenase activity was inhibited by both fly ashes in both the soils with maximum inhibition observed in the IP fly ash-amended Alfisol. No significant effect of fly ash amendment was observed on the fluorescein diacetate activity.
Subject(s)
Acetamides/analysis , Atrazine/analysis , Coal Ash , Environmental Monitoring/methods , Herbicides/analysis , Soil Microbiology , Soil Pollutants/analysis , Biodegradation, Environmental , Biomass , India , Soil/chemistry , Soil/standardsABSTRACT
Public exposure to pesticide residues through the main/side-stream smoke of tobacco (Nicotiana tabacum L.) is an international concern. This article reports optimization and validation of large-scale multiresidue analysis methods involving low pressure and traditional gas chromatography tandem mass spectrometry in compliance with the guidance residue levels (GRLs) of Cooperative Centre for Scientific Research Relative to Tobacco (CORESTA). Analysis by low pressure GC-MS/MS offered three times rapid turn around time over the traditional GC-MS/MS with limits of quantifications (LOQs) less than 2µg/L for all the 259 test compounds and the recoveries in the range of 70-118% (±20%) at 10 and 20µg/kg levels of fortification.
Subject(s)
Nicotiana/chemistry , Pesticide Residues/analysis , Smoke/analysis , Gas Chromatography-Mass Spectrometry/methods , Tandem Mass Spectrometry/methodsABSTRACT
Using 108 petroleum contaminated soil samples, this pilot study proposed a new analytical approach of combining visible near-infrared diffuse reflectance spectroscopy (VisNIR DRS) and portable X-ray fluorescence spectrometry (PXRF) for rapid and improved quantification of soil petroleum contamination. Results indicated that an advanced fused model where VisNIR DRS spectra-based penalized spline regression (PSR) was used to predict total petroleum hydrocarbon followed by PXRF elemental data-based random forest regression was used to model the PSR residuals, it outperformed (R(2)=0.78, residual prediction deviation (RPD)=2.19) all other models tested, even producing better generalization than using VisNIR DRS alone (RPD's of 1.64, 1.86, and 1.96 for random forest, penalized spline regression, and partial least squares regression, respectively). Additionally, unsupervised principal component analysis using the PXRF+VisNIR DRS system qualitatively separated contaminated soils from control samples. CAPSULE: Fusion of PXRF elemental data and VisNIR derivative spectra produced an optimized model for total petroleum hydrocarbon quantification in soils.
Subject(s)
Petroleum Pollution/analysis , Petroleum/analysis , Soil Pollutants/analysis , Soil/chemistry , Environmental Monitoring/methods , Least-Squares Analysis , Petroleum Pollution/statistics & numerical data , Principal Component AnalysisABSTRACT
The present study evaluated rice husk ash (RHA) as an adsorbent for simultaneous removal of a mixture of seven different pesticides (alachlor, metolachlor, chlorpyriphos, fipronil, α-endosulfan, ß-endosulfan, and p,p'-DDT) and two metabolites (p,p'-DDE and endosulfan sulfate) from water. The adsorbent RHA was prepared in the laboratory and characterized by techniques such as X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy/energy-dispersive X-ray spectrometry. Adsorption kinetics were well described by the pseudo-second-order kinetic model. The Freundlich isotherm model fitted the equilibrium data better than the Langmuir model, and the maximum sorption capacity varied from 0.078 to 0.166 mg/g. The column elution studies showed that 10 L of mixed pesticide-contaminated water (0.05 mg/L) can be treated with only 10 g of RHA at a removal efficiency of 90%. The results implied that RHA can be used as a low-cost, easily available, and efficient adsorbent for the simultaneous removal of pesticides from contaminated water.
Subject(s)
Oryza/chemistry , Pesticides/chemistry , Water Pollutants, Chemical/chemistry , Adsorption , Microscopy, Electron, ScanningABSTRACT
A selective and sensitive multiresidue analysis method, comprising 4 7pesticides, was developed and validated in tobacco matrix. The optimized sample preparation procedure in combination with gas chromatography mass spectrometry in selected-ion-monitoring (GC-MS/SIM) mode offered limits of detection (LOD) and quantification (LOQ) in the range of 3-5 and 7.5-15ng/g, respectively, with recoveries between 70 and 119% at 50-100ng/g fortifications. In comparison to the modified QuEChERS (Quick-Easy-Cheap-Effective-Rugged-Safe method: 2g tobacco+10ml water+10ml acetonitrile, 30min vortexing, followed by dispersive solid phase extraction cleanup), the method performed better in minimizing matrix co-extractives e.g. nicotine and megastigmatrienone. Ambiguity in analysis due to co-elution of target analytes (e.g. transfluthrin-heptachlor) and with matrix co-extractives (e.g. δ-HCH-neophytadiene, 2,4-DDE-linolenic acid) could be resolved by selective multi-dimensional (MD)GC heart-cuts. The method holds promise in routine analysis owing to noticeable efficiency of 27 samples/person/day.
Subject(s)
Gas Chromatography-Mass Spectrometry/methods , Nicotiana/chemistry , Pesticides/analysis , Solid Phase Extraction/methods , Solvents/chemistryABSTRACT
Presence of pesticide residues in tobacco increases health risk of both active and passive smokers, apart from the imminent potential health problems associated with it. Thus, monitoring of pesticide residue is an important issue in terms of formulating stringent policies, enabling global trade and safeguarding the consumer's safety. In this study, a gas chromatography-single quadrupole mass spectrometry (GC-MS) method based upon quantifier-qualifier ions (m/z) ratio was employed for detecting and assessing ten organochlorine pesticide residues (α-HCH, ß-HCH, γ-HCH, δ-HCH, 2,4-DDT, 4,4-DDT, endrin, α-endosulfan, ß-endosulfan and endosulfan sulphate) in 152 flue-cured (FC) tobacco leave samples from two major tobacco growing states, Karnataka and Andhra Pradesh, of India. In the majority of samples, pesticide residue levels were below the limit of quantification (LOQ). In few samples, pesticide residues were detected and they found to comply with the guidance residue levels (GRL) specifications of the Cooperation Center for Scientific Research Relative to Tobacco (CORESTA). Detection of the phase out pesticides like DDT/HCH might be due to transfer of persistent residues from the environmental components to the plant. This is the first report on these ten organochlorine pesticide residues in Indian FC tobacco.
Subject(s)
Environmental Monitoring , Hydrocarbons, Chlorinated/analysis , Nicotiana/chemistry , Pesticide Residues/analysis , Endosulfan/analogs & derivatives , Endosulfan/analysis , Gas Chromatography-Mass Spectrometry/methods , Hexachlorocyclohexane/analysis , India , Pesticides/analysisABSTRACT
Application of low cost amendment for pesticide retention in soil is an important area of research in environmental sciences. The present study reports the potential of coal fly ash (Inderprastha and Badarpur), a waste from thermal power stations, for retaining soil applied metolachlor and atrazine within the application zone. Both the fly ashes were highly effective in reducing the leaching losses of metolachlor and atrazine and at 2% and 5% fly ash amendment levels the herbicides were retained in the top 15 cm profile of the column. However, fly ashes varied in their capacity in reducing the downward mobility of herbicides, as the Inderprastha fly ash was more effective than the Badarpur fly ash. Although fly ash contained heavy metals like Cr, Cu or Pb, but they were not detected in the leachate. Also, concentration of other metals like Zn, Mn and Fe in leachate decreased after fly ash amendment. Results of this study have implications in reducing the leaching losses of these herbicides in agricultural soils.
Subject(s)
Acetamides/chemistry , Atrazine/chemistry , Coal Ash/chemistry , Soil/chemistry , Agriculture , Herbicides/chemistry , Metals, Heavy/analysisABSTRACT
BACKGROUND: Azoxystrobin [methyl (E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate], a strobilurin fungicide, is a broad-spectrum, systemic and soil-applied fungicide. Azoxystrobin has been registered for rice cultivation in India, but no information is available on its leaching behaviour in Indian soils. Therefore, leaching behaviour of azoxystrobin was studied in packed and intact soil columns under different irrigation regimes. RESULTS: Azoxystrobin did not leach out of the 300 mm long columns after 126 and 362 mm rainfall. After percolating water equivalent to 362 mm rainfall, azoxystrobin leached down to 10-15 cm (packed columns) and 15-20 cm (intact columns) depth. Azoxystrobin was not detected in the leachate from the packed column leached with 94.5 mL water every week (140 mm rainfall per month) during the 28 weeks of the study period. However, azoxystrobin acid, formed by azoxystrobin degradation, was detected in the leachate after 18 weeks. At the end of the study, azoxystrobin had leached down to 5-10 cm depth, and only 60% of initially applied azoxystrobin was recovered from the soil. CONCLUSION: The results indicate that azoxystrobin is fairly immobile in sandy loam soil, but azoxystrobin acid, a major metabolite of azoxystrobin, is quite mobile and may pose a threat of soil and groundwater contamination.
Subject(s)
Fungicides, Industrial/chemistry , Methacrylates/chemistry , Pyrimidines/chemistry , Soil/analysis , Strobilurins , Water MovementsABSTRACT
Information on pesticide degradation and factors influencing are important in predicting the levels of pesticide remaining in soils and allow assessment of potential risk associated with exposure. The present study reports the sorption and degradation of azoxystrobin [methyl (E)-2-{2-(6-(2-cyanophenoxy)pyrimidin-4-yloxy)phenyl}-3-methoxyacrylate] in a sandy loam soil. The fungicide was moderately sorbed, and the Freundlich adsorption parameter K(f) (1/n) values in natural and 5% compost-amended soils were 9.31 and 13.72, respectively. Sorption showed hysteresis with 32.5 and 14.7% of sorbed fungicide desorbed from the natural and 5% compost-amended soils, respectively. Azoxystrobin was more persistent in the aerobic soil than the anaerobic soil with half-life values of 107.47 and 62.69 days, respectively. Amendment of compost (5%) to the soil enhanced the degradation of fungicide, and the respective half-life values in aerobic and anaerobic soils were 73.39 and 38.58 days, respectively. Azoxystrobin acid was recovered as the only metabolite of azoxystrobin degradation in soils. Both sunlight and UV light affected the persistence of azoxystrobin with fungicide degraded at a faster rate in UV light than in sunlight. Soil acts as a screen and slows the fungicide degradation under sunlight and UV light.