This review presents the application of carbon nanotubes as sorbent materials in the analysis of pesticide residues in fruits and vegetables. The advantages, limitations, and challenges of carbon nanotubes, with respect to their use in analytical chemistry, are presented. The efficiency of their application as extraction sorbent materials (in terms of LOD, LOQ, linearity, relative recovery, and RSD) in SPE, solid-phase microextraction, multi-plug filtration clean-up, matrix solid-phase dispersion, and the quick, easy, cheap, effective, rugged and safe method is reported. The synthesis, functionalization, purification, and characterization methods of carbon nanotubes are also discussed.
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.
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.
This study determined the concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), organochlorine (OC) pesticides, and tris(4-chlorophenyl) methane (TCPMe) in human breast milk samples collected in 2003 from primipara mothers living in Penang, Malaysia. OCs were detected in all the samples analyzed with DDTs, hexachlorocyclohexane isomers (HCHs), and PCBs as the major contaminants followed by chlordane compounds (CHLs), hexachlorobenzene (HCB), and TCPMe. The residue levels of DDTs, HCHs, and CHLs were comparable to or higher than those in general populations of other countries, whereas PCBs and HCB were relatively low. In addition, dioxins and related compounds were also detected with a range of dioxin equivalent concentrations from 3.4 to 24 pg-TEQs/g lipid wt. Levels of toxic equivalents (TEQs) were slightly higher than those in other developing countries but still much lower than those of industrialized nations. One donor mother contained a high TEQs level, equal to the mean value in human breast milk from Japan, implying that some of the residents in Malaysia may be exposed to specific pollution sources of dioxins and related compounds. No association was observed between OCs concentrations and maternal characteristics, which might be related to a limited number of samples, narrow range of age of the donor mothers, and/or other external factors. The recently identified endocrine disrupter, TCPMe, was also detected in all human breast milk samples of this study. A significant positive correlation was observed between TCPMe and DDTs, suggesting that technical DDT might be a source of TCPMe in Malaysia. The present study provides a useful baseline for future studies on the accumulations of OCs in the general population of Malaysia.
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
Paddy fish (Trichogaster pectoralis Regan) were collected from five sampling locations in a major paddy-growing area of Malaysia and analysed for organochlorine residues. During the same period, ten farming families, chosen at random from each of the five sampling sites, were interviewed. Information was obtained about the quantity of paddy fish consumed, the amount and type of pesticide used on the paddy-field, and the frequency of application.The pesticide residues found in the fish samples were aldrin/dieldrin, chlordane, HCH, and DDT. Only the projected maximum intake level for aldrin/dieldrin approached the acceptable daily intake as recommended by FAO/WHO; other residue levels were relatively low. However, this study considered only fish; the total daily intake of pesticide residues by the Malaysian paddy farmer may be considerably increased by consumption of other contaminated food.
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%.
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
A novel sol-gel hybrid methyltrimethoxysilane-tetraethoxysilane (MTMOS-TEOS) was produced and applied as sorbent for solid phase extraction (SPE). Five selected organophosphorus pesticides (OPPs) were employed as model compounds to evaluate the extraction performance of the synthesized sol-gel organic-inorganic hybrid MTMOS-TEOS. Analysis was performed using gas chromatography-mass spectrometry. Several important SPE parameters were optimized. Under the optimum extraction conditions, the method using the sol-gel organic-inorganic hybrid MTMOS-TEOS as SPE sorbent showed good linearity in the range of 0.001-1 μg L(-1), good repeatability (RSD 2.1-3.1%, n=5), low limits of detection at S/N=3 (0.5-0.9 pg mL(-1)) and limit of quantification (1-3 pg mL(-1), S/N=10). The performance of the MTMOS-TEOS SPE was compared to commercial C18 Supelclean SPE since C18 SPE is widely used for OPPs. The MTMOS-TEOS SPE method LOD was 500-600 × lower than the LOD of commercial C18 SPE. The LOD achieved with the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent allowed the detection of these OPPs in drinking water well below the level set by European Union (EU) at 0.1 μg L(-1) of each pesticides. The developed MTMOS-TEOS SPE method was successfully applied to real sample analysis of the selected OPPs from several water samples and its application extended to the analysis of several fruits samples. Excellent recoveries and RSDs of the OPPs were obtained from the various water samples (recoveries: 97-111%, RSDs 0.4-2.8%, n=3) and fruit samples (recoveries: 96-111%), RSDs 1-4%, n=5) using the sol-gel organic-inorganic hybrid MTMOS-TEOS SPE sorbent. Recoveries and RSDs of OPPs from river water samples and fruit samples using C18 Supelclean SPE sorbent were 91-97%, RSD 0.9-2.6, n=3 and 86-96%, RSD 3-8%, n=5, respectively). The novel sol-gel hybrid MTMOS-TEOS SPE sorbent demonstrate the potential as an alternative inexpensive extraction sorbent for OPPs with higher sensitivity for the OPPs.
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.
Solid-phase microextraction (SPME) is a solvent-less sample preparation method which combines sample preparation, isolation, concentration and enrichment into one step. In this study, multivariate strategy was used to determine the significance of the factors affecting the solid phase microextraction of pesticide residues (fenobucarb, diazinon, chlorothalonil and chlorpyrifos) using a randomised factorial design. The interactions and effects of temperature, time and salt addition on the efficiency of the extraction of the pesticide residues were evaluated using 2(3) factorial designs. The analytes were extracted with 100 μm PDMS fibres according to the factorial design matrix and desorbed into a gas chromatography-mass spectrometry detector. The developed method was applied for the analysis of apple samples and the limits of detection were between 0.01 and 0.2 μg kg(-)(1), which were lower than the MRLs for apples. The relative standard deviations (RSD) were between 0.1% and 13.37% with average recovery of 80-105%. The linearity ranges from 0.5-50 μg kg(-)(1) with correlation coefficient greater than 0.99.
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.
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.
Pesticides are the leading defence against pests, but their unsafe use reciprocates the pesticide residues in highly susceptible food and is becoming a serious risk for human health. In this study, mint extract and riboflavin were tested as photosensitisers in combination with light irradiation of different frequencies, employed for various time intervals to improve the photo-degradation of deltamethrin (DM) and lambda cyhalothrin (λ-CHT) in cauliflower. Different source of light was studied, either in ultraviolet range (UV-C, 254 nm or UV-A, 320-380 nm) or sunlight simulator (> 380-800 nm). The degradation of the pesticides varied depending on the type of photosensitiser and light source. Photo-degradation of the DM and λ-CHT was enhanced by applying the mint extracts and riboflavin and a more significant degradation was achieved with UV-C than with either UV-A or sunlight, reaching a maximum decrement of the concentration by 67-76%. The light treatments did not significantly affect the in-vitro antioxidant activity of the natural antioxidants in cauliflower. A calculated dietary risk assessment revealed that obvious dietary health hazards of DM and λ-CHT pesticides when sprayed on cauliflower for pest control. The use of green chemical photosensitisers (mint extract and riboflavin) in combination with UV light irradiation represents a novel, sustainable, and safe approach to pesticide reduction in produce.
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.
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.
Studies on persistence, mobility and the effect of repeated application of permethrin on its half-life were carried out under field conditions. The half-life of permethrin in the top 20 cm of the soil increased from 11.5 to 23.6 days as the application rates increased from 35 to 140 g ha(-1). Induced by heavier rainfall, more residues moved downward in trial 2 than in trial 1. Repeated applications enhanced degradation rates and mobility of permethrin in the soil. The residue level in the 0-5-cm layer was reduced at day 28 after 17 consecutive applications to a level lower than after 5 applications. The half-life of permethrin was reduced from 15.9 days to 11.2 days after 5 and 17 applications, respectively. The residue reached the 15-20 cm layer much earlier (approximately 3 days after treatment) in soil that received 17 applications as compared to those with two applications.