Solid phase extraction (SPE) and dispersive solid-phase extraction (d-SPE) were compared and evaluated for the determination of λ-cyhalothrin and cypermethrin in palm oil matrices by gas chromatography with an electron capture detector (GC-ECD). Several SPE sorbents such as graphitised carbon black (GCB), primary secondary amine (PSA), C(18), silica, and florisil were tested in order to minimise fat residues. The results show that mixed sorbents using GCB and PSA obtained cleaner extracts than a single GCB and PSA sorbents. The average recoveries obtained for each pesticide ranged between 81% and 114% at five fortification levels with the relative standard deviation of less than 7% in all cases. The limits of detection for these pesticides were ranged between 0.025 and 0.05 μg/g. The proposed method was applied successfully for the residue determination of both λ-cyhalothrin and cypermethrin in crude palm oil samples obtained from local mills throughout Malaysia.
The efficacy of chitin synthesis inhibitors (CSIs) against fungus-growing termites is known to vary. In this study, 0.1% chlorfluazuron (CFZ) cellulose bait was tested against medium and large field colonies of Macrotermes gilvus (Hagen). The termite mounds were dissected to determine the health of the colony. Individual termites (i.e., workers and larvae) and fungus combs were subjected to gas chromatography-mass spectrometry (GC-MS) analysis to detect the presence of CFZ. In this study, 540.0 ± 25.8 g (or equivalent to 540.0 ± 25.8 mg active ingredient) and 680.0 ± 49.0 g (680.0 ± 49.0 mg active ingredient) of bait matrix were removed by the medium- and large-sized colonies, respectively, after baiting. All treated medium-sized colonies were moribund. The dead termites were scattered in the mound, larvae were absent, population size had decreased by 90%, and the queens appeared unhealthy. In contrast, no or limited effects were found in large-sized colonies. Only trace amounts of CFZ were detected in workers, larvae, and fungus combs, and the population of large-sized colonies had declined by only up to 40%. This might be owing to the presence of large amount of basidiomycete fungus and a drastic decrease of CFZ content per unit fungus comb (a main food source of larvae) in the large-sized colonies, and hence reduced the toxic effect and longer time is required to accumulate the lethal dose in larvae. Nevertheless, we do not deny the possibility of CSI bait eliminating or suppressing the higher termite if the test colonies could pick up adequate lethal dose by installing more bait stations and prolonging the baiting period.
An HS-SPME method was developed using multivariate experimental designs, which was conducted in two stages. The significance of each factor was estimated using the Plackett-Burman (P-B) design, for the identification of significant factors, followed by the optimization of the significant factors using central composite design (CCD). The multivariate experiment involved the use of Minitab® statistical software for the generation of a 2(7-4) P-B design and CCD matrices. The method performance evaluated with internal standard calibration method produced good analytical figures of merit with linearity ranging from 1 to 500 μg/kg with correlation coefficient greater than 0.99, LOD and LOQ were found between 0.35 and 8.33 μg/kg and 1.15 and 27.76 μg/kg respectively. The average recovery was between 73% and 118% with relative standard deviation (RSD=1.5-14%) for all the investigated pesticides. The multivariate method helps to reduce optimization time and improve analytical throughput.
Paddy (unmilled rice), milled rice and maize-bound 14C residues were prepared using 14C-succinate-labelled malathion at 10 and 152 ppm. After 3 months, the bound residues accounted for 12%, 6.5% and 17.7% of the applied dose in paddy, milled rice and maize respectively in the grains treated at 10 ppm. The corresponding values for the 152 ppm were 16.6%, 8.5% and 18.8%. Rats fed milled rice - bound 14C-residues eliminated 61% of the 14C in the faeces and 28% in the urine. The corresponding percentages for paddy and maize were 72%, 9% and 53%, 41% respectively; indicating that bound residues from milled rice and maize were moderately bioavailable. When rice-bound malathion residues (0.65 ppm in feed) were administered to rats in a 5 week feeding study, no signs of toxicity were observed. Plasma and RBC cholinesterase activities were slightly inhibited: blood urea nitrogen was significantly elevated in the test animals. Other parameters examined showed no or marginal changes.
This paper reviews the application of various modes of solid-phase microextraction (SPME) for the analysis of pesticide residues in fruits and vegetables. SPME is a simple extraction technique that eliminates the use of solvent, and it is applied for the analysis of both volatile and nonvolatile pesticides. SPME has been successfully coupled to both GC and LC. The coupling with GC has been straightforward and requires little modification of existing equipment, but interfacing with LC has proved challenging. The external standard calibration technique is widely used for quantification, while standard addition and internal or surrogate standards are mainly used to account for matrix effects. All parameters that affect the extraction of pesticide residues from fruits and vegetables, and therefore need to be optimized, are also reviewed. Details of the characteristics of analytical procedures and new trends in fiber production using sol-gel technology and molecularly imprinted polymers are discussed.
This review intends to integrate the relevant information that is related to pesticide applications in food commodities and will cover three main sections. The first section encompasses some of the guidelines that have been implemented on management of pesticide application worldwide, such as the establishment of a value called Maximum Residue Level (MRL) through the application of Good Agricultural Practices (GAPs) into daily agricultural activities. A brief overview of the methods adopted in quantification of these trace residues in different food samples will also be covered. Briefly, pesticide analysis is usually performed in two stages: sample preparation and analytical instrumentation. Some of the preparation methods such as QuEChERs still remain as the technique of choice for most of the analytical scientists. In terms of the instrumentation such as the gas chromatography-mass spectrophotometry (GC-MS) and high performance-liquid chromatography (HPLC), these are still widely used, in spite of new inventions that are more sustainable and efficient such as the capillary electrophoresis (CE). Finally, the third section emphasizes on how pesticides can affect our health significantly whereby different types of pesticides result in different adverse health implications, despite its application benefits in agriculture in controlling pests. To date, there are limited reviews on pesticide usage in many agricultural-based nations; for the purpose of this review, Malaysia is selected to better illustrate pesticide regulations and implementation of policies. Finally, the review aims to provide an insight on how implementation of GAP and food safety assurance are inter-related and with this established correlation, to identify further measures for improvement to enable reinforcement of optimised agricultural practices specifically in these countries.
This study investigates pest management practices among lowland farmers on growing
leafy and fruit vegetables, particularly focusing on the pesticide usage in controlling pest. In
Malaysia, vegetable productions in lowland areas are to some extent really important as in the
highland areas due to the wide marketing channel, from local till traded across border. Yet, the
ignorance of vegetables safety regarding the appropriate of pesticide usage by farmers was
undeniable, as the market demands only products with good extrinsic quality. Thus a survey
was conducted among of 85 of lowland vegetable farmers to get information on their pest
management practices in farms. Result showed that the pesticide application by farmers on
vegetables crops still indicated a calendar spraying practices. In most cases, farmers tend to
harvest the vegetable products shortly after a few days of last pesticide spraying. In order to
enhance the food safety control starting from the primary production, extensive monitoring of
the current pesticide usage by farmers in vegetable productions is vital to provide an updated
data on the food safety risk regarding to the pesticide residues. Therefore, the thrust of this
paper was to get a better understanding on the level of safe pesticide usage among vegetables
farmers especially in areas of growing vegetables productions.
Laboratory experiments were conducted to evaluate adsorption, desorption and mobility of metsulfuron-methyl in soils of the oil palm agroecosystem consisting of the Bernam, Selangor, Rengam and Bongor soil series. The lowest adsorption of metsulfuron-methyl occurred in the Bongor soil (0.366 ml g(-1)), and the highest in the Bemam soil (2.837 ml g(-1). The K(fads) (Freundlich) values of metsulfuron-methyl were 0.366, 0.560, 1.570 and 2.837 ml g(-1) in Bongor, Rengam, Selangor and Bemam soil, respectively. The highest K(fdes) value of metsulfuron-methyl, observed in the Bemam soil, was 2.563 indicating low desorption 0.280 (relatively strong retention). In contrast, the lowest K(fdes) value of 0.564 was observed for the Bongor soil, which had the lowest organic matter (1.43%) and clay content (13.2%). Soil organic matter and clay content were the main factors affecting the adsorption of metsulfuron-methyl. The results of the soil column leaching studies suggested that metsulfuron-methyl has a moderate potential for mobility in the Bernam and Bongor soil series with 19.3% and 39%, respectively for rainfall at 200 mm. However, since metsulfuron-methyl is applied at a very low rate (the maximum field application rate used was 30 g ha(-1)) and is susceptible to biodegradation, the potential forground water contamination is low.
In this study, a rapid, specific and sensitive multi-residue method based on acetonitrile extraction followed by dispersive solid-phase extraction (d-SPE) clean-up was implemented and validated for multi-class pesticide residues determination in palm oil for the first time. Liquid-liquid extraction followed by low-temperature precipitation procedure was evaluated in order to study the freezing-out clean-up efficiency to obtain high recovery yield and low co-extract fat residue in the final extract. For clean-up step, d-SPE was carried out using a combination of anhydrous magnesium sulphate (MgSO(4)), primary secondary amine, octadecyl (C(18)) and graphitized carbon black. Recovery study was performed at two concentration levels (10 and 100 ng g(-1)), yielding recovery rates between 74.52% and 97.1% with relative standard deviation values below 10% (n = 6) except diuron. Detection and quantification limits were lower than 5 and 9 ng g(-1), respectively. In addition, soft matrix effects (≤±20%) were observed for most of the studied pesticides except malathion that indicated medium (20-50%) matrix effects. The proposed method was successfully applied to the analysis of suspected palm oil samples.