Regulatory landscape of risk assessment of pesticide residues in processed foods in India: a perspective.

In India, the levels of pesticide residues in Raw Agricultural Commodities (RAC) are being subjected to adequate legal regulations, and the health-risks associated with them are determined from time to time adhering to global standards. Since RACs are generally consumed by humans as the processed foods (PF), it is imperative to monitor the levels of pesticide residues in them in order to approach a realistic analysis of dietary exposure and concomitant health risk assessment. In India, production and consumption of PFs have a rising trend and hence it is indispensable to monitor the residue levels of pesticides in largely consumed PFs. Depending on the processing methods and physicochemical properties of pesticides, the residue levels may decrease or increase in a PF when compared to the corresponding RAC. While obtaining data on processing factors (Pf), it is pragmatic to focus on those situations in which the residues get concentrated following the processing step. Currently, regulatory agencies of several countries and the CODEX have determined the levels of pesticide residues in processed agriculture commodities, arrived at the Pfs, and fixed the maximum residue levels. Since consumption of PFs in India has tremendously increased in recent times and there is paucity of data about their health risks/benefits, it is imminent to deliberate on the complexities associated with the issues of adopting the Pfs generated by other regulatory agencies and subsequently examine the possibilities of generating the required data on Pfs on a priority basis to enable a comprehensive risk assessment.

Bioefficacy, residue dynamics and dietary risk assessment of gibberellic acid in improving the potential yield of tomato (Solanum lycopersicum L.).

The increasing use of gibberellic acid (GA3) to promote fruit growth and yield has necessitated research into its trace level determination and estimation in harvested product. The phytohormone has increased the tomato yield (tonne ha-1) up to 24.7% with uniform fruit shape, size colour and lustre. A fast, simple, high-throughput analytical method was standardised based on electrospray ionisation - liquid chromatography-tandem mass spectrometry (LC-MS/MS). The samples were extracted using acidified (1% formic acid) methanol. The method was validated as per the SANTE/12682/2019 guidelines. The limits of detection (LOD) and quantification (LOQ) were 0.01 and 0.05 mg kg-1. The average recoveries at LOQ and higher levels were in the range of 86-108% with relative standard deviation (RSD) < 20%. The validated method was successfully applied under field condition by following first-order kinetics with half-lives (T1/2) 1.76 days (recommended dose) and 1.99 days (double dose). The estimated pre-harvest intervals (PHIs) were 6 days (recommended dose) and 8 days (double dose). Studies on dietary risk assessment concluded that even after spray of GA3 at recommended dose, the harvested produce (tomato) could be consumed safely.

Amelioration of diabetic nephropathy using pomegranate peel extract-stabilized gold nanoparticles: assessment of NF-κB and Nrf2 signaling system.

BACKGROUND: Diabetic nephropathy (DN), an end-stage renal disorder, has posed a menace to humankind globally, because of its complex nature and poorly understandable intricate mechanism. In recent times, functional foods as potential health benefits have been gaining attention of consumers and researchers alike. Rich in antioxidants, the peel and seed of pomegranate have previously demonstrated protection against oxidative-stress-related diseases, including cardiovascular disorders, diabetes, and cancer. PURPOSE: This study was designed to investigate the ameliorative role of pomegranate peel extract-stabilized gold nanoparticle (PPE-AuNP) on streptozotocin (STZ)-induced DN in an experimental murine model. METHODS: Following the reduction methods, AuNP was prepared using the pomegranate peel ellagitannins and characterized by particle size, physical appearance, and morphological architecture. Modulatory potential of PPE-AuNP was examined through the plethora of biochemical and high throughput techniques, flow cytometry, immunoblotting, and immunofluorescence. RESULTS: The animals treated with PPE-AuNP markedly reduced the fasting blood glucose, renal toxicity indices, and serum TC and TG in a hyperglycemic condition. As evident from an increased level of plasma insulin level, PPE-AuNP normalized the STZ-induced pancreatic ß-cell dysfunction. The STZ-mediated suppression of endogenous antioxidant response was restored by the PPE-AuNP treatment, which reduced the generation of LPO as well as iROS. Furthermore, the hyperglycemia-mediated augmentation of protein glycation, followed by the NOX4/p-47phox activation, diminished with the application of PPE-AuNP. The histological and immunohistochemical findings showed the protective efficacy of PPE-AuNP in reducing STZ-induced glomerular sclerosis and renal fibrosis. In addition, it reduced proinflammatory burden through the modulation of the MAPK/NF-κB/STAT3/cytokine axis. Simultaneously, PI3K/AKT-guided Nrf2 activation was evident upon the PPE-AuNP application, which enhanced the antioxidant response and maintained hyperglycemic homeostasis. CONCLUSION: The findings indicate that the use of PPE-AuNPs might act as an economic therapeutic remedy for alleviating DN.

Development of a District-Level Programmatic Assessment Tool for Risk of Measles Virus Transmission.

All six World Health Organization (WHO) regions have now set goals for measles elimination by or before 2020. To prioritize measles elimination efforts and use available resources efficiently, there is a need to identify at-risk areas that are offtrack from meeting performance targets and require strengthening of programmatic efforts. This article describes the development of a WHO measles programmatic risk assessment tool to be used for monitoring, guiding, and sustaining measles elimination efforts at the subnational level. We outline the tool development process; the tool specifications and requirements for data inputs; the framework of risk categories, indicators, and scoring; and the risk category assignment. Overall risk was assessed as a function of indicator scores that fall into four main categories: population immunity, surveillance quality, program performance, and threat assessment. On the basis of the overall score, the tool assigns each district a risk of either low, medium, high, or very high. The cut-off criteria for the risk assignment categories were based on the distribution of scores from all possible combinations of individual indicator cutoffs. The results may be used for advocacy to communicate risk to policymakers, mobilize resources for corrective actions, manage population immunity, and prioritize programmatic activities. Ongoing evaluation of indicators will be needed to evaluate programmatic performance and plan risk mitigation activities effectively. The availability of a comprehensive tool that can identify at-risk districts will enhance efforts to prioritize resources and implement strategies for achieving the Global Vaccine Action Plan goals for measles elimination.

Assessment of polyaromatic hydrocarbons and pesticide residues in domestic and imported pangasius (Pangasianodon hypophthalmus) fish in India.

BACKGROUND: The pangasius catfish (Pangasianodon hypophthalmus) is a ubiquitous item of seafood in global markets. However, pesticide residues in aquaculture fish, arising from agricultural run-off and/or direct application during pond preparation, pest control and harvest, are a potential food safety concern. This study assessed the level of chemical hazard in domestic and imported pangasius fish in India. RESULTS: A total of 119 contaminants, including polyaromatic hydrocarbons (PAHs), organochlorines (OCs) and other groups of pesticides, were screened in 148 samples during 2014-2015 as the first endeavour of its kind in an Indian context, employing a validated gas chromatography/tandem mass spectrometry (GC/MS/MS) method. Apart from the low-level incidence of OCs, pesticides such as quinalphos, malathion, parathion-methyl, etc. were detected in 38% of the samples. In comparison with Indian pangasius, fewer contaminants at low residue level were detected in pangasius fillets imported from Vietnam. CONCLUSION: The human dietary exposures of the residue concentrations detected were less than the maximum permissible intakes and hence appeared safe. However, detection of commonly used pesticides indicated their direct application in aquaculture and contamination from agricultural run-off. This emphasizes the need for continual residue monitoring in aquaculture fish. © 2015 Society of Chemical Industry.

Assessment of organochlorine pesticide residues in Indian flue-cured tobacco with gas chromatography-single quadrupole mass spectrometer.

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.

Bioefficacy, residue dynamics and safety assessment of the combination fungicide trifloxystrobin 25% + tebuconazole 50%-75 WG in managing early blight of tomato (Lycopersicon esculentum Mill.).

This paper reports the in vitro and in vivo bioefficacy of a combination fungicide trifloxystrobin (25%) + tebuconazole (50%) against early blight disease of tomato (Lycopersicon esculentum Mill.) caused by Alternaria solani and their corresponding pre-harvest intervals (PHI) with reference to the maximum residue limits (European Union). Bioefficacy of the test fungicide combination revealed that in vitro conditions manifested the best control (75.1%) at 350 mg kg(-1) against 76.2% control under field conditions. A sample preparation method based on ethyl acetate extraction and estimation by LC-MS multiple reaction monitoring (MRM) was validated in tomato fruits at 0.01 mg/kg and dissipation studies were conducted in field at single and double doses. The residues of both the compounds on all the sampling days were below the European Union maximum residue limits (EU-MRLs) and the maximum permissible intakes (MPIs) were calculated on the basis of prescribed acceptable daily intake (ADI). The combined bioefficacy and residue dynamics information will support label-claim of this fungicide combination for the management of early blight in tomato.

Dissipation kinetics, safety evaluation, and assessment of pre-harvest interval (PHI) and processing factor for kresoxim methyl residues in grape.

A field dissipation study was conducted to evaluate the pre-harvest interval (PHI) and processing factor (PF) for kresoxim methyl (Ergon 44.3 SC) residues in grapes and during raisin making process at recommended dose (RD) and double the recommended dose (DRD). Kresoxim methyl residues dissipated following 1st-order kinetics with a half-life of 10 and 18 days at RD and DRD, respectively. The PHIs with respect to the European Union maximum residue limit (EU-MRL) of 1 mg kg(-1) for grapes were 13 and 30 days at RD and DRD, respectively. The degradation data during grape to raisin making process were best fitted to nonlinear 1st + 1st-order kinetics with a half-life ranging between 4 and 8 days for both shade drying and with raisin dryer at different doses. The PFs were 1.19 and 1.24 with shade drying and 1.09 and 1.10 with raisin dryer, respectively, which indicates concentration of the residues during raisin making process. The dietary exposure of kresoxim methyl on each sampling day was less than the respective maximum permissible intake both at RD and DRD. The residues of kresoxim methyl in market samples of grapes and raisins were well below the EU-MRL and were also devoid of any risk of acute toxicity related to dietary exposure.

Reasons related to non-vaccination and under-vaccination of children in low and middle income countries: findings from a systematic review of the published literature, 1999-2009.

OBJECTIVE: Despite increases in routine vaccination coverage during the past three decades, the percent of children completing the recommended vaccination schedule remains below expected targets in many low and middle income countries. In 2008, the World Health Organization Strategic Advisory Group of Experts on Immunization requested more information on the reasons that children were under-vaccinated (receiving at least one but not all recommended vaccinations) or not vaccinated in order to develop effective strategies and interventions to reach these children. METHODS: A systematic review of the peer-reviewed literature published from 1999 to 2009 was conducted to aggregate information on reasons and factors related to the under-vaccination and non-vaccination of children. A standardized form was used to abstract information from relevant articles identified from eight different medical, behavioural and social science literature databases. FINDINGS: Among 202 relevant articles, we abstracted 838 reasons associated with under-vaccination; 379 (45%) were related to immunization systems, 220 (26%) to family characteristics, 181 (22%) to parental attitudes and knowledge, and 58 (7%) to limitations in immunization-related communication and information. Of the 19 reasons abstracted from 11 identified articles describing the non-vaccinated child, 6 (32%) were related to immunization systems, 8 (42%) to parental attitudes and knowledge, 4 (21%) to family characteristics, and 1 (5%) to communication and information. CONCLUSIONS: Multiple reasons for under-vaccination and non-vaccination were identified, indicating that a multi-faceted approach is needed to reach under-vaccinated and unvaccinated children. Immunization system issues can be addressed through improving outreach services, vaccine supply, and health worker training; however, under-vaccination and non-vaccination linked to parental attitudes and knowledge are more difficult to address and likely require local interventions.

A fast, inexpensive, and safe method for residue analysis of meptyldinocap in different fruits by liquid chromatography/tandem mass spectrometry.

An analytical method is reported for residue analysis of the fungicide meptyldinocap in different fruit matrixes that involves extraction with ethyl acetate, hydrolysis of the residues with ethanolamine, and determination by LC/MS/MS. The method involves extraction of 10 g sample with 10 mL ethyl acetate; evaporation of the ethyl acetate phase to dryness, and subsequent hydrolysis of the residues to 4,6-dinitro-2-(1-methylheptyl) phenol on reaction with 1% ethanolamine. The pH of this hydrolyzed product was neutralized with formic acid and analyzed by LC/MS/MS. The hydrolysis reaction followed pseudo-first-order kinetics, and the reaction product was spectroscopically confirmed as 2-(1-methylheptyl)-4,6-dinitrophenol. The method offered > 80% recoveries at an LOQ of 10 ng/g for grape and mango, 25 ng/g for pomegranate with intralaboratory Horwitz ratio < 0.5, and measurement uncertainties < 10% at LOQ levels. Considering first-order rate kinetics, activation energy, enthalpy of activation, and entropy of activation varied as solvent > mango > grape > pomegranate. Free energy of activation at 298 K was higher than at 280 K and was similar for solvent and three matrixes at both temperatures.

Multiresidue determination and uncertainty analysis of 87 pesticides in mango by liquid chromatography-tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry (LC-MS/MS)-based method was optimized and validated for the multiresidue analysis of 87 pesticides in mango at the ≤ 10 ng g(-1) level. The method involves extraction of 10 g of homogenized mango samples (+10 mL of water + 1 g of sodium acetate + 10 g of sodium sulfate) with 10 mL of ethyl acetate; cleanup by dispersive solid-phase extraction with a combination of primary secondary amine (PSA, 50 mg), graphitized carbon black (GCB, 25 mg), and anhydrous sodium sulfate (150 mg); and final estimation by LC-MS/MS with multiple reaction monitoring. Direct analysis (no clean up) resulted in significant suppression in ionization of the majority of the test compounds over the electrospray ionization probe. However, clean up with the above combination of PSA + GCB reduced the matrix-induced signal suppressions significantly, and the signals in the cleaned extracts were nearly equivalent to the corresponding solvent standards. Substitution of PSA with florisil also gave equivalent clean up effects. The method was quite rugged as evident from a low Horwitz ratio (mostly <0.5) and low measurement uncertainties at 10 ng g(-1). The limit of quantification was <10 ng g(-1) for all of the pesticides with recoveries within 70-120% for most pesticides even at 2.5 ng g(-1). The method offers a significantly effective, sensitive, cheaper, and safer alternative to the existing methods of multiresidue analysis.

Multiresidue analysis of 83 pesticides and 12 dioxin-like polychlorinated biphenyls in wine by gas chromatography-time-of-flight mass spectrometry.

A multiresidue method is described for simultaneous estimation of 83 pesticides and 12 dioxin-like polychlorinated biphenyls (PCBs) in red and white wines. The samples (20mL wine, acidified with 20 mL 1% HCl) were extracted with 10 mL ethyl acetate (+20 g sodium sulphate) and cleaned by dispersive solid-phase extraction (DSPE) with anhydrous calcium chloride and Florisil successively. The final extract (5 mL) was solvent exchanged to 1mL of cyclohexane:ethyl acetate (9:1), further cleaned by DSPE with 25mg primary secondary amine sorbent and analyzed by gas chromatography-time-of-flight mass spectrometry (GC-TOF-MS) within 31 min run time. The limits of quantification of most analytes were 80% for most analytes except cyprodinil, buprofezin and iprodione. The expanded uncertainties at 10 ng/mL were <20% for most analytes. Intra-laboratory precision in terms of Horwitz ratio of all the analytes was below 0.5, suggesting ruggedness of the method. Effectively, the method detection limit for most analytes was as low as up to 1 ng/mL in both red and white wine, except for cyfluthrin and cypermethrin.