Determination of organochlorine pesticide and polychlorinated biphenyl residues in fatty fish by tandem solid-phase extraction cleanup

A rapid, multiresidue solid-phase extraction (SPE) technique for determination of organochlorine pesticide and polychlorinated biphenyl (PCB) residues in nonfatty fish was modified for use with fatty fish. In the modified procedures, samples are extracted with acetonitrile, and the extract is cleaned up with both C18 and Florisil SPE columns. Residues are determined by gas chromatography with electron capture detection. The original method was modified for use with fatty fish by reducing the amount of tissue extracted and by using an improved Florisil SPE cleanup. Recovery data are presented for 24 fortified organochlorine pesticide residues (0.12 ppm) and 3 fortified PCB residues (0.80 ppm) from flounder, bluefish, and shad samples, which contained 0.8, 5.4, and 22.6% fat, respectively. For the 3 types of fish, recoveries of 23 of 24 fortified organochlorine pesticide residues ranged from 55 to 129%, and recoveries of 3 fortified PCB residues ranged from 55 to 104%. There were no significant differences in recovery based on fish species and/or fat content for the majority of residues studied. This SPE method and the official AOAC method yielded comparable results for fish containing incurred organochlorine residues.     

Technical problems in determining safe re-entry intervals

Organophosphate pesticide residues have been responsible for periodic outbreaks of acute intoxication among California fieldworkers for over 30 years. In 1971, California established 're-entry intervals' to protect workers against overexposure to these residues. These intervals are stipulated times which must elapse between pesticide application and entry into the field for work involving substantial foliar or soil contact. The re-entry strategy depends upon a relatively predictable relation between time post-application and the level of the pesticide residue. It now appears that there are thiophosphates for which the residue hazard is not related to time in a stable way. This circumstance and the continued occurrence of poisoning incidents have focused attention on the quantitative aspects of the relationships between pesticide residue and toxicological response in humans. In the last decade, considerable progress has been made in elucidating these relationships and it now appears to be possible to outline the data requirements for a comprehensive regulatory solution to this longstanding occupational health problem.     

Pesticide residues in eggs and chicks from laying hens fed low levels of several chlorinated hydrocarbon pesticides

Eighty-four Single-Comb While Leghorn laying hens housed individually in laying cages were fed rations containing less than 0.1 p.p.m. of dieldrin, DDT, heptachlor and mirex individually or in combination for 7 days and in combination for 15 weeks. DDT residues in egg yolk reached 0.043 p.p.m. by 7 days when fed in combination with the other pesticides. None of the residues were above FDA action level at 7 days and all had declined to below trace levels by 8 weeks after termination of pesticide feeding. Residues in eggs from hens fed all four pesticides for 15 weeks increased steadily for the first few weeks and then reached a plateau or increased only slightly until pesticide feeding was terminated. By the end of the 5th week of pesticide feeding all pesticides except DDT had exceeded FDA action levels for pesticides in eggs. DDT residues reached a level of 0.139 p.p.m. by 8 weeks and did not increase thereafter. Traces of the pesticides were still present 24 weeks after termination of pesticide feeding. The pesticides tested did not affect fertility of hatchability of eggs collected during the 14th and 15th weeks of pesticide feeding. Total carcass fat of chicks hatched from these eggs had 0.024 p.p.m. dieldrin, .049 p.p.m. DDT, .001 p.p.m. heptachlor epoxide and, 0.47 mirex at 1 day of age.     

Analysis of 2,2,2-trifluoroethyl derivatives of carboxylic acid herbicides by gas chromatography with mass-selective and electron capture detection

A method for derivatizing carboxylic acid herbicides with 2,2,2-trifluoroethanol (TFE) in preparation for gas chromatographic (GC) analysis was developed. Esterification efficiency was determined by GC with electron capture detection (ECD), and esters were identified by GC with mass-selective detection (MSD). On the basis of reaction temperature for optimum esterification efficiency, 13 common carboxylic acid herbicides were separated into 2 groups before reaction with TFE. TFE derivatization was optimized for simultaneous analyses by altering reaction temperature, re action time, and concentration of sulfuric acid in reaction solutions. The method is simple, safe, and economical, and it gives good resolution without a laborious cleanup. Recovery of 13 analytes from water, taken from a pesticide residue well, was greater than 80% for all except 2 analytes. The well-water was fortified with analytes at the lower microgram-per-liter concentrations required for detection of pesticide residues in potable water systems. The method can simultaneously determine multiple herbicide residues in water samples with a high degree of accuracy and precision.     

Organochlorine and organophosphorus pesticide residues in food from Egyptian local markets

A market basket survey was conducted to monitor organochlorine and organophosphorus pesticide residues in potatoes, citrus fruits, and fish collected from local Egyptian markets. Maximum Residue Limits (MRLs) of the Codex Committee on Pesticide Residues for gamma-hexachlorocyclohexane (HCH) in potatoes were exceeded in 8 samples and for DDT in 2 samples. The aging of HCH and DDT indicated a recent use of both pesticides during the potato storage period between cultivation seasons. However, such use is illegal because HCH mixture isomers (gammaxane) and DDT have been officially prohibited from agricultural use in Egypt since 1980. The highest residue levels of fenitrothion (3.8 ppm) in potatoes may be due to its repeated use before and after harvest. No organochlorine pesticide residues were found in citrus fruits. None of the detected organophosphorus pesticides exceeded their MRLs. HCH and DDT residue limits were exceeded in 5 and 7 fish samples, respectively, collected from 12 markets throughout the country. The heptachlor MRL was violated in only one fish sample (3.9 ppm).     

Epidemiologic study of physiological effects in usual and volunteer citrus workers from organophosphate pesticide residues at reentry

Biological parameters associated with organophosphate (OP) pesticide exposure were evaluated in a study of citrus harvesters. Changes in these parameters related to environmental residues of cholinesterase (ChE) inhibiting pesticides were studied. Further, it was determined whether usual and volunteer workers differed in their biochemical parameters after exposure to pesticide residues during field operations. Urine metabolite findings for usual farm workers showed that some exposure to OP pesticides had occurred. Too few workers were available during the reentry stage of the field study to evaluate the effect of this exposure on blood ChE. Baseline (nonexposure) acetylcholinesterase (AChE) and plasma cholinesterase (PChE) activities were significantly higher in usual (Mexican American) workers than in volunteer workers (student volunteers). Student volunteers in the test citrus grove showed statistically significant declines in PChE during the exposure period, yet changes in AChE activity, urine metabolites, and residue levels were very small. The implications of these findings are discussed in light of current reentry standards as well as future epidemiologic studies on reentry research.     

Determination of pesticide residues in fruit and vegetables

A review concerning the determination of pesticide residues in fruit and vegetables is presented. The basic principles and recent developments in the extraction and quantitation of pesticides are discussed. Consideration is given to solid phase and supercritical extraction techniques, automation and robotic systems, and immunoassay procedures.     

Organochlorine residues in fish oil dietary supplements: comparison with industrial grade oils

The market for fish oils as dietary supplements is of global importance. Although it is widely recognised that lipophilic organic chemicals, particularly organochlorines, can accumulate in fish oils, dietary supplements are not routinely considered when estimating average daily intakes for these contaminants. This paper reports levels of organochlorine residues in 44 fish oils, collected from 15 countries between 1994 and 1995, including 38 purchased over the counter as dietary supplements. Despite controls on the use of persistent organochlorine substances, appreciable quantities are found in oils sold as dietary supplements. Levels are discussed in relation to the significance of fish oil dietary supplements as contributors to daily intake of PCBs and pesticide residues.     

Modeling Sorption Behavior of Atrazine on Intact Soil Columns

The sorption behavior of atrazine (2-chloro-4-ethylamino-6-isopropylamino-s-triazine), a commonly used herbicide for corn, on intact soil columns was studied by incorporating a new two-stage sorption mechanism into PESTFADE, a pesticide fate and transport model. This mechanism takes into account intraparticle diffusion of pesticide into the soil matrix (also sometimes known as bound residues), the sorption capacity of soil, and a variable pesticide distribution coefficient Kd. The modified model's performance was verified by comparing simulated values with those obtained from an intact column study in the laboratory. The two-stage mechanism was also compared and contrasted with the conventional adsorption approach based on a constant Kd. Simulations with the two-stage mechanism indicated a closer agreement with measured values (deviations in the range of 5–65%) than that of the conventional adsorption approach (deviations in the range of 10–700%). Furthermore, it was found that simulated values were particularly sensitive to soil tortuosity τ, soil bulk density ρ, soil moisture content θw, labile sorption capacity θc, and intraparticle diffusion parameters.     

Caring in grief

Coming into the milk and dairy products from animals, pesticides exert a high effect on human health. Depending on the fatness of dairy products and a process, the levels of pesticide residues vary greatly. Toxic agents and their metabolic products are most completely removed by vacuum deodorization. Monitoring the levels of pesticides in the milk and dairy products requires introduction of new methods for determining toxic agents and use of well-studied and less toxic compounds.     

Aldicarb Transport in Subsurface Environment: Comparison of Models

In this paper, two different pesticide transport simulation models are presented and compared to carry out preliminary analysis on the applicability of those models in determining ground-water vulnerability to aldicarb contamination. The first model is a physically based analytical model that simulates 1D pesticide movement in soils, based on the concept of complete mixing and 2D advective-dispersive transport in the aquifer. The second model is a numerical simulation model that links the existing numerical codes PRZM2, MODFLOW, and MT3D to simulate pesticide transport in the subsurface. The concentrations of aldicarb residues in soil and in the aquifer calculated by the two models are found to be in good agreement. However, the analytical model tends to produce an earlier arrival of the peak concentration in each year due to the assumption of complete mixing. It is also found that the infiltrating water following aldicarb application plays a significant role on the leaching potential of aldicarb, which is also affected by various meteorological and hydrological factors as well as by agricultural practices.     

固相萃取-气相色谱法测定大米中有机氯有机磷农药残留

采用固相萃取方法,结合气相色谱建立了同时检测大米中15种有机氯、有机磷农药残留的分析方法。样品用乙腈提取,氨基固相萃取柱净化,经DB-5石英毛细管柱分离后,直接用气相色谱(GC)检测,外标法定量。结果表明15种农药在0.01~0.2μg/mL浓度范围内呈现良好的线性关系,相关系数r均大于0.9951,样品在2个添加水平时的回收率为85.9%~103%,相对标准偏差(RSD)为1.3%~7.3%,检出限为0.002~0.004 mg/kg。该方法样品前处理简单、高效,测定的准确性好,灵敏度高,适用于大米中多种类农药残留的分析。     

Methods for the determination of organochlorine pesticide residues in human serum

The effectiveness of solid-phase extraction with Florisil for the determination of 12 organochlorine pesticide residues from human serum was examined. Recoveries greater than 84% and coefficients of variation better than 19% were obtained. Others methods, such as column partition and matrix solid-phase dispersion, were compared. The better method provides quantification limits ranging from 1.08 microg/l for gamma-HCH and 37.5 microg/l for p,p'-DDT when capillary gas-liquid chromatography with electron-capture detection is used for the final determination.     

The postcoital copper-T

Sediments, water, and oysters from the receiving waters of the Hahaione Valley, a suburban development in south-easter Oahu, Hawaii, were analyzed for organochlorine pesticidal compounds. The insecticides dieldrin, alpha- and gamma- chlordane, and p,p'-DDT were found in the study site environment. Levels were in the low parts per billion range for oysters and sediments and in the low parts per trillion range for water. During the past several years dieldrin residues in the marina study site have increased, even though the only activity known to influence pesticide levels in the valley is the chronic treatment for subterranean and dry wood termites. If present trends continue, dieldrin may pose a threat to biota of the aquatic environment. Findings have shown that residue levels of dieldrin and p,p'-DDT in the sediments are within the LD50 (median lethal dose) range for estuarine fish and thus may have a deleterious effect on bottom-feeding organisms. According to present standards of the Food and Agriculture Organization/World Health Organization, pesticide residue levels within the study site do not appear to constitute a health hazard to humans.     

Supercritical fluid extraction of pesticides from meat: a systematic approach for optimisation

A method for quantification of pesticide residues in meat and fatty matrices was developed using supercritical fluid extraction (SFE). The SFE method allows selective extraction of residues and subsequent gas chromatography analysis without further clean-up. Quantification was done by GC using nitrogen-phosphorus detection and electron capture detection. Initial method development was made using organophosphorus pesticides (OPPs). The dependence of fat and OPP residue recovery on supercritical fluid density, temperature, flow rate and extraction time was investigated through a reduced factorial design. Since temperature and density were found to have pronounced effect on the recovery of OPPs these extraction parameters were studied using a new arbitrary measure for co-extractivity. An optimisation score was established as relative pesticide recovery subtracted by relative fat recovery. Using this algorithm a response plane was modelled varying the primary factors temperature and density. The applicability of this approach and the algorithm was verified. The polarity range covered by the SFE method was demonstrated using OPPs: chlorpyrifos, chlorpyrifos-methyl, malathion, pirimifos-methyl and prothiofos. Additionally the final method was evaluated using four pesticides that are not OPPs: carbofuran, phorate, procymidone and vinclozolin. All pesticides showed good recovery (78-95%), and limits of detection (0.01-0.03 mg kg-1) and limits of determination (0.01-0.05 mg kg-1) meet the requirements set by the European Council (Directive 96/33/EEC). Compared to traditional methods based on organic solvent extraction, the SFE method is fast, less labour intensive, uses smaller amounts of potentially harmful solvents and has the potential to be fully automated.     

Photocatalytic degradation of pesticide residues with RE³⁺-doped nano-TiO₂

The photocatalytic degradation effects of carbofuran solution under concentration of 0.2,0.4,0.8 g/L Re3+-doped nano-TiO2 were studied.The highest degradation rate of 54.89% was obtained after 4 h degradation when the concentration of nano-TiO2 was 0.4 g/L.Then field trials of photocatalytic degradation with suspension nano-TiO2 were conducted.The photocatalytic degradation effect of organic phosphorus and carbamate pesticides in tomato leaves and soil with different concentratio catalyst(0,0.2,0.4,0.6,0.8 g/L) were studied.The results showed that nano-TiO2 could significantly increase photocatalytic degradation rate of pesticide residues in tomato leaves and soil.Pesticide residues degradation rate could be increased by 20%-30% on the tomato leaves and 15%-20% in soil,and the best concentration of photocatalytic degradation was 0.2-0.4 g/L.     

Effect of insulin on triacylglycerol synthesis and secretion by chicken hepatocytes in primary culture

Organophosphates are the most widely used pesticides throughout the world. The considerable amount brought out to the environment poses a risk on the whole population. As organophosphates are neurotoxic substances and their residues can persist in the environment for several weeks, their influence on the nervous system of humans and animals is of principal interest. In the present study, we investigated the alterations induced by dichlorvos, a common pesticide substance, in parameters of somatosensory evoked potentials and hippocampal evoked population spikes of rats. The changes of the cortical vs. hippocampal evoked responses were opposite and only hippocampal effects could be directly explained through an increased cholinergic activity.     

Report of a panel on the relationship between public exposure to pesticides and cancer. Ad Hoc Panel on Pesticides and Cancer. National Cancer Institute of Canada

BACKGROUND: Pesticides, which by their nature are biologically active compounds, continue to raise public concern regarding their possible role as important etiologic agents in the development of human cancer. METHODS: To examine this potential role, the National Cancer Institute of Canada convened an Ad Hoc Panel on Pesticides and Cancer to examine the possible contribution of pesticide exposure, particularly in the general population, to the development of human cancer. RESULTS: The Panel focused primarily on exposure in the general population and reviewed a range of studies that addressed issues related to dietary exposure as well as incidental home and garden uses. In addition, the Panel examined the regulatory framework that exists to safeguard the public from potentially carcinogenic pesticides and also reviewed some potential benefits of pesticide use, including the availability of an abundant and low cost supply of fresh fruits and vegetables as an important strategy in the overall mitigation of cancer risk. CONCLUSIONS: The Panel concluded that it was not aware of any definitive evidence to suggest that synthetic pesticides contribute significantly to overall cancer mortality. The Panel also concluded that it did not believe that any increased intake of pesticide residues associated with increased intake of fruits and vegetables poses any increased risk of cancer. The Panel further concluded, among other things, that tobacco use continues to be the most important preventable cause of cancer and premature mortality and thus is an appropriate focus for cancer control strategy.     

Determination and degradation of methomyl in tomatoes and green beans grown in greenhouses

A liquid chromatographic (LC) method using UV detection at 233 nm was used to study the degradation of methomyl in tomatoes and green beans grown in greenhouses. A liquid-liquid extraction with CH2Cl2-methanol (90 + 10, v/v) and a cleanup step with Florisil were combined with LC to isolate, recover, and quantitate the pesticide. Average recoveries obtained at spike levels of 0.03 and 0.40 mg/kg were 83.2-84.7% for tomatoes and 83.3-87.5% for green beans. Determination limits were 0.03 mg/kg for tomatoes and 0.01 mg/kg for green beans. Levels of methomyl residues were studied in tomatoes and green beans grown in an experimental greenhouse to establish the effect of the kind of greenhouse, application dose, species grown, and climatic conditions on the degradation of this pesticide. Analysis of variance showed that doses did not affect the response. The half-life, however, is greater in a flat-roof greenhouse than in an asymmetric-roof greenhouse and is significantly longer for green beans than for tomatoes and longer in winter than in spring. A preharvest time of about 5 days may be suitable for green beans sprayed with methomyl. Tomatoes show residue levels at the time of application lower than Spanish minimum residue levels.     

Degradation of Extraction from Seaweed and Its Complex with Rare Earths for Organophosphorous Pesticides

On the basis of several experiments carried out in China, it was proved that both seaweed liquid fertilizer and rare earth （RE） could promote the growth of crops and increase their yield. The effects of extraction from seaweed and its complex with RE on the degradation of organophosphorous pesticides and the yield of vegetables were investigated. The resuits showed that the extract and its complex with RE could degrade organophosphorous pesticides in neutral solvent. The residues of the pesticides treated by the extract decreased by 96.88 %, 52.30%, 49.52%, and 22.88 %, respectively, for chlorpyrifos, dichlorvos, omethoate, and dimethoate, and those by the complex decreased by 95.99%, 54.23%, 48.79%, and 25.66%, respectively, when compared with the control. The residues of chlorpyrifos and dimethoate in spinach sprayed with the complex were decreased by 90.64% and 76.56%, respectively, compared with those in spinach from control plots when the interval between spraying and sampling was 8 d. The fresh weight of brassica chinensis and cabbage increased by 28.62% and 18.72%, and their dry weight increased by 44.49% and 14.74%, respectively, compared with those of the controls. The chlorpyrifos and dimethoate residues in brasscia chinese were decreased by 36.36% and 50.00%, respectively, and their rate of decrease in cabbage was 40.00% and 75.00%, respectively, on 5th day after spraying with the complex, when compared with those in the vegetable from control. These results suggest that this complex can increase the agricultural productivity and reduce the use of pesticide residues in the production of vegetables.