A new graphene-based tetraethoxysilane-methyltrimethoxysilane sol-gel hybrid magnetic nanocomposite (Fe3O4@G-TEOS-MTMOS) was synthesised, characterized and successfully applied in magnetic solid-phase extraction (MSPE) for simultaneous analysis of polar and non-polar organophosphorus pesticides from several water samples. The Fe3O4@G-TEOS-MTMOS nanocomposite was characterized using Fourier transform-infrared spectroscopy, energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy and X-ray diffraction. Separation, determination and quantification were achieved using gas chromatography coupled with micro electron capture detector. Adsorption capacity of the sorbent was calculated using Langmuir equation. MSPE was linear in the range 100-1000 pg mL(-1) for phosphamidon and dimethoate, and 10-100 pg mL(-1) for chlorpyrifos and diazinon, with limit of detection (S/N = 3) of 19.8, 23.7, 1.4 and 2.9 pg mL(-1) for phosphamidon, dimethoate, diazinon and chlorpyrifos, respectively. The LODs obtained is well below the maximum residual level (100 pg mL(-1)) as set by European Union for pesticides in drinking water. Acceptable precision (%RSD) was achieved for intra-day (1.3-8.7%, n = 3) and inter-day (7.6-17.8%, n = 15) analyses. Fe3O4@G-TEOS-MTMOS showed high adsorption capacity (54.4-76.3 mg g(-1)) for the selected OPPs. No pesticide residues were detected in the water samples analysed. Excellent extraction recoveries (83-105%) were obtained for the spiked OPPs from tap, river, lake and sea water samples. The newly synthesised Fe3O4@G-TEOS-MTMOS showed high potential as adsorbent for OPPs analysis.
A headspace solid-phase microextraction method has been developed for the determination of 8 pesticides in vegetables and fruits by using gas chromatography with an electron capture detector. Two types of fibers (polyacrylate, 85 microm and polydimethylsiloxane, 100 microm) have been assayed and compared. The main factors: extraction and desorption parameters, ionic strength, and the effects of dilution and organic solvents, were studied and optimized. The optimized procedures resulted in more than 80% recovery for all the investigated vegetable and fruit samples with RSD values below 10%.
Soil columns were collected from a blueberry field, and insecticide solutions were allowed to leach through these columns. Insecticides from four different chemical classes were applied at two different rates: the concentration at which the insecticides wash off blueberries under rainfall conditions and the labeled field rate at which they are sprayed. The soil columns were divided into thirds; top, middle and bottom. Soil bioassays using Eisenia foetida Savigny, as an indicator species, were set up to determine the toxicity of the insecticides at a top, middle and bottom layer of the soil column. The mass of E. foetida was also measured after the bioassay experiment was completed. The concentrations at which insecticides wash-off of blueberries from rainfall were not lethal to E. foetida. In order to support mortality data, insecticide residues were quantified in the soil layers for each insecticide. Under field rate leaching conditions, carbaryl showed the high levels of toxicity in the top and middle layers of soil suggesting that it has the highest risk to organisms from leaching. This study will help blueberry growers make informed decisions about insecticide use, which can help minimize contamination of the environment.
The proximate composition including mineral and vitamin contents of 16 fruits and 46 vegetables (leaves, fruits, palm hearts and shoots) of indigenous origin in Sarawak are provided. Fruits like dabai (Canarium odontophyllum), kembayau (Dacryodes rostrata f. cuspidata), durian nyekak (Durio kutejensis) and durian kuning (Durio graveolens) are very nutritious with high values for energy, protein and potassium. Among the vegetables, the protein content of letup (Passiflora foetida), kepayang (Pangium edule) and tubu (Pycnarrhena tumetacta) is high, ranging from 6 to 7%. The range of nutrients among foods of indigenous origin are generally comparable with those of many cultivated species except for vitamin C, which is lower. Teh Kampung (Leucosyke capitellata) leaves are particularly high in magnesium (626 mg/100 g). Some of the indigenous vegetables contain antinutritional factors. Kepayang has very high levels of hydrogen cyanide (1834 µg/g on dry basis) but this poison can be completely evaporated by boiling. Indigenous fruits and vegetables which are pesticide residue free are important food sources for rural populations. Nutritious indigenous fruits and vegetables have the potential to be promoted for wider use, domestication and commercialization.
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.
An efficient and rapid method for the analysis of pesticide residues in cocoa beans using gas and liquid chromatography-tandem mass spectrometry was developed, validated and applied to imported and domestic cocoa beans samples collected over 2 years from smallholders and Malaysian ports. The method was based on solvent extraction method and covers 26 pesticides (insecticides, fungicides, and herbicides) of different chemical classes. The recoveries for all pesticides at 10 and 50 μg/kg were in the range of 70-120% with relative standard deviations of less than 20%. Good selectivity and sensitivity were obtained with method limit of quantification of 10 μg/kg. The expanded uncertainty measurements were in the range of 4-25%. Finally, the proposed method was successfully applied for the routine analysis of pesticide residues in cocoa beans via a monitoring study where 10% of them was found positive for chlorpyrifos, ametryn and metalaxyl.
Improved methods for extraction and clean up of fluroxypyr residue in water have been established. Two methods of fluroxypyr extraction were used, namely, Direct Measurement of fluroxypyr and Concentration of fluroxypyr onto A Solid Phase Extraction (SPE) Adsorbent, followed by elution with solvent before determination of fluroxypyr. The recovery for Direct Measurement of fluroxypyr in water containing 8-100 microg L(-1), ranged from 86 to 110% with relative standard deviation of 0.7 to 2.15%. For the second method, three types of SPE were used, viz. C18, C18 end-capped and polyvinyl dibenzene (ISOLUTE ENV+). The procedure involved concentrating the analyte from fluroxypyr-spiked water at pH 3, followed by elution of the analyte with 4 mL of acentonitrile. The recovery of fluroxypyr from the spiked sample at 1 to 50 microg L(-1) after eluting through either C18 or C18 end-capped ranged from 40-64% (with relative standard deviation of 0.7 to 2.15) and 41-65% (with standard deviation of 1.52 to 11.9). The use of ISOLUTE ENV+, gave better results than the C18, C18 end-capped or the Direct Measurement Methods. The recovery and standard deviation of fluroxypyr from spiked water using ISOLUTE ENV+ ranged from 91-102% and 2.5 to 5.3, respectively.
Concern about environmental protection has increased over the years from a global viewpoint. To date, the percolation of pesticide waste into the groundwater tables and aquifer systems remains an aesthetic issue towards the public health and food chain interference. With the renaissance of activated carbon, there has been a consistent growing interest in this research field. Confirming the assertion, this paper presents a state of art review of pesticide agrochemical practice, its fundamental characteristics, background studies and environmental implications. Moreover, the key advance of activated carbon adsorption, its major challenges together with the future expectation are summarized and discussed. Conclusively, the expanding of activated carbon adsorption represents a plausible and powerful circumstance, leading to the superior improvement of environmental preservation.
A headspace single-drop microextraction (HS-SDME) procedure is optimized for the analysis of organochlorine and organophosphorous pesticide residues in food matrices, namely cucumbers and strawberries by gas chromatography with an electron capture detector. The parameters affecting the HS-SDME performance, such as selection of the extraction solvent, solvent drop volume, extraction time, temperature, stirring rate, and ionic strength, were studied and optimized. Extraction was achieved by exposing 1.5 microL toluene drop to the headspace of a 5 mL aqueous solution in a 15-mL vial and stirred at 800 rpm. The analytical parameters, such as linearity, correlation coefficients, precision, limits of detection (LOD), limits of quantification (LOQ), and recovery, were compared with those obtained from headspace solid-phase microextraction (HS-SPME) and solid-phase extraction. The mean recoveries for all three methods were all above 70% and below 104%. HS-SPME was the best method with the lowest LOD and LOQ values. Overall, the proposed HS-SDME method is acceptable in the analysis of pesticide residues in food matrices.
The purpose of this study was to develop a method for the determination of fluroxypyr (4-amino-3,5-dichloro-6-fluro2-pyridyloxyacetic acid) residue in palm oil namely crude palm oil (CPO) and crude palm kernel oil (CPKO). The method involves the extraction of the herbicide from the oil matrix followed by low temperature precipitation and finally quantification of the residues using the high performance liquid chromatography (HPLC). The extraction efficiency of the method was evaluated by conducting recovery studies. The recovery of fluroxypyr from the fortified CPO samples ranged from 78%-111% with the relative values for the coefficient of variation ranging from 1.4 to 8.6%. Furthermore, the recovery of fluroxypyr from the spiked CPKO samples ranged from 91-107% with the relative values for the coefficient of variation ranging from 0.6 to 4.5%. The minimum detection limit of fluroxypyr in CPO and CPKO was 0.05 microg/g. The method was used to determine fluroxypyr residues from the field-treated samples of CPO and CPKO. When fluroxypyr was used for weed control in oil palm plantations no residue was detected in CPO and CPKO irrespective of the sampling interval and the dosage applied at the recommended or double the manufacturer's recommended dosage.
Land application of sludge as fertilizers is a way of disposal and recycling of sludge. However, public concern has arisen due to the fact that organic contaminants in sludge may ultimately enter the food chain. Hence the need arises to analyse the organic contaminants such as PAHs and OCPs in sludge. In this study, Soxhlet was utilised as the extraction method and the extracts subjected to extensive cleanup via either silica columns or solid phase extraction cartridges prior to analysis using gas chromatography or high performance liquid chromatography. Sludge samples were collected from the drying beds of oxidation ponds in three locations in South Johore. OCPs such as heptachlor, dieldrin and pp-DDT were detected in low amounts (52-159 mg/kg) whereas PAHs such as naphthalene, phenanthrene, fluoranthene and benzo(a)pyrene were detected in the range of 0.2-5.5 mg/kg dry mass. Subcritical water extraction (SWE) recovery studies of PAHs were also performed from spiked sludge samples. Although a recovery range of 41-68% was obtained using the SWE method, the results indicated the usefulness of the technique as an alternative to Soxhlet extraction for the analysis of PAHs in sludge samples.
Public concern about the adverse environmental and human health impacts of organochlorine contaminants led to strict regulations on their use in developed nations two decades ago. Nevertheless, DDT and several other organochlorine insecticides are still being used for agriculture and public health programs in developing countries in Asia and the South Pacific. As a consequence, humans in this region are exposed to greater dietary levels of organochlorines. In this review, published information on organochlorine concentrations in foodstuffs from South and Southeast Asia and Oceanic countries has been compiled. Foodstuffs that contribute to human exposures and dietary intakes of organochlorines were examined, and the data compared with those reported from more developed nations. Among various developing countries in Asia, considerable information on organochlorines in foodstuffs has been available from India since the late 1960s. DDT and HCH were the major insecticides in Indian foodstuffs. Concentrations of these insecticides have declined more than two orders of magnitude in farm products, such as food grains and vegetables, in two decades. Milk and milk products are the major sources of dietary exposure to DDT and HCH in India. The residues of these insecticides in dairy products were close to or above the MRLs of the FAO/WHO. Dietary intake of DDT and HCH by Indians was > 100 fold that in more developed nations. Sporadic incidences of greater concentrations (> 1 microgram/g) of aldrin, dieldrin, and heptachlor have been measured in Indian vegetables. Untreated surface waters could be a potential source of DDT and HCH exposure. In most Southeast Asian countries DDT was the common contaminant in animal origin foodstuffs. The higher percentage of p,p'-DDT in meat and fish from Southeast Asian countries, except Japan and Korea, indicated the recent use of DDt in vector control operations. Dietary intakes of DDt and HCH in Southeast Asia were an order of magnitude less than those of Indians but 5- to 10 fold greater than in more developed nations. In addition to DDT, aldrin and dieldrin were prominent in meat collected from Thailand and Malaysia. Aquatic food products from more industrialized countries, such as Japan, South Korea, Hong Kong, and Taiwan, contained significant levels of PCBs. In South Pacific countries, particularly in Australia and New Zealand, chlordanes and PCBs were the most prevalent organochlorines in foodstuffs. Food contamination by DDT, HCH, aldrin, and dieldrin was less than in developing countries in Asia but greater than in the U.S. and Japan. Intake of PCBs in Australia was greater than in the U.S. Meat and fish were the major sources of organochlorine exposure by Australians. Human dietary intake of organochlorines has been declining more slowly in developing countries in Asia. Current intakes were at least 5- to 100 fold greater than those in more developed nations, suggesting a greater risk from organochlorine exposure. Factors such as malnutrition, common among rural poor in developing nations, can increase these risks. Of greatest concern is the magnitude of exposure to organochlorines to which infants and children are subjected through human and dairy milk. The estimated intake of DDT by infants was at least 100 fold greater than the ADI of the FAO/WHO. In addition to DDT, excessive exposures to HCH and dieldrin may cause potential health effects in infants because they are more vulnerable to toxic effects. The design and implementation of appropriate epidemiological studies and their integration with monitoring of human, food, and environmental samples would be a major step in assessing the risks of organochlorine residues in foods and controlling or eliminating them. With the continued globalization of trade in food products, and the concomitant risk that food contaminated through point-source pollution may be widely distributed, identification of sources and their control should be matters of
Fruits and vegetables constitute a major type of food consumed daily apart from whole grains. Unfortunately, the residual deposits of pesticides in these products are becoming a major health concern for human consumption. Consequently, the outcome of the long-term accumulation of pesticide residues has posed many health issues to both humans and animals in the environment. However, the residues have previously been determined using conventionally known techniques, which include liquid-liquid extraction, solid-phase extraction (SPE) and the recently used liquid-phase microextraction techniques. Despite the positive technological effects of these methods, their limitations include; time-consuming, operational difficulty, use of toxic organic solvents, low selective property and expensive extraction setups, with shorter lifespan of instrumental performances. Thus, the potential and maximum use of these methods for pesticides residue determination has resulted in the urgent need for better techniques that will overcome the highlighted drawbacks. Alternatively, attention has been drawn recently towards the use of quick, easy, cheap, effective, rugged and safe technique (QuEChERS) coupled with dispersive solid-phase extraction (dSPE) to overcome the setback challenges experienced by the previous technologies. Conclusively, the reviewed QuEChERS-dSPE techniques and the recent cleanup modifications justifiably prove to be reliable for routine determination and monitoring the concentration levels of pesticide residues using advanced instruments such as high-performance liquid chromatography, liquid chromatography-mass spectrometry and gas chromatography-mass spectrometry.
Dicofol, a recommended Stockholm convention persistent organic pollutants (POPs) candidate is well known for its endocrine disruptive properties and has been extensively used as an organochlorine pesticide worldwide. The hydrodynamic cavitation (HC) treatment of Dicofol in aqueous media induced by a liquid whistle hydrodynamic cavitaion reactor (LWHCR) has been investigated while considering important parameters such as inlet pressure, initial concentration of Dicofol, solution temperature, pH, addition of H2O2 and radical scavenger for the extent of degradation. The pseudo-first-order degradation rate constant (k) was determined to be 0.073 min-1 with a cavitational yield of 1.26 × 10-5 mg/J at optimum operating conditions and a complete removal of Dicofol was achieved within 1 h of treatment. Considering the removal rate and energy efficiency, the optimal inlet pressure was found to be 7 bar, resulting in a cavitation number of 0.17. High performance liquid chromatography (HPLC) and Gas chromatography mass spectroscopy (GC-MS) analyses indicated a sharp decline in the concentration of Dicofol with treatment time and indicated the presence of degraded products. An 85% total organic carbon (TOC) removal was achieved within 1 h of treatment time, demonstrating successful mineralization of Dicofol. The obtained results suggest that the degradation of Dicofol followed thermal decomposition and successive recombination reactions at bubble-vapor interface. Overall, the attempted hydrodynamic cavitation demonstrated successful and rapid removal of endocrine disruptive chemicals such as Dicofol and is expected to provide efficient solution for wastewater treatment.
The residual activity of herbicides may be detrimental to the environment, requiring analysis of the persistent residues in the soil and water. A field study was conducted to measure the residues of Imidazolinone (IMI) in three Clearfield® rice field soils at three different locations in Malaysia. The analyses of IMI in the soil samples were carried out using a high-performance liquid chromatography (HPLC). These herbicides are widely used; however, few studies have been conducted on both residues, especially in the context of Malaysian soil. Residues of imazapic and imazapyr were found to fall within 0.03-0.58 µg/mL and 0.03-1.96 µg/mL, respectively, in three locations. IMI herbicides are persistent in the soil, and their residues remain for up to 85 days after application. A pre-harvest study was suggested for these herbicides on water, which will provide a clearer indicator on the use of IMI in Clearfield® rice fields.
This study focused on the residue detection of the herbicides triclopyr and glufosinate ammonium in the runoff losses from the Tasik Chini oil palm plantation area and the Tasik Chini Lake under natural rainfall conditions in the Malaysian tropical environment. Triclopyr and glufosinate ammonium are post-emergence herbicides. Both herbicides were foliar-sprayed on 0.5 ha of oil palm plantation plots, which were individualized by an uneven slope of 10-15%. Samples were collected at 1, 3, 7, 15, 30, 45, 60, 90, and 120 days after treatment. The concentrations of both herbicides quickly diminished from those in the analyzed sample by the time of collection. The highest residue levels found in the field surface leachate were 0.031 (single dosage, triclopyr), 0.041 (single dosage, glufosinate ammonium), 0.017 (double dosage, triclopyr), and 0.037 μg/kg (double dosage, glufosinate ammonium). The chromatographic peaks were observed at "0" day treatment (2 h after herbicide application). From the applied active ingredients, the triclopyr and glufosinate losses were 0.025 and 0.055%, respectively. The experimental results showed that both herbicides are less potent than other herbicides in polluting water systems because of their short persistence and strong adsorption onto soil clay particles.
This study investigates the presence and distribution of organochlorine pesticides in streams and the lake in the Sembrong Lake Basin in Malaysia. The catchment of Sembrong Lake has been converted to agricultural areas over the past 30 years, with oil palm plantations and modern agricultural farming being the main land use. Surface water samples were collected from eight sites comprising the stream and lake and analysed for 19 organochlorine pesticides (OCPs). In situ measurement of temperature, dissolved oxygen, pH and conductivity were also undertaken at each site. Aldrin, endrin, δ-BHC, 4,4-DDT, methoxychlor and endosulfan were the main OCPs detected in the lake basin. The total OCP concentration ranged between 5.42 and 349.2 ng/L. The most frequently detected OCPs were δ-BHC, heptachlor and aldrin. The maximum values detected were 23.0, 43.2 and 50.4 ng/L respectively. The highest concentration of OCPs was attributed to 4,4-DDT, but such high residue was rare and only detected once. Other OCP residues were low. Significant differences in the mean values were observed between lake and stream for dichlorodiphenyldichloroethylene (DDE) and α-endosulfan concentration (p
Occurrence and distribution of organochlorine pesticides (OCPs), organophosphate pesticides (OPPs), and pyrethroid pesticides (PYRs) residues in the leafy vegetables were analyzed together with the soil samples using gas chromatography-electron capture detector. Edible tissues of vegetables showed detectable residues of these compounds indicating the influence of the conventional farms and nearby organic farms. In the vegetables, the OCPs concentrations were recorded as nd-133.3 ng/g, OPPs as nd-200 ng/g, and PYRs as nd-33.3 ng/g. In the soil, the OCPs concentrations were recorded as nd-30.6 ng/g, OPPs as nd-26.6 ng/g, and for PYRs as nd-6.7 ng/g. Bioconcentration factor (BCF) was higher for the OPPs (0.3) than the OCPs and PYRs (1.1). The OCPs concentration in the vegetables decreased in the following order: spinach > celery > broccoli > cauliflower > cabbage > lettuce > mustard. For OPPs, the concentration decreased in the following order: cauliflower > spinach > celery > cabbage > broccoli > lettuce > mustard and for PYRs as spinach > celery > lettuce > cabbage > broccoli. Principal component analysis indicates that the sources of these pesticides are not the same, and the pesticide application on the vegetables depends on the type of crop. There is a significant positive correlation between OPPs and the soil (r = 0.65) as compared to OCPs and PYRs (r = 0.1) as the vegetables accumulated OPPs more efficiently than OCPs and PYRs.