A comparison of dissipation of chlorothalonil, chlorpyrifos, and profenofos in a Malaysian agricultural soil between the field experiment and simulation by the PERSIST model was studied. A plot of sweet pea (Pisum sativum) from a farm in the Cameron Highlands was selected for the field experiment. The plot was treated with chlorothalonil, chlorpyrifos, and profenofos. Core soil collection was conducted according to the sampling schedule. Residues of the three pesticides were analyzed in the laboratory. Simulations of the three pesticides' persistency were also conducted using a computer-run software PERSIST. Generally, predicted data obtained using PERSIST were found to be high for the three pesticides except for one field measurement of chlorpyrifos. The predicted data for profenofos, which is the most mobile of the three pesticides tested, was not well matched with the observed data compared to chlorothalonil and chlorpyrifos.
Pesticides are of great concern because of their existence in ecosystems at trace concentrations. Worldwide pesticide use and its ecological impacts (i.e., altered environmental distribution and toxicity of pesticides) have increased over time. Exposure and toxicity studies are vital for reducing the extent of pesticide exposure and risk to the environment and humans. Regional regulatory actions may be less relevant in some regions because the contamination and distribution of pesticides vary across regions and countries. The risk quotient (RQ) method was applied to assess the potential risk of organophosphorus pesticides (OPPs), primarily focusing on riverine ecosystems. Using the available ecotoxicity data, aquatic risks from OPPs (diazinon and chlorpyrifos) in the surface water of the Langat River, Selangor, Malaysia were evaluated based on general (RQm) and worst-case (RQex) scenarios. Since the ecotoxicity of quinalphos has not been well established, quinalphos was excluded from the risk assessment. The calculated RQs indicate medium risk (RQm = 0.17 and RQex = 0.66; 0.1 ≤ RQ 1 (high risk) was observed for both the general and worst cases of chlorpyrifos, but only for the worst cases of diazinon at all sites from downstream to upstream regions. Thus, chlorpyrifos posed a higher risk than diazinon along the Langat River, suggesting that organisms and humans could be exposed to potentially high levels of OPPs.
Preventive treatment with insecticides at high dosing rates before planting of a new crop- soil drenching- is a common practice in some tropical intensive cropping systems, which may increase the risk of leaching, soil functioning, and pesticide uptake in the next crop. The degradation rates and migration of acephate and chlorpyrifos and their primary metabolites, methamidophos and 3,5,6-trichloropyridinol (TCP), have been studied in clayey red yellow podzolic (Typic Paleudults), alluvial (Typic Udorthents), and red yellow podzolic soils (Typic Kandiudults) of Malaysia under field conditions. The initial concentrations of acephate and chlorpyrifos in topsoils were found to strongly depend on solar radiation. Both pesticides and their metabolites were detected in subsoils at the deepest sampling depth monitored (50 cm) and with maximum concentrations up to 2.3 mg kg(-1) at soil depths of 10 to 20 cm. Extraordinary high dissipation rates for weakly sorbed acephate was in part attributed to preferential flow which was activated due to the high moisture content of the soils, high precipitation and the presence of conducting macropores running from below the A horizons to at least 1 m, as seen from a dye tracer experiment. Transport of chlorpyrifos and TCP which both sorb strongly to soil organic matter was attributed to macropore transport with soil particles. The half-lives for acephate in topsoils were 0.4 to 2.6 d while substantially longer half-lives of between 12.6 and 19.8 d were observed for chlorpyrifos. The transport through preferential flow of strongly sorbed pesticides is of concern in the tropics.
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.
Whole cell biosensors always face the challenge of low stability of biological components and short storage life. This paper reports the effects of poly(2-hydroxyethyl methacrylate) (pHEMA) immobilization on a whole cell fluorescence biosensor for the detection of heavy metals (Cu, Pb, Cd), and pesticides (dichlorophenoxyacetic acid (2,4-D), and chlorpyrifos). The biosensor was produced by entrapping the cyanobacterium Anabaena torulosa on a cellulose membrane, followed by applying a layer of pHEMA, and attaching it to a well. The well was then fixed to an optical probe which was connected to a fluorescence spectrophotometer and an electronic reader. The optimization of the biosensor using several factors such as amount of HEMA and drying temperature were undertaken. The detection limits of biosensor without pHEMA for Cu, Cd, Pb, 2,4-D and chlorpyrifos were 1.195, 0.027, 0.0100, 0.025 and 0.025 µg/L respectively. The presence of pHEMA increased the limits of detection to 1.410, 0.250, 0.500, 0.235 and 0.117 µg/L respectively. pHEMA is known to enhance the reproducibility of the biosensor with average relative standard deviation (RSD) of ±1.76% for all the pollutants tested, 48% better than the biosensor without pHEMA (RSD = ±3.73%). In storability test with Cu 5 µg/L, the biosensor with pHEMA performed 11.5% better than the test without pHEMA on day-10 and 5.2% better on day-25. pHEMA is therefore a good candidate to be used in whole cell biosensors as it increases reproducibility and enhances biosensor storability.
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.
The application of organophosphorus pesticides (OPPs) increased gradually because of the rise in global food demand that triggered the agriculture sector to increase the production, leading to OPP residues in the surface water. This study elucidated the presence of OPPs and estimated its ecological risk in the riverine ecosystem of the urbanised Linggi River, Negeri Sembilan, Malaysia. The OPP concentration in surface water was determined using solid-phase extraction method and high-performance liquid chromatography coupled with diode array detection. Further, the ecological risk was estimated by using the risk quotient (RQ) method. The three OPPs, i.e. chlorpyrifos, diazinon, and quinalphos were detected with mean concentrations of 0.0275 µg/L, 0.0328 µg/L, and 0.0362 µg/L, respectively. The OPPs were at high risk (in general and worst cases) under acute exposure. The estimated risk of diazinon was observed as medium for general (RQm = 0.5857) and high for worst cases (RQex = 4.4678). Notably, the estimated risk for chlorpyrifos was high for both general and worst cases (RQm = 1.9643 and RQex = 11.5643) towards the aquatic ecosystem of the Linggi River. Chronic risk of quinalphos remains unknown because of the absence of toxicity endpoints. This study presented clear knowledge regarding OPP contamination and possible risk for aquatic ecosystems. Hence, OPPs should be listed as one of the main priority contaminants in pesticide mitigation management in the future.