Evaluation of the QuEChERS Method and Gas Chromatography-Mass Spectrometry for the Analysis Pesticide Residues in Water and Sediment

A method for the determination of pesticide residues in water and sediment was developed using the QuEChERS method followed by gas chromatography - mass spectrometry. The method was validated in terms of accuracy, specificity, linearity, detection and quantification limits. The recovery percentages obtained for the pesticides in water at different concentrations ranged from 63 to 116%, with relative standard deviations below 12%. The corresponding results from the sediment ranged from 48 to 115% with relative standard deviations below 16%. The limits of detection for the pesticides in water and sediment were below 0.003 mg L(-1) and 0.02 mg kg(-1), respectively.

Plasma cholinesterase characteristics in native Australian birds : significance for monitoring avian species for pesticide exposure

Cholinesterase-inhibiting pesticides are applied throughout Australia to control agricultural pests. Blood plasma cholinesterase (ChE) activity is a sensitive indicator of exposure to organophosphorus insecticides in vertebrates. To aid biomonitoring and provide reference data for wildlife pesticide-risk assessment, plasma acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities were characterised in nine species of native bird: King Quails (Excalfactoria chinensis), Budgerigars (Melopsittacus undulatus), White-plumed Honeyeaters (Lichenostomas penicillatus), Yellow-throated Miners (Manorina flavigula), Willie Wagtails (Rhipidura leucophrys), Australian Reed-Warblers (Acrocephalus australis), Brown Songlarks (Cincloramphus cruralis), Double-barred Finches (Taeniopygia bichenovii) and Australasian Pipits (Anthus novaeseelandiae). Plasma ChE activities in all species were within the range of most other avian species and all but one contained AChE and BChE; no AChE was present in King Quail, which has not previously been reported for any species. The lowest detectable plasma AChE activity was 0.10 μmol min^–1 mL^–1 in Budgerigars and the highest was 0.86 μmol min^–1 mL^–1 in Australian Reed-Warblers. BChE in the plasma ranged from 0.37 μmol min^–1 mL^–1 in Double-barred Finches to 0.90 μmol min^–1 mL^–1 in White-plumed Honeyeaters and Australian Reed-Warblers. The lowest proportion of AChE was found in Budgerigars (12.8%) and highest in Willie Wagtails (67.8%). No differences were detected in ChE activity at any time of day in Budgerigars and Zebra Finches (Taeniopygia guttata), although there was a significant difference in all ChE activity between seasons in Zebra Finches.

Physiological assessment of avian exposure to fipronil, a new-generation pesticide

Fipronil, a phenyl pyrazole pesticide, is aerially applied in semi-arid and agricultural areas of Australia to control locust outbreaks. Locust populations build to plague proportions when rainfall occurs in late winter and spring, promoting early vegetation growth. These conditions also attract breeding birds. Over 100 species have been observed coincident with locust control operations. Avian exposure to fipronil occurs via direct contact and by ingesting contaminated insects or seeds. Avian toxicity information demonstrates there is high species-specific variability in fipronil sensitivity in the few avian species studied. There is no research, however, explaining this variability, nor is there research regarding physiological or behavioural sub-lethal effects on avian species. This makes it extremely difficult to predict the toxicity of fipronil on unstudied species at high risk of exposure. Our research aims to resolve this lack of essential information in two ways: firstly we examine whether fipronil has identifiable sublethal effects in exposed birds and their offspring that compromise population health, and secondly evaluate avian metabolism of fipronil in selected species to gain insight into the mechanisms underlying variation in species sensitivity. Our results provide critically needed information for evaluating field effects of locust-control spraying in Australia.

Effects of invertebrate predators and a pesticide on temporary pond microcosms used for aquatic toxicity testing

The effects of increased trophic complexity, through the addition of predatory notonectids (Anisops deanei), on temporary pond microcosms used for aquatic toxicity testing were studied. Replicate microcosms were established using sediment from a dried temporary pond, and treated with one of four concentrations of the organochlorine pesticide endosulfan (0, 1, 10 or 50 μg/L), in the presence or absence of six A. deanei. The tanks were sampled regularly for nine weeks following the addition of the predators and the entire contents of each tank counted after 12 weeks. Analysis using non-metric multidimensional scaling (MDS) and non-parametric MANOVA showed that both Anisops and endosulfan at concentrations >10 μg/L significantly altered community structure. However, an interaction between the effects of Anisops and the effects of endosulfan was not detected. The addition of Anisops did not increase the variability of response and thus did not reduce the sensitivity of the test method.

Cholinesterase Research Outreach Project (CROP): measuring cholinesterase activity and pesticide use in an agricultural community

BACKGROUND: Australian farmers and their workers are exposed to a wide variety of pesticides. Organophosphate (OP) insecticides are a widely used class of pesticide used for animal husbandry practices (Naphthalophos for sheep dipping, jetting and drench), crop production for pest control (Dimethoate) and in public health (Maldison for head lice). Acute poisonings with this class of insecticide are reported among agricultural workers and children around the globe, due to the inhibition of acetylcholinesterase (AChE). Less is known about chronic exposures. Regular monitoring of erythrocyte AChE will enable farmers to identify potential exposure to organophosphate insecticides and take action to reduce exposures and improve their health and safety practices. This study aims to assess and improve the integration of AChE monitoring into routine point of care health clinics, and provide farming and non-farming people with a link between their AChE activity and their household chemical and agrichemical use. METHODS/DESIGN: The research will target individuals who work on mixed farming enterprises and routinely using OPs (n = 50) and non-farmers (n = 30). Baseline data are collected regarding demographic, health conditions and behaviours, Kessler 10 (K10) scores, chemical use and personal protection. Baseline anthropometric measures include height, weight, hip and waist circumference, body fat analysis and, biochemical analysis of fasted total serum cholesterol, triglycerides, low-density cholesterol (LDL), high-density cholesterol (HDL) and blood glucose. Analysis of erythrocyte cholinesterase (EAChE) activity is also conducted using a finger prick test. Testing of EAChE is then repeated in all participants every 3 weeks for a maximum of three times over a period 10 weeks. Participants are provided with full feedback and counselling about their EAChE activity after each reading and a detailed summary provided to all participants at the completion of the study. Data will be analysed using repeated measures within a general linear model. DISCUSSION: This work will provide an evidence base and recommendations for the integration of EAChE monitoring into Australian rural health clinics, leading to research which will further quantify pesticide exposure both on the farm and in the home, highlighting the importance of sustaining and providing a safe work and home environment for farming communities. TRIAL REGISTRATION: ACTRN12613001256763.

Supercritical fluid extraction for pesticide multiresidue analysis in honey: determination by gas chromatography with electron-capture and mass spectrometry detection

An analytical procedure using supercritical fluid extraction (SFE) and capillary gas chromatography with electron-capture detection was developed to determine simultaneously residues of different pesticides (organochlorine, organophosphorus, organonitrogen and pyrethroid) in honey samples. Fortification experiments were conducted to test conventional extraction (liquid-liquid) and optimize the extraction procedure in SFE by varying the CO2-modifier, temperature, extraction time and pressure. Best efficiency was achieved at 400 bar using acetonitrile as modifier at 90 degreesC. For the clean-up step, Florisil cartridges were used for both methods LLE and SFE. Recoveries for majority of pesticides from fortified samples of honey at fortification level of 0.01-0.10 mg/kg ranged 75-94% from both methods. Limits of detection found were less than 0.01 mg/kg for ECD and confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in selected-ion monitoring mode. The multiresidue methods in real honey samples were applied and the results of developed methods were compared. (C) 2004 Elsevier B.V. All rights reserved.

Design of a simple detection cell with extended optical path length for capillary electrophoresis: Application to multiresidue pesticide analysis

Absorbance detection in capillary electrophoresis (CE), offers an excellent mass sensitivity, but poor concentration detection limits owing to very small injection volumes (normally I to 10 nL). This aspect can be a limiting factor in the applicability of CE/UV to detect species at trace levels, particularly pesticide residues. In the present work, the optical path length of an on-column detection cell was increased through a proper connection of the column (75 mu m i.d.) to a capillary detection cell of 180 mu m optical path length in order to improve detectability. It is shown that the cell with an extended optical path length results in a significant gain in terms of signal to noise ratio. The effect of the increase in the optical path length has been evaluated for six pesticides, namely, carbendazim, thiabendazole, imazalil, procymidone triadimefon, and prochloraz. The resulting optical enhancement of the detection cell provided detection limits of ca. 0.3 mu g/mL for the studied compounds, thus enabling the residue analysis by CE/UV.

Evaluation of the performance of a castor-oil based formulation in limiting pesticide residues in strawberry crops

A study was made to evaluate the effect of a castor oil-based detergent on strawberry crops treated with different classes of pesticides, namely deltamethrin, folpet, tebuconazole, abamectin and mancozeb, in a controlled environment. Experimental crops of greenhouse strawberries were cultivated in five different ways with control groups using pesticides and castor oil-based detergent. The results showed that the group 2, which was treated with castor oil-based detergent, presented the lowest amount of pesticide residues and the highest quality of fruit produced.

A rapid, environmentally friendly, and reliable method for pesticide analysis in high-fat samples

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

ORGANOCHLORINE PESTICIDE-RESIDUES IN HUMAN-MILK IN THE RIBEIRAO-PRETO REGION, STATE OF SAO-PAULO, BRAZIL

Thirty-seven samples of human milk (colostrum) from donors living in the Ribeirao Preto region were analyzed to determine the levels of organochlorine pesticide residues. Donors were classified into two groups, i.e., occupationally exposed and non-exposed to pesticides. Other factors such as age, previous lactations, race, smoking habit, occupation, family income and educational level were also considered. Analysis was performed by preliminary lipid extraction followed by fractional partition on a column and finally by gas chromatography with an electron capture detector. Lindane was found in 32% of the samples in amounts of less than 0.001 mg/kg; heptachlor was found in 65% of the samples at mean levels of 0.001 mg/kg, i.e., a level five-fold lower than that established by FAO/WHO (1970) for cow's milk. Aldrin and endrin were not detected in any of the samples. Dieldrin was detected in only one sample at a level of 0.038 mg/kg, which is considered high. DDT and DDE amounts are reported as total DDT and at least one of these compounds was present in every sample. Amounts detected in donors occupationally exposed to pesticides ranged from 0.008 to 0.455 mg/kg (mean, 0.149 mg/kg), i.e., three times the limit established by FAO/WHO (1970), while values for donors who had not been exposed ranged from 0.002 to 0.072 mg/kg (mean, 0.025 mg/kg), i.e., half the limit. Considering the level of acceptable daily intake proposed by FAO/WHO (1973), lactents ingested 1% of the acceptable intake of lindane (all donors), 30% of the acceptable intake of heptachlor (all donors), 60% of the acceptable intake of DDT (non-exposed donors), and 3.7 times the acceptable intake of DDT (exposed donors). Comparing the present results with those obtained 10 years ago, the total DDT level in human milk is decreasing in this part of the country. The mean amount of organochlorine residues in non-exposed women's milk was one of the lowest levels among those recorded in the literature. DDT levels of occupationally exposed women's milk were comparable with those reported for developed countries and lower than those detected in Latin American countries. When the results of this survey are considered in relation to the advantages of breast-feeding, the risk-benefit balance is still favorable to breast-feeding. However, given the lack of long-term epidemiological studies, undesirable or harmful long-lasting effects cannot be excluded.