Untying arsenite tolerance mechanisms in contrasting maize genotypes attributed to NIPs-mediated controlled influx and root-to-shoot translocation, redox homeostasis and phytochelatin-mediated detoxification pathway.

Contamination of ground water and soil with toxic metalloids like arsenic (As) poses a serious hazard to the global agricultural food production. One of the best ways to restrict entry of As into the food chain is selection of germplasms which accrue extremely low level of As in grains. Here, we screened diverse maize genotypes under high arsenite (100 µM AsIII) stress and identified PMI-PV-9 and PMI-PV-3 as AsIII-tolerant and -sensitive maize genotype respectively. Expression of genes associated with As uptake, vacuolar sequestration, biosynthesis of phytochelatins, root-to-shoot translocation, in vivo ROS generation, fine tuning of antioxidant defense system, DNA and membrane damage, H2O2 and superoxide anion (O2•-) levels were compared among the selected genotypes. PMI-PV-9 plants performed much better than PMI-PV-3 in terms of plant growth with no visible symptom of As toxicity. Susceptibility of PMI-PV-3 to AsIII stress may be attributed to comparatively low expression of genes involved in phytochelatins (PCs) biosynthesis. Concomitant decrease in ABCC1 expression might be another key factor for futile sequestration of AsIII into root vacuoles. Moreover, up-regulation of ZmNIP3;1 might contribute in high root-to-leaf As translocation. Substantial spike in H2O2, O2•- and MDA levels indicates that PMI-PV-3 plants have experienced more oxidative stress than PMI-PV-9 plants. Appearance of prominent deep brown and dark blue spots/ stripes on leaves as revealed after DAB and NBT staining respectively suggest severe oxidative burst in PMI-PV-3 plants. Marked reduction in DHAR and MDAR activity rendered PMI-PV-3 cells to recycle ascorbate pool ineffectively, which might have exacerbated their susceptibility to AsIII stress. In a nutshell, incompetent PCs mediated detoxification system and disruption of cellular redox homeostasis owing to feeble antioxidant defence system resulting oxidative burst might be the prime reasons behind reduced performance of PMI-PV-3 plants under AsIII stress.

Bioaccumulation of Potentially Toxic Elements in Commercially Important Food Fish Species from Lower Gangetic Stretch: Food Security and Human Health Risk Assessment.

Ganga river is the inhabitant of more than 190 fish species and important river system of India. Potentially toxic elements (PTEs) in the Gangetic riverine ecosystem are a hot environmental issue. A detailed evaluation of PTEs bioaccumulation in Gangetic fishes is required to safeguard human health. The present study investigated the bioaccumulation of PTEs (Cd, Co, Cr, Cu, Li, Ni, Pb, Se, Zn, and Mn) within 12 economic fish species (n = 72) collected from the lower Gangetic stretch. The mean concentrations of PTEs followed the order Zn > Cu > Mn > Ni > Se > Cr > Pb > Co ~ Li > Cd. Li and Se bioaccumulation were studied first time from Gangetic fishes. Results demonstrated that all the selected PTEs were below the maximum permissible limit recommended by reference standards except for Zn in L. catla and L. rohita. For all PTEs, the metal pollution index (MPI), hazard quotient (THQ), and hazard index (HI) were < 1, indicating that these PTEs do not pose a health risk to the public through the dietary intake of fish in this study area. All studied fish were acceptable in terms of carcinogenic risk (CR) from exposure to Cd, Cr, and Pb. Multivariate statistical analysis suggests that inter-correlated metals have similar dispersion properties and bioaccumulation homology within the body. This study provides a scientific basis for food safety assessment and continuous monitoring of PTEs in Gangetic fishes is suggested in the future to safeguard human health.

Determination of quizalofop-p-ethyl in onion: residual dissipation pattern, weed control efficiency, and food safety assessment under field conditions.

Monitoring pesticide residue levels becomes crucial to maintain quality and guarantee food safety as the consumption of onion green leaves and immature and mature bulbs (either raw or processed) rises. A field experiment was conducted for two consecutive seasons with quizalofop-p-ethyl (5% EC) at 50 and 100 g a.i. ha-1 to evaluate weed control efficiency and to determine terminal residues. Post-emergence application of fop herbicide at 100 g a.i. ha-1 kept the weed density and dry weight reasonably at a lower level and enhanced the productivity of onion with higher economic returns. A rapid, sensitive, and analytical method was developed using high-performance liquid chromatography (HPLC) with excellent linearity (r2 > 0.99). The limit of quantification for quizalofop-p-ethyl was established at 0.04 mg kg-1 with signal to noise (S/N) ratio ≥ 10. The method was successfully applied and initial quantified residues were in the range of 2.5-4.4 mg kg-1 irrespective of seasons and doses. Finally, the presence of targeted herbicide residues in harvested samples was confirmed by liquid chromatography tandem mass spectrometry (LC-MS/MS) under optimized operating conditions. Dietary risk assessment assured harvested onions were safe for consumption at the recommended dose. It also can be concluded that quizalofop ethyl did not adversely influence soil micro-organisms at standard rates of application.

Integrated biomarker approach strongly explaining in vivo sub-lethal acute toxicity of butachlor on Labeo rohita.

Butachlor herbicide belongs to the family of chloroacetanilide group, widely used for control of grass and broadleaf weeds in paddy fields however, its repeated application may result in aquatic pollution. Butachlor residue has been detected in aquatic environments, which may produce toxic effects on non-target organisms including fish. Keeping this in mind, the present study was designed to estimate the LC50 of butachlor (Shaktiman®), and to evaluate the sub-lethal toxicity at two concentrations (12.42 µg L-1 and 62.10 µg L-1) in Labeo rohita for a period of 24, 48, and 72 h. Fish exposed to butachlor reduced the counts of red blood cells (RBC), haemoglobin (HGB), hematocrit (HCT), and white blood cells (WBC). A significant (p < 0.05) increase in the antioxidant enzyme (superoxide dismutase-SOD, glutathione-s-transferase-GST), and hepatic enzyme (glutamate-oxaloacetate transaminase-GOT, glutamate-pyruvate transaminase-GPT) were noticed in butachlor exposed fish. Heat shock protein 70 (HSP70) and HSP90 in gill; cortisol, protein, albumin, globulin, and triglyceride in serum were increased upon exposure of butachlor. On the contrary, complement 3 (C3) and immunoglobulin (IgM) in serum was found to be decreased compared to control fish. The findings thus suggest that the fish upon exposure to butachlor disrupts the biomarkers which ultimately leads to growth retardation in fish.

Impact of soil type and temperature on dissipation dynamics of a new readymix formulation of halauxifen-methyl + pyroxsulam.

The persistence and dissipation of a new readymix formulation of halauxifen-methyl + pyroxsulam was investigated in three soils viz. red lateritic (Soil A), coastal saline (Soil B) and black soil (Soil C) under three incubation temperatures (20, 30 and 40° C). Soil samples were fortified at 1.0 (T1) and 2.0 (T2) mg kg- 1 doses separately for both compounds. The analytical methods showed satisfactory mean recovery, precision and linearity and therefore accepted for analysis. Both molecules followed single first-order kinetics. A significant influence of soil type on the persistence of both herbicides was observed. The order of stability of halauxifen-methyl was Soil A > B > C and for pyroxsulam was Soil B > C > A. Besides, a faster rate of dissipation of halauxifen-methyl and pyroxsulam was recorded at elevated temperatures, regardless of soil type. This research will help to understand the effect of temperature on the fate of the herbicide mixture in soils of diverse agro-climatic regions.

Assessment of the effect of sub-lethal acute toxicity of Emamectin benzoate in Labeo rohita using multiple biomarker approach.

Emamectin benzoate (EMB) is a potent neurotoxin agent, widely used for ectoparasites control in aquaculture, but their detailed toxicological implications in Labeo rohita are unknown. Thus, this study was conceptualized to determine the LC50 and to investigate the effects of two sub-lethal concentrations 1/50th of 96 h LC50 (1.82 µgL-1) and 1/10thof 96 h LC50 (9.1 µgL-1) on hemato-immunological and biochemical responses in L. rohita (mean weight 25.54 ± 2.3 g and length 10.35 ± 2.4 cm) for a period of 24 h, 48 h, and 72 h. LC50 of EMB were 163 µgL-1, 112 µgL-1, 99 µgL-1 and 91 µgL-1 at 24 h, 48 h, 72 h, and 96 h respectively. The safe limit at 96 h LC50 of EMB was 2.30 µgL-1. In EMB treated fish, red blood cells, white blood cells, hemoglobin, and hematocrit counts were reduced (p < 0.05) significantly. Superoxide dismutase (SOD) activity in the liver and kidney declined (p < 0.05) at 72 h while in gill and muscle the activity increased significantly. Glutathione-s-transferase (GST) activity in the liver, gill, and kidney increased (p < 0.05) while muscle decreased significantly. Catalase (CAT) activity in liver, gill, and muscle decreased while in kidney increases. Glutamic-oxaloacetic acid transaminase (GOT) activity and Glutamate pyruvate transaminase (GPT) activity were increased in liver, kidney, and muscle tissue. The change in serum triglycerides, serum protein level was noticed. The level of cortisol, heat shock protein 70 (HSP70), and HSP90 increased (p < 0.05) while the immunological responses like immunoglobulin M (IgM) and complement 3(C3) activity decreased (p < 0.05) in EMB exposed fish. Thus, EMB exposure at two sub-lethal concentrations in L. rohita induces several hemato-immuno, and biochemical alterations in blood, serum, and different organs. The overall result of the present study indicated that EMB is toxic to fish even for a short-term exposure and low doses, and therefore utmost caution should be taken to prevent their drainage into water bodies.

Effect of Soil Type and Temperature on Persistence and Dissipation Kinetics of a New Readymix Formulation of Fomesafen + Quizalofop-ethyl.

The research portrays the fate of a new herbicide mixture of fomesafen and quizalofop-ethyl. The soil samples viz. red lateritic soil (A), coastal saline soil (B) and black soil (C) were fortified separately for fomesafen and quizalofop-ethyl at 0.5 (T1) and 1.0 mg kg-1 (T2) doses and incubated at 20, 30 and 40°C. A satisfactory mean recovery, precision and linearity proved that the methods were accurate. Both the herbicides followed first + first order kinetics. Higher persistence of fomesafen was observed in Soil C than Soil B and Soil A with 22.38-53.75 days half-life, whereas quizalofop-ethyl showed higher stability in Soil A than Soils B and C with half-life of 0.93-12.07 days. Both compounds showed faster rates of dissipation at increased temperature, irrespective of soil type. The current study will help to predict the effect of temperature on the dissipation of herbicides in different soil under real field scenario.

Effect of pH on the Hydrolytic Transformation of a New Mixture Formulation of Fomesafen and Quizalofop-ethyl in Water.

A hydrolytic transformation study was conducted in water of pH 4.0, 7.0 and 9.2 to evaluate the effect of pH on persistence of a new readymix formulation of fomesafen and quizalofop-ethyl. The water samples were fortified at 0.5 and 1 µg mL-1 levels and analysed at 0 (2 h), 1, 3, 7, 15, 30, 60, 90, 120, 150 days interval. Both the analytical methods were validated following SANTE guideline and found accurate based on average recovery of 80-100%, Relative standard deviation (RSD) < 20% and Coefficient of Determination (R2) 0.99. The dissipation of both the molecules was pH dependent and followed first order kinetics. Higher persistence of fomesafen was observed in alkaline pH as compared to neutral and acidic pH with half-life of 41.56-63.24 days, whereas higher stability of quizalofop-ethyl was observed in the water of acidic pH followed by neutral and alkaline pH with half-life of 1.26-8.09 days.

Validation of a Multiresidue Method for the Analysis of 86 Multiclass Pesticides in Litchi Fruit by Gas Chromatography-Tandem Mass Spectrometry.

BACKGROUND: Although India is an important producer of litchi fruit, there is hardly any validated method available for its pesticide residue analysis. This strongly warrants the need to standardize a simple multiresidue analytical method for efficient analysis of multiclass pesticides with specificity, sensitivity, and accuracy in a single chromatographic run in combination with MS determination. OBJECTIVE: The aim of this study was to develop and validate a rapid ethyl-acetate-based sample preparation method for a simultaneous determination of 86 pesticides in litchi fruit by using GC-tandem MS. METHODS: The method involved ethyl acetate as an extracting solvent and a combined salt system comprising sodium chloride and sodium sulphate for the organic layer separation. To obtain satisfactory recovery percentage of each pesticide studied here, this combination was selected for further validation based on selectivity, sensitivity, linearity, precision, and accuracy values. RESULTS: The correlation coefficient (r2) of studied pesticides ranged between 0.97 and 0.99 at six concentration levels from 5 to 250 ng/mL. Furthermore, the average recovery values were within 70 and 120%, with repeatability relative SD below 20% for all 86 pesticides at the LOQ level and with an appreciable Horwitz ratio distribution that ranged between 0.5 and 2. CONCLUSIONS: All data demonstrate that the proposed method is adequately linear, accurate, and repeatable. Therefore, it can be widely used in commercial laboratories for analyzing pesticide residues for both domestic and export purposes. The method is in support of protecting consumer health. HIGHLIGHTS: A large-scale multiresidue method is reported for simultaneous analysis of a wide range of pesticides in litchi. The method complies with the regulatory requirements in terms of sensitivity for maximum residue limit compliance. The performance of the method complied with the SANTE guidelines of analytical QC.

Effect of pH on the Transformation of a New Readymix Formulation of the Herbicides Bispyribac Sodium and Metamifop in Water.

A laboratory experiment was conducted to investigate the effect of pH on the persistence and the dissipation of the new readymix formulation of bispyribac sodium and metamifop. The experiment was conducted in water of three different pH viz. 4.0, 7.0 and 9.2. The spiking level of both the compounds in water was 1.0 and 2.0 µg/mL. The residues were extracted by a simple, quick and reliable method and quantified by liquid chromatography tandem mass spectrometry (LC-MS/MS). The method was justified based on the recovery study, which was > 85%. The dissipation of both compounds followed first order kinetics. The half-life values ranged between 19.86-36.29 and 9.92-19.69 days for bispyribac sodium and metamifop, respectively. The pH of water has a prominent effect on degradation of both the compounds. The rate of dissipation of both the compounds was highest in water of acidic pH followed by neutral and alkaline pH.

Persistence of chlorfluazuron in cabbage under different agro-climatic conditions of India and its risk assessment.

A multilocational field trial was conducted at 4 locations in India-Rajasthan, Gujarat, Madhya Pradesh, and West Bengal-to determine the persistence in cabbage of chlorfluazuron applied twice at 75 and 150 g active ingredient ha-1 . Cabbage head samples were collected from each replicated plot on 0 (2 h after spraying), 1, 3, 5, 7, 10, and 15 d after final insecticide application, including an untreated control. Chlorfluazuron residue in cabbage and field soil was estimated by high-performance liquid chromatography using a photo diode array detector. The limit of determination and limit of quantification of the method were recorded as 0.05 and 0.10 µg g-1 , respectively. Results revealed that chlorfluazuron dissipated linearly with progress of time, following first-order kinetics. The mean (± standard deviation) half-life value of chlorfluazuron in cabbage was found to be 7.18 ± 0.71 d, considering different locations and treatments. The residue was below the level of quantification in the harvested cabbage and soil samples. Harvesting cabbage in the experimental location, at least on day 7, after 2 applications of chlorfluazuron at the recommended dose, may not pose any ill effect for Indian adults. Environ Toxicol Chem 2017;36:3028-3033. © 2017 SETAC.

Photodegradation of Oryzalin in aqueous isopropanol and acetonitrile.

The phototransformation of Oryzalin was studied under UV light (λmax ≥ 290 nm) and sunlight (λmax ≥ 250 nm) in aqueous isopropanol and acetonitrile solution in absence and presence of TiO2 as sensitizer. The rate of photodegradation of Oryzalin in different solvent system followed first-order kinetics, and calculated half-lives were found to be in the range of 23.52-53.75 h for UV light and 41.23-61.43 h for sunlight. From this study, total 12 photoproducts were identified and characterized on the basis of column chromatography and Q-Tof micromass spectral data. The plausible mechanism of phototransformation involved was hydrolysis, breaking of sulfonic bond, and loss of amino and sulfonic acid group.

ß-aminobutyric acid mediated drought stress alleviation in maize (Zea mays L.).

The present study highlights the role of ß-aminobutyric acid (BABA) in alleviating drought stress effects in maize (Zea mays L.). Chemical priming was imposed by pretreating 1-week-old plants with 600 µM BABA prior to applying drought stress. Specific activities of key antioxidant enzymes and metabolites (ascorbate and glutathione) levels of ascorbate-glutathione cycle were studied to unravel the priming-induced modulation of plant defense system. Furthermore, changes in endogenous ABA and JA concentrations as well as mRNA expressions of key genes involved in their respective biosynthesis pathways were monitored in BABA-primed (BABA+) and non-primed (BABA-) leaves of drought-challenged plants to better understand the mechanistic insights into the BABA-induced hormonal regulation of plant response to water-deficit stress. Accelerated stomatal closure, high relative water content, and less membrane damage were observed in BABA-primed leaves under water-deficit condition. Elevated APX and SOD activity in non-primed leaves found to be insufficient to scavenge all H2O2 and O2 (·-) resulting in oxidative burst as evident after histochemical staining with NBT and DAB. A higher proline accumulation in non-primed leaves also does not give much protection against drought stress. Increased GR activity supported with the enhanced mRNA and protein expressions might help the BABA-primed plants to maintain a high GSH pool essential for sustaining balanced redox status to counter drought-induced oxidative stress damages. Hormonal analysis suggests that in maize, BABA-potentiated drought tolerance is primarily mediated through JA-dependent pathway by the activation of antioxidant defense systems while ABA biosynthesis pathway also plays an important role in fine-tuning of drought stress response.

Persistence and risk assessment of spiromesifen on tomato in India: a multilocational study.

Supervised field trials were conducted at four different agro-climatic locations of India to evaluate the dissipation pattern and risk assessment of spiromesifen on tomato. Spiromesifen 240 SC was sprayed on tomato at 150 and 300 g a.i. ha(-1). Samples of tomato fruits were drawn at 0, 1, 3, 5, 7, 10 and 15 days after treatment and soil at 15 days after treatment. Quantification of residues was done on gas chromatograph-mass spectrophotometer in selective ion monitoring mode in the mass range of 271-274 (m/z). The limit of quantification of the method was found to be 0.05 mg kg(-1), while the limit of determination was 0.015 mg kg(-1). Residues were found below the LOQ of 0.05 mg kg(-1) in 10 days at both the doses of application at all the locations. Spiromesifen dissipated with a half-life of 0.93-1.38 days at the recommended rate of application and 1.04-1.34 days at the double the rate of application. Residues of spiromesifen in soil were detectable level (<0.05 mg kg(-1)) after 15 days of treatment. A preharvest interval (PHI) of 1 day has been recommended on tomato on the basis of data generated under All India Network Project on Pesticide Residues. Spiromesifen 240 SC has been registered for its use on tomato by Central Insecticide Board and Registration Committee, Ministry of Agriculture, Government of India. The maximum residue limit (MRL) of spiromesifen on tomato has been fixed by Food Safety Standard Authority of India, Ministry of Health and Family Welfare, Government of India as 0.3 µg/g after its risk assessment.

A comparative study on the persistence of imidacloprid and beta-cyfluthrin in vegetables.

In an effort to compare the persistence of imidacloprid and beta-cyfluthrin, when applied through a ready mix formulation, Solomon 300 OD @ 200 and 400 mL ha(-1) in the fruits of brinjal, tomato and okra, the present study has been made. The study indicated that the dissipation of these insecticides irrespective of fruits followed concentration dependent first order kinetics. The degradation constant and half live value of beta-cyfluthrin varies between -0.287 and -0.642 day(-1) and 1.07 and 2.41 days while that of imidacloprid between -0.21 and -0.34 day(-1) and 1.98 and 3.30 days respectively suggesting that the persistence of beta-cyfluthrin is lower than that of imidacloprid in fruits of these vegetables. Moreover, the persistence of these insecticides when compared between different fruits, it is highest in brinjal followed by tomato and least in okra, a probable clue of which has been proposed based on the non-enzymatic antioxidant content of the fruits.

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.