Determination of propineb and its metabolites propylenethiourea and propylenediamine in banana and soil using gas chromatography with flame photometric detection and LC-MS/MS analysis.

A sensitive and specific method for the determination of propineb and its metabolites, propylenethiourea (PTU) and propylenediamine (PDA), using gas chromatography with flame photometric detection (GC-FPD) and LC-MS/MS was developed and validated. Propineb and its metabolite residue dynamics in supervised field trials under Good Agricultural Practice (GAP) conditions in banana and soil were studied. Recovery of propineb (as CS2), PDA and PTU ranged from 75.3 to 115.4% with RSD (n = 5) of 1.3-11.1%. The limit of quantification (LOQ) of CS2, PDA and PTU ranged from 0.005 to 0.01 mg kg-1, and the limit of detection (LOD) ranged from 0.0015 to 0.0033 mg kg-1. Dissipation experiments showed that the half-life of propineb in banana and soil ranged from 4.4 to 13.3 days. PTU was found in banana with a half-life of 31.5-69.3 days, while levels of PDA were less than 0.01 mg kg-1 in banana and soil. It has been suggested that PTU is the major metabolite of propineb in banana. The method was demonstrated to be reliable and sensitive for the routine monitoring of propineb and its metabolites in banana and soil. It also serves as a reference for the detection and monitoring of dithiocarbamates (DTCs) residues and the evaluation of their metabolic pathway.

In vitro and field efficacy of fungicides against sheath blight of rice and post-harvest fungicide residue in soil, husk, and brown rice using gas chromatography-tandem mass spectrometry.

Rice is a staple food for about 65% of the India's population. India ranks first in area under rice and second in production of rice in the world. In India, it is cultivated over 43.39 m ha with a production and productivity of 104.32 million tons and 2404 kg/ha, respectively. Besides ensuring food security of the nation, it is an export commodity and earns a huge foreign exchange. In this study, we investigated the efficacy of five fungicides against Rhizoctonia solani Kuhn AG-1 IA, inciting sheath blight of rice in vitro and under field conditions along with post-harvest residue of the fungicides found effective in disease management. In vitro growth inhibition tests revealed that the EC50 values of azoxystrobin 18.2% + difenoconazole 11.4% SC, pencycuron 22.9% SC, thifluzamide 23.9% SC, hexaconazole 4% + zineb 68% WP, and validamycin 3% L against Rhizoctonia solani ranged from 0.006 to 354.81 ppm a.i., whereas the corresponding EC90 values were 0.758 to 1202.26 ppm a.i. Thifluzamide 23.9% SC was found to be the most inhibitory with EC50 and EC90 values of 0.006 and 0.758 ppm a.i. followed by hexaconazole 4% + zineb 68% WP. The complete inhibition of sclerotia formation was observed at 1 ppm, 20 ppm, and 25 ppm a.i. of thifluzamide 23.9% SC, hexaconazole 4% + zineb 68% WP, and azoxystrobin 18.2% + difenoconazole 11.4% SC, respectively. In field trials, azoxystrobin 18.2% + difenoconazole 11.4% SC was the best treatment in reducing sheath blight and in enhancing grain yield of rice followed by thifluzamide 23.9% SC, pencycuron 22.9% SC, and validamycin 3% L, whereas hexaconazole 4% + zineb 68% WP was the least effective fungicide. Benefit-cost ratio (B:C) of different fungicides reflected that pencycuron 22.9% SC (B:C 5.06) and azoxystrobin 18.2% + difenoconazole 11.4% SC(B:C 4.65) sprayed at single/recommended doses of 1 ml/l were highly economical in managing sheath blight disease of rice. Double dose of pencycuron 22.9% SC further enhanced the B:C to 7.24 while the double dose of azoxystrobin 18.2% + difenoconazole 11.4% SC was less economical (B:C 2.84) compared to their recommended doses. Samples of rice matrices were processed using QuEChERS method and analyzed for the presence of fungicide residues by gas chromatography-tandem mass spectrometry (GC-MS/MS). The post-harvest residues of azoxystrobin, difenoconazole, and pencycuron, sprayed at single/recommended and double doses with a pre-harvest interval (PHI) of 44 days, were found below the limit of quantification (LOQ), i.e., 0.01 and 0.005 mg kg-1 for azoxystrobin and difenoconazole and 0.05 mg kg-1 for pencycuron in brown rice, cropped soil, paddy straw, and husk. These results clearly demonstrated that treatment of azoxystrobin 18.2% + difenoconazole 11.4% SC and pencycuron 22.9% SC could be taken as safe for crop protection and environmental contamination point of view. The findings of this research work will have a positive impact on rice export and use.

Determination of mancozeb residue in fruit by derivatization and a modified QuEChERS method using ultraperformance liquid chromatography-tandem mass spectrometry.

A liquid chromatography-tandem mass spectrometry method with derivatization and a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation was developed for the determination of mancozeb in fruits. The target compound was determined in less than 4.0 min with use of an electrospray ionization source in positive mode. The limits of detection and the limits of quantification ranged from 1.0 to 3.2 µg kg-1 and from 10 to 15 µg kg-1 in fruit respectively. The linearity was excellent for mancozeb (R 2 ≥ 0.9920). Recoveries in five matrices were obtained at three spiking levels (0.02, 0.1, and 1 mg kg-1). For all concentrations, the mean recoveries ranged from 84.0% to 95.9%, with repeatability relative standard deviation (n = 5) of 0.6 - 7.0%. The interday reproducibility relative standard deviation (n = 3) ranged from 1.4% to 5.5%. This method could be used for the routine detection of mancozeb residues in fruit. Graphical abstract The derivation of mancozeb and the detection process of derivative product by UPLC-MS/MS.

Effects of washing, peeling, storage, and fermentation on residue contents of carbaryl and mancozeb in cucumbers grown in greenhouses.

Cucumbers grown in two different greenhouses were exposed to mancozeb and carbaryl at different times. The effects of 10-day preharvest period, water and detergent washing, peeling, predetermined storage period at 4°C (refrigeration), and fermentation on the reduction of residue levels in the plant tissues were investigated. Mancozeb and carbaryl residues in cucumbers were determined by gas chromatography-electron capture detection. Results showed that residue levels in samples, which were collected after 10 days following the pesticide application, were significantly lower than the samples collected after 2 h subsequent to the pesticide application. The culinary applications were effective in reducing the residue levels of the pesticides in cucumbers. As a result, non-fermentative pickling in sodium chloride and acetic acid was the most effective way to reduce the mancozeb and carbaryl residues of the cucumbers.

Contribution to the food products' analysis: A research and evaluation on the hemolytic effect of some pesticides used in Lebanon.

Pesticides are a real concern for the society as their use has become critical, leading sometimes to their accumulation as residues in fruits and vegetables. After examining the pesticides sold in Northern Lebanon, this study is focused on the analysis and identification of pesticides residues in fruits and vegetables that are harvested in this region and treated with the locally sold pesticides. Results show: first, (i) a use of Zineb by the name of another pesticide Micronized Sulfur to avoid prosecution; (ii) a significant presence of Metalaxyl in lemons and oranges; (iii) a significant presence of Trifluralin in strawberries; and (iv) a significant presence of Zineb in lemons and tomatoes. Second, with the use of hemolytic tests on human blood results show: (i) a critical concentration and a significant hemolytic effect of some pesticides used in Lebanon; and (ii) an absence of hemolytic effect in the collected fractions of the different analyzed fruit extracts containing pesticides. Finally, this work is the first step for pesticides' analysis in vegetables and fruits in Lebanon, initiating a wider analytical study in order to control and examine the use of pesticides which, according to our results, could have an adverse effect on human health over a long term.

Degradation pattern and risk assessment of carbendazim and mancozeb in mango fruits.

A supervised field trial was conducted at four different agroclimatic locations in India to evaluate the dissipation pattern and risk assessment of carbendazim and mancozeb in mango fruits following foliar application of mixed formulation of carbendazim 12% and mancozeb 63% fungicide (SAAF-75WP) at recommended dose (90 + 472.5) and double the recommended dose (180 + 945 g a.i. ha(-1)). Average initial deposition of carbendazim was in the range of 1.12 to 2.7 and 1.95 to 4.09 mg kg(-1) and for mancozeb in the range of 2.25 to 2.71 and 4.17 to 5.96 mg kg(-1), given at respective doses. Residues of carbendazim and mancozeb were dissipated to the below detectable limit 7 days after spray at recommended dosage in all the locations. The fungicide degradation followed a first order kinetics with half-lives of 1-5 and 1-3 days, for carbendazim and mancozeb, respectively. The TMRC values, calculated from residue data generated from all four locations, were found to be below the MPI in mango fruit, and hence, the fungicide will not cause any adverse effect after consumption of mango fruits. This data could provide guidance for the proper and safe use of this fungicide mixture for managing disease incidence in mango in India.

Dynamics and residues of mixed formulation of fenamidone and mancozeb in gherkin field ecosystem.

The dynamics and residues of mixed formulation of fenamidone and mancozeb in a gherkin field ecosystem were investigated. The quantification was performed using gas chromatography-electron capture detection (GC-ECD) and UV-vis spectrophotometry for fenamidone and mancozeb residues, respectively. The method was validated using blank samples spiked at three levels and the results showed that recoveries ranged from 92 to 98 and 90 to 96 percent with relative standard deviations (RSD) ranging of 0.78-5.9 and 2.04-4.41 percent for fenamidone and mancozeb, respectively. The compound degradation followed a first order kinetics with half-lives of 2.8-2.82 and 2.02-2.26 days, for fenamidone and mancozeb, respectively. Pesticide residues in fruit were below the EU maximum residue level (MRL) after 10 days for fenamidone (0.02 µg/g) and just after treatment for mancozeb (2 µg/g). These results can be utilized in formulating the spray schedule and safety evaluation for these pesticides in gherkin.

Kinetic and thermodynamic investigation of mancozeb degradation in tomato homogenate during thermal processing.

BACKGROUND: The kinetic and thermodynamic parameters of mancozeb degradation in tomato homogenates under the conditions prevailing in the manufacture of tomato products (at 60-100 °C for 0-60 min) were investigated. A gas chromatography-mass spectrometry method was used to analyse residual mancozeb in tomato homogenate. Ethylenethiourea (ETU), the main toxic degradation product of mancozeb, was measured by high-performance liquid chromatography (HPLC)-with photodiode array detector (PDA). RESULTS: The degradation of mancozeb and the formation of ETU in tomato homogenates were adequately described as first-order kinetics. Dependence of the rate constant followed the Arrhenius relationship. Apparent activation energies, temperature coefficients, half time and time to reduce to 90% of the initial value of mancozeb were calculated as kinetic parameters. The thermodynamic parameters of mancozeb were also described as Δg(d) = - 2.440 and 7.074 kJ mol⁻¹; Δh(d) = - 32.555 and - 42.767 kJ mol⁻¹; Δs(d) = - 0.090 and - 0.150 kJ mol⁻¹ K⁻¹; K(e) = 0.414 and 9.797 L g⁻¹ for 333 and 373 K respectively. CONCLUSION: Current findings may shed light on the reduction of mancozeb residue and its toxic degradation product during thermal processing of tomatoes and may also be valuable in awareness and prevention of potential risks from dietary exposure.

The effects of pesticide mixtures on degradation of pendimethalin in soils.

Most agronomic situations involve a sequence of herbicide, fungicide, and insecticide application. On the other hand, use of pesticidal combinations has become a standard practice in the production of many agricultural crops. One of the most important processes influencing the behavior of a pesticide in the environment is its degradation in soil. It is known that due to several pesticide applications in one vegetation season, the pesticide may be present in mixtures with other pesticides or xenobiotics in soil. This study examines the role which a mixture of chemicals plays in pesticide degradation. The influence of other pesticides on the rate of pendimethalin (PDM) degradation in soil was measured in controlled conditions. Mixtures of PDM with mancozeb or mancozeb and thiamethoxam significantly influenced the degradation of pendimethalin under controlled conditions. The second type of mixtures, with metribuzin or thiamethoxam, did not affect the behavior of pendimethalin in soil. Also, we determined the influence of water content on the rate of pendimethalin degradation alone in two soils and compared it to the rate in three pesticide mixtures. We compared two equations to evaluate the predictors of the rate of herbicide dissipation in soil: the first-order kinetic and the non-linear empirical models. We used the non-linear empirical model assuming that the degradation rate of a herbicide in soil is proportional to the difference of the observed concentration of herbicide in soil at time and concentration of herbicide in the last day of measurement.

Persistence behaviour of fungicide mixture (benalaxyl-M 4% + mancozeb 65%) WP in grapes.

Benalaxyl-M [methyl N-phenylacetyl-N-2, 6-xylyl-DL-alaninate] is a newly introduced phenyl-amide fungicide whereas Mancozeb is one of the member of ethylenebisdiothiocarbamate (EBDC) fungicide. Benalaxyl-M in combination with Mancozeb effectively controls downy mildew of grapes. A two season field trial was conducted under West Bengal climatic condition during 2009-2010 to evaluate the dissipation pattern of fungicide mixture (Benalaxyl-M 4 % + Mancozeb 65 %) WP in grapes at two application rates (2,750 g and 5,500 g ha(-1)). The quantitative analysis was performed using liquid chromatography-mass spectrometry (LC-MS/MS) and UV-Vis spectrophotometer for Benalaxyl-M and Mancozeb residues respectively. Following the first order kinetics the fungicide Benalaxyl-M dissipates in grapes with half-life (T(1/2)) value ranges between 2.59 and 2.79 days irrespective of seasons and doses. The dissipation pattern of Mancozeb also follows first order kinetics with half-life (T(1/2)) value ranges between 3.86 and 4.93 days irrespective of seasons and doses.

Residue dynamics of fenamidone and mancozeb on gherkin under two agro climatic zones in the state of Karnataka, India.

Residue dynamics of fenamidone and mancozeb on gherkin was evaluated at two different agro climatic zones i.e. at Bangalore (Zone-1) and Dharwad (Zone-2) in the state of Karnataka, India. Two treatments of the combination formulation (fenamidone 10% + mancozeb 50%) were given at the standard dose 150 + 750 g a.i. ha(-1) and double dose 300 + 1,500 g a.i. ha(-1). Initial residue deposits of fenamidone were 0.467 and 0.474 mg kg(-1) at Zone-1 and 2, respectively from standard dose treatment. From double dose treatment they were 0.964 and 0.856 mg kg(-1), respectively. Fenamidone residues persisted for 15 and 10 days and dissipated with the half-life of 4 and 3 days at Zone-1 and 2, respectively. Mancozeb residue deposits on gherkin were 0.383 and 0.428 mg kg(-1) from standard dose and 0.727 and 0.626 mg kg(-1) from double dose treatment at Zone-1 and 2, respectively. Mancozeb residues dissipated with the half-life of 2 and 1 day, respectively. Residues of both fenamidone and mancozeb dissipated faster at Zone-2 compared to Zone-1. The limit of quantification of fenamidone and mancozeb were 0.02 and 0.1 mg kg(-1), respectively in both gherkin and soil. Residues of fenamidone and mancozeb in soil collected on the 20th day from the 2 locations were found to be below quantifiable limit of both fungicides.

Persistence of propineb (polymeric zinc 1,2-propylene bisdithiocarbamate) fungicide in onion and cropped soil.

To study the persistence of propineb in/on onion a field experiment was conducted during 2007 at Agricultural Research Station, Durgapura, Jaipur Propineb70WP @ 1,225 and 2,450 g a. i. ha(-1) dose was applied as foliar spray to the crop thrice at an interval of 10 days. After third spray, onion samples comprising of green leaves and immature bulb were collected at 0,1,3,5,7,10 and 15 days. The initial deposit was 2.32 and 4.89 ppm of propineb (on CS(2) basis) which persisted up to the 10 and 15 days at normal 1,225 g a.i. ha(-1) and higher 2,450 g a.i. ha(-1) dose of fungicide application. The half life values of propineb ranged from 3.27 to 4.60 days.

Persistence and safety risk assessment of propineb in Indian tea.

A supervised field trial was conducted on tea with propineb at 1,750 and 3,500 g a.i./ha at two locations (Assam and Darjeeling), applied thrice at an interval of 10 days during the year 2006-2007. Propineb residue was measured spectrophotometrically at 435 nm in terms of CS2. The initial deposit of propineb in green tea leaves were found to be in the range of 16.26-35.96 mg/kg and the residue persisted up to 10 days irrespective of doses and locations with half-life value ranging from 2.24 to 2.43 days and preharvest interval of 17.17-21.37 days. Made tea residues ranged from 9.27 to 20.86 mg kg(-1) on 7 days and no residues could be detected on 14 days. Infusion study indicated that propineb did not infuse into tea liquor from made tea. The limit of determination was found to be 0.1 mg kg(-1) in terms of propineb for green tea leaves, made tea, and tea liquor. The tea applied with the recommended dose of propineb is safe for consumption as liquor.

Soil and water pollution in a banana production region in tropical Mexico.

The effects of abundant Mancozeb (Mn, Zn-bisdithiocarbamate) applications (2.5 kg ha⁻¹week⁻¹ for 10 years) on soil and surface-, subsurface- and groundwater pollution were monitored in a banana production region of tropical Mexico. In soils, severe manganese accumulation was observed, wheras the main metabolite ethylenethiourea was near the detection limit. Surface and subsurface water was highly polluted with ethylenethiourea, the main metabolite of Mancozeb (22.5 and 4.3 µg L⁻¹, respectively), but not with manganese. In deep ground water, no ethylenethiourea was detected. The level of pollution in the region presents a worrisome risk for aquatic life and for human health.

The fungicide mancozeb affects soil invertebrates in two subtropical Brazilian soils.

Mancozeb is a dithiocarbamate non-systemic fungicide widely used to control fungal diseases of plants, commonly applied in apple orchards in Brazil. Instead of its common use, there are no reports about the risk to non-target organisms in Brazilian soils. We studied the risk of Mancozeb (in the commercial formulation Dithane® NT) for standard invertebrate species (Folsomia candida, Eisenia andrei and Enchytraeus crypticus) in two subtropical Brazilian soils, Oxisol and Ultisol, which are representative of apple production areas in Brazil. Reproduction and survival tests were carried out following ISO guidelines. Results showed that Mancozeb in Oxisol reduced the survival and reproduction of collembolans (LC50 54.43 and EC50 2.72 mg a.i. kg-1) and enchytraeids (LC50 6.97 and EC50 3.56 mg a.i. kg-1), in lowest values than those observed in Ultisol (F. candida LC50 > 1000 and EC50 > 100 mg a.i. kg-1; E. crypticus LC50 280.21 and EC50 29.67). Effects to E. andrei were similar in both soils and indicated a lower sensitivity of this species to Mancozeb. The species F. candida and E. crypticus were more sensitive than E. andrei. These results reinforce the need to include other soil organisms besides earthworms, using chronical endpoints and considering different types of soils, to better predict the risk of pesticides for subtropical soils.

Surface-Enhanced Raman Spectroscopy (SERS) of Mancozeb and Thiamethoxam Assisted by Gold and Silver Nanostructures Produced by Laser Techniques on Paper.

Advanced gold (Au) and silver (Ag) nanostructures were produced by laser techniques on printer paper substrate. Surface-enhanced Raman spectroscopy (SERS) analyses of the fungicide mancozeb (Dithane DG) and insecticide thiamethoxam (Aktara 25 BG) in quantities smaller than usually applied in agricultural medicine were performed for the first time assisted by the structures fabricated. The investigations and results show an easy alternative and cheap way to detect small amounts or residue of harmful environmental pollutants, which has a direct bearing on food quality and thus on human health.

Method development and validation for low-level propineb and propylenethiourea analysis in baby food, infant formula and related matrices using liquid chromatography-tandem mass spectrometry.

Two simple, selective and rugged liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods were developed and validated for determination of propineb and propylenethiourea (PTU) in infant formula, fruit-based and cereal-based baby food and raw materials used in production of infant formula, including carbohydrates, protein isolates, vegetable oils and emulsifiers. The sample preparation procedure for propineb analysis was based on streamlined derivatisation to form and stabilise the target analyte (propylenebisdithiocarbamate-dimethyl), followed by extraction using a modified QuEChERS procedure with a dispersive solid phase extraction (d-SPE). The PTU determination employed an aqueous extraction with optimised protein precipitation and single-step SPE clean-up. To achieve maximum sensitivity, electrospray ionisation and atmospheric-pressure chemical ionisation were employed for LC-MS/MS analysis of propineb and PTU, respectively. Validation of the developed methods was performed in accordance with Document SANTE/11813/2017. Mean recoveries were in the range of 86-120% for propineb and PTU, respectively, with interday and intraday repeatabilities below 13%. A limit of quantification (LOQ) of 0.003 mg kg-1 was validated for most of the evaluated analyte/sample matrix combinations with the exception of PTU in soy protein isolate and soybean oil, for which an LOQ of 0.01 mg kg-1 was obtained. This is the first report that provides validated methods for monitoring propineb and PTU in infant formula and baby foods at concentrations compliant with the maximum residue levels established in the EU legislation.

Environmental and biological monitoring for the identification of main exposure determinants in vineyard mancozeb applicators.

Grapevine is a vulnerable crop to several fungal diseases often requiring the use of ethylenebisdithiocarbamate (EBDC) fungicides, such as mancozeb. This fungicide has been reported to have goitrogenic, endocrine disrupting, and possibly immunotoxic effects. The aim of this study was to assess workers' exposure in two scenarios of mancozeb application and analyse the main determinants of exposure in order to better understand their mechanism of influence. Environmental monitoring was performed using a modified Organisation for Economic Co-operation and Development (OECD) "patch" methodology and by hand-wash collection, while mancozeb's metabolite, ethylenethiourea (ETU), was measured in 24-h preexposure and postexposure urine samples. Liquid chromatography-mass spectrometry was used for determination of mancozeb and ETU in different kinds of samples. Closed tractor use resulted in 40 times lower potential exposure compared with open tractor. Coveralls reduced skin exposure 4 and 10 times in case of open and closed tractors, respectively. Gloves used during application resulted in 10 times lower hand exposure in open but increased exposure in closed tractors. This study has demonstrated that exposure to mancozeb is low if safe occupational hygiene procedures are adopted. ETU is confirmed as suitable biological marker of occupational exposure to mancozeb, but the absence of biological exposure limits significantly reduces the possibility to interpret biological monitoring results in occupationally exposed workers.

Capillary electrophoretic-ultraviolet method for the separation and estimation of zineb, maneb, and ferbam in food samples.

A simple and sensitive capillary electrophoretic method with ultraviolet detection has been developed for the separation and determination of ferbam [iron(III)-dimethyldithiocarbamate], maneb [manganese(II)-ethylenebisdithiocarbamate] and zineb [zinc(II)-ethylenebisdithiocarbamate], in borate buffer, after their acidic decomposition and complexation with CDTA (trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid monohydrate), as CDTA-metal complexes of Fe+3, Mn +2, and Zn+2. The determination is dependent on the pH and the nature of the buffer solutions. In this method, the detection limit (signal-to-noise ratio = 3) is 0.0013, 0.0022, and 0.0023 mM for ferbam, maneb, and zineb, respectively. The relative standard deviation for the analysis of 1 mM of each was found to be 1.5 +/- 0.2%. The method was successfully applied for the analysis of red beans and grain samples spiked with ferbam, maneb, and zineb. The applicability of capillary electrophoresis as a useful tool for the simultaneous determination and analysis of ferbam, maneb, and zineb is demonstrated.

Leaf surface characteristics of apple seedlings, bean seedlings and kohlrabi plants and their impact on the retention and rainfastness of mancozeb.

A study was made of the influence of the upper leaf surface characteristics on the retention and rainfastness of the contact fungicide mancozeb with and without tank-mix adjuvants (RSO 5 and RSO 60) on apple seedlings, bean seedlings and kohlrabi plants. Large differences in roughness, in the amount and composition of surface waxes and in the retention and rainfastness of mancozeb were found among species. Strong correlations between roughness and total amount of surface waxes and mass of C29 alkane in the wax mass were also found. Fungicide retention was strongly, negatively correlated with surface roughness, total epicuticular wax, amount of C29 alkane and the total mass of alkanes. Rainfastness correlated strongly or very strongly with the amount of C28 alcohol and C33 alkane. The addition of a more hydrophobic (RSO 5) or a more hydrophilic (RSO 60) adjuvant to the spray solution influenced retention and rainfastness, and also altered the correlation coefficients. The present results support earlier observations which show that the success of adjuvants in enhancing the retention and rainfastness of agrochemicals depends on the characteristics of the leaf surface.