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Distribution, fate and effects of pesticide residues in tropical coastal lagoons of northwestern Mexico.

Analyses of pesticide residues in sediments, water and biota of the Altata-Ensenada del Pabellon coastal lagoon system in Sinaloa, Mexico, showed the presence of organochlorine and organophosphorus compounds. For all the compounds analysed, concentrations in sediments were higher near the points of water discharge from ponds and drainage from the agricultural area. Among the organochlorines, total DDTs displayed the largest sedimentary reservoir, followed by total endosulfans and chlorpyrifos. In sediments, as well as in biota, pp'-DDT concentrations were lower than those of DDT metabolites, which confirms the reduction in the previous massive use of this compound in agriculture. Endosulfan is currently used in the region and endosulfan residues in lagoon sediments attained levels considered to be toxic to meiofauna, therefore constituting an ecological risk to lagoon ecosystems. There was a large sedimentary reservoir of chlorpyrifos but its ecotoxicological risk is difficult to assess due to lack of adequate comparative data. Nevertheless, concentrations of chlorpyrifos which approach acute toxic levels for shrimp were recorded in lagoon water. This suggests that drainage from agricultural fields during high runoff may, on occasion, cause mass mortality of shrimp and fish Organophosphorus pesticides are widely regarded to degrade very rapidly in aquatic systems. Experimental research performed with 14C-labelled chlorpyrifos and parathion has shown that they may be stabilised for relatively long periods of time through sediment-water partitioning. This extension of their environmental half-lives increases their potential for impacting on coastal ecosystems. Since organophosphorus pesticides are highly toxic for aquatic organisms at concentrations generally lower than organochlorines, their presence in the lagoon water and sediment is a matter for much concern. The increased use of tropical coastal lagoons for shrimp and fish farming requires the implementation of environmental management practices to protect these ecosystems from the impact of agricultural activities. Environmental management aims to preserve the ecosystem integrity of these coastal lagoons and, through improving the water quality, to allow the development of aquaculture and reduce human exposure to pesticide residues in food.

Ecosystem↗

Removal of pesticides from aqueous solution: Quantitative relationship between activated carbon characteristics and adsorption properties.

The adsorption of pesticides (atrazin, atrazin-desethyl and triflusulfuron-methyl) from aqueous solution is performed by activated carbon fibers (ACF) and granular activated carbons (GAC) in static and dynamic reactors, in order to study the co-influence of adsorbent and adsorbate characteristics on the adsorption mechanisms. First, mono-component adsorption equilibrium is carried out in a batch reactor for a wide range of concentrations (from 5 microg 1(-1) to 21.4 mg 1(-1)). Classic models, like Freundlich and Langmuir equations, are applied: the maximum adsorption capacities are high, ranging between 63 and 509 mg g(-1). The comparison of single-solute isotherms tends to confirm the decisive role of the adsorbent properties in the adsorption capacity of pesticides by the activated carbons: the performance of ACF is significantly higher than that of GAC due to a narrower pore size distribution of fibers in the area of micropores. Furthermore, their small diameter (10 microm compared with 1 mm for grains) enables faster adsorption kinetics because of the larger surface area exposed to the fluid. The influence of adsorbate size is also demonstrated. A multiple linear regression enables the co-influence of adsorbent and adsorbate properties to be quantified, a relationship being assessed between Langmuir maximum adsorption capacity and pesticide molecular weight and adsorbent diameter (R2 = 0.90). Secondly, the adsorption of the three pesticides is studied in a dynamic reactor: in this case, the influence of operating conditions (inlet concentration C0, flow velocity U0) is also taken into account. As the initial concentration or flow velocity decreases, the column performance significantly improves. Both operating factors are included in a multiple linear regression (R2 = 0.91) used to predict saturation adsorption capacity, with molecular weight and particle diameter being again designed as influent explicative variables.

Adsorption↗

Pesticide residues in table-ready foods in Tanzania.

This study investigated the presence of pesticide residues in table-ready foods in Tanzania. One-hundred-and-eighty nine samples of 11 widely used foods at table ready stage were analysed using US FDA multi-residue methods. Pesticide residues were detected in 29% of all samples analysed. The spread of contamination in individual foods was: spinach 72.7%, rice 50%, beef meat 42.1%, stiff porridge 8.6%, and beans 6.7%. After allocating Non-detects levels a half value of Method Detection Limit i.e., (MDL)/2, the mean concentrations of the pesticide residues in the foods were; In spinach: g-HCH 0.08 microg/kg; DDT 2.89 microg/kg; Chlorpyrifos 0.02 microg/kg. In rice: g-HCH 0.08 microg/kg; DDT 1.70 microg/kg; and Chlorpyrifos 0.02 microg/kg. In beef meat: g-HCH 0.14 microg/kg; DDT 0.76 microg/kg. In stiff porridge: g-HCH 0.06 microg/kg; and DDT 0.30 microg/kg. In beans: g-HCH 0.04 microg/kg; and DDT 0.13 microg/kg. In fish variety: g-HCH 0.05 microg/kg. Converted into consumer Average Daily Doses, these concentrations were within ADI/ PTDI levels set by CODEX and, therefore, posed no significant health risk. However, the presence of pp-DDT in many samples indicates a possible recent contamination of food raw materials with DDT. A more effective pesticides control system should be put in place before lifting the ban on DDT for restricted uses in vector control programs in Tanzania.

Environmental Monitoring↗

Evaluation of estrogenic activities of pesticides using an in vitro reporter gene assay.

The estrogenic activities of 32 pesticides in agricultural products were evaluated using the E-CALUX assay system developed by Xenobiotic Detection Systems Inc (North Carolina, USA). This system utilizes human ovarian carcinoma cells (BG1) stably transfected with an estrogen-responsive luciferase reporter gene plasmid. It was found that tolclofos-methyl, prothiofos, diazinon, Thiabenclazole (TBZ) and pyriproxyfen had estrogenic activity. Several pesticides are often present in agricultural products. Therefore the estrogenicity of the mixtures of two kinds of pesticides was evaluated. The activity of diazinon/tolclofos-methyl, pyriproxyfen/prothiofos and TBZ/o-phenylphenol (OPP) was increased up to 1.2-5.3 fold. On the other hand, chlorfluazuron, imazalil and chlorfenapyr had anti-estrogenic activity. Further, to evaluate the change in the estrogenic activity of pesticide metabolites, an experimental system was established using a rat S9 mixture. Metabolites of permethrin and OPP had no estrogenic activity, but they had weak activity after the metabolism. On the other hand, the metabolites of TBZ exhibited less estrogenic activity than the original compounds.

Agriculture↗

General evaluation of risk associated with the use of pesticides and other chemical substances on animal breeding and plant production farms.

A general characteristic of chemical risk on plant production farms in Poland is presented. The paper describes risk associated with the natural occurrence of chemical substances (such as ammonium and hydrogen sulfide) in the process of animal breeding and risk connected with the use of artificial fertilizers and pesticides. Pesticides are briefly described taking into consideration toxicity classes and the toxic effect of individual compounds. Exposure to pesticides is presented for individual methods and related activities. Finally, the author discusses pesticide risk on fruit-growing farms and in greenhouses.

Agriculture↗

Health risk of low-dose pesticides mixtures: a review of the 1985-1998 literature on combination toxicology and health risk assessment.

A literature review covering the last 14 yr has been performed in the field of combination toxicology and human risk assessment from exposure to chemical mixtures, with special emphasis on mixtures of pesticides at low doses, that is, at levels likely to occur in human diet and environment. Despite a large body of knowledge in the field of risk assessment methodologies for exposure to chemical and pesticide mixtures, there is no single methodological approach in "combination toxicology" and health risk assessment of chemical mixtures, and therefore professional judgment is still required. Generally, the dose or response additivity approach that may be applied to evaluate potential risk for chemical mixtures in human toxicology overestimates the risk of a combination of chemicals. The recent endocrine disrupter issue demonstrated the difficulty of reproducibility of data when testing environmental toxicants at very low levels, and the need for more basic work in this field. The use of integrated methodological approaches may provide more reliable predictive data in the risk assessment of chemical mixtures in future. Yet data have demonstrated that exposure to a combination of compounds does not cause effects stronger than the ones of their most active component, provided components are present at low concentration levels, like acceptable daily intake (ADI) or reference dose (RfD) levels, well below their respective no-observed-adverse-effect levels (NOAELs). Although it has been demonstrated that a combination of compounds with the same target organ and the same or very similar mechanisms of action may cause additive or synergistic effects, the chance of such effects will most likely diminish with decreasing exposure levels to such combinations. Synergism and antagonism may both occur at the same time at different organs or targets in the same organism. However, and despite some exceptions, it has been demonstrated that interaction between components is not a common event at low levels of human exposure such as those that may occur through pesticides residues in food or drinking water. The introduction of a special safety factor as a standard for mixtures in addition to those normally used for deriving ADIs, RfDs, or minimal risk levels is not supported by data. It can be concluded from our review that, as a general rule, exposure to mixtures of pesticides at low doses of the individual constituents does not represent a potential source of concern to human health.

Environmental Pollutants↗

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.

Cholinesterases↗

In vivo percutaneous absorption and decontamination of pesticides in humans.

Regulators today face complex problems in assessing the health hazards associated with the use of pesticides. Pesticide exposure occurs at manufacturing, application, work area, and consumption situations, and in the air, water, and soil of our daily lives. The skin is the largest organ of the body and thus has become a major environmental port for pesticides to enter the body. In this paper, we review the principles of percutaneous absorption--the rate and extent that chemicals enter the body through the skin--using data currently available for pesticides.

Animals↗

Regulation of pesticides in Cameroon.

To fight against pests and vectors of certain diseases, Cameroon imports and makes use of pesticides. Importation and utilization are subject to regulation from importers to users. The goal of this study is to evaluate the actual regulatory system of pesticides in Cameroon. From this study has emerged the fact that Cameroon has insufficient legislation for pesticides. Registration does not exist, and the ministry of agriculture restricts itself to issuing attestation of importation, if the product is effective, to those who write an application. Importation and distribution are done in conditions that are far from ideal. To remedy this inadequacy, it is necessary to train and inform all those intervening in this domain and put in place research infrastructures. Appropriate legislation elaborated in a broad consultation with competent authorities in pesticides is also needed.

Cameroon↗

An evaluation of 24-hour urinary creatinine excretion for use in identification of incomplete urine collections and adjustment of absorbed dose of pesticides.

The accurate quantification of the absorbed dose of pesticides following occupational exposures generally requires complete 24-hour urine collections, often over extended periods of time. Difficulty in obtaining volunteer cooperation may result in incomplete urine collections. Traditionally, 24-hour urinary creatinine has been used to identify incomplete urine samples and has been used to standardize pesticide and other chemical dose estimates. More recently, the use of creatinine to standardize dose estimates has been questioned, as has its utility in the identification of incomplete urine collections. This research evaluates the use of personal observation, statistical methods, and published models to predict creatinine excretion to identify and adjust for incomplete urine collections. Based on the use of published creatinine prediction models, an evaluation of the day-to-day creatinine excretion within subjects, and personal observation, a small number of suspected urine samples were identified. Although it is likely that these samples were incomplete, correction of these urine volumes based on the published models did little to improve pesticide dose prediction. Further, results indicate that subjects who report missed urine samples may be able to estimate the missing volumes with some accuracy. In future pesticide exposure studies, the use of self-reported missed volumes may help to increase the accuracy of dose prediction when there is strong cooperation with collection procedures. A statistical model to predict creatinine excretion in professional turf applicators was developed to provide a preliminary screening for urinary completeness for future studies in which compliance with urinary collection is thought to be insufficient.

Adult↗

Pesticide residues in thermal mineral water in Greece.

Eight different hot springs (SPA) in Greece were monitored over a one-year survey for priority pesticide residues. A specific and effective procedure including solid phase extraction in combination with HPLC and GC analytical methods were applied. Samples that were sensitive to nitrogen-phosphorus (NPD) and/or electron capture (ECD) detectors were analysed by capillary gas chromatography. From the twenty-six water samples, pesticide residues were detected in fourteen of them (54%) but no one exceeding the European Union Maximum Acceptable Concentration (MAC). Lindane (gamma-BHC) was the most frequently detected pesticide. It was found in nine samples (35%) in concentrations from < 0.005 to 0.01 microg/L. Other pesticides detected were phorate (in five samples), propachlor (in two samples) and chlorpyriphos ethyl (in three samples) but in concentrations far below the permissible levels.

Chromatography, Gas↗

Multiresidue screening methods for the determination of pesticides in tomatoes.

The possibility of applying thin layer chromatography (TLC) detection for the analysis of pesticide residues in tomatoes was investigated. Samples of tomatoes that have never been treated with pesticide were fortified with atrazine, carbaryl, carbofuran, chloroxuron, diuron, dimethoate, imazalil, oxamyl and methamidophos. The samples were extracted, cleaned-up by gel permeation chromatography and then applied on silica gel plates. The pesticides were eluted with ethyl acetate and dichloromethane. Two eluting solvent systems were tested, one using the reagents o-toluidine + potassium iodite (o-TKI) and the other p- nitrobenzene fluoroborate (NBFB). After the development of the plates, the diameter of the spots was measured. The lowest minimum detection quantity (MDQ) for o-TKI system for atrazine was 12 ng. The highest was 125 ng for carbofuran. Using NBFB system, the lowest MDQ was 60 ng for carbaryl and the highest was 70 ng obtained for carbofuran. Considering the concentration of these pesticides in the spiked tomato samples, the minimum concentration was 1.1 ng/microL and 32.3 ng/microL for atrazine and carbofuran, respectively, by using o-TKI system. For NBFB system the minimum concentration reached was 3.5 ng/microL and 4.3 ng/microL for carbaryl and carbofuran, respectively. This study showed that TLC can be used for semi-quantitative analysis.

Calibration↗

PeLM: modeling of pesticide-losses through runoff and sediment transport.

A GIS-aided pesticide loss model (PeLM) was developed to simulate pesticide losses through surface runoff and sediment transport in watershed systems. The PeLM could tackle the movement of eroded soil along with surface runoff as well as the pesticide losses in adsorbed and dissolved phases. The contributions of different soil types in the sediment were also examined. The model was applied to the Kintore Creek Watershed of southern Ontario, Canada. The simulation results were verified through observed data, indicating a correlation level of 0.89-0.98. The results also showed that clay particles usually held the largest share of contributions to pesticide losses through soil erosion. This study is significant in the efforts for modeling nonpoint source pollution in watershed systems. It provides useful information and support for the related decisions of watershed management.

Geographic Information Systems↗

A cost-effective screening method for pesticide residue analysis in fruits, vegetables, and cereal grains.

This paper reports the results of studies performed to investigate the potential of applying thin layer chromatography (TLC) detection in combination with selected extraction and cleanup methods, for providing an alternative cost-effective analytical procedure for screening and confirmation of pesticide residues in plant commodities. The extraction was carried out with ethyl acetate and an on-line extraction method applying an acetone-dichloromethane mixture. The extracts were cleaned up with SX-3 gel, an adsorbent mixture of active carbon, magnesia, and diatomaceous earth, and on silica micro cartridges. The Rf values of 118 pesticides were tested in eleven elution systems with UV, and eight biotest methods and chemical detection reagents. Cabbage, green peas, orange, and tomatoes were selected as representative sample matrices for fruits and vegetables, while maize, rice, and wheat represented cereal grains. As an internal quality control measure, marker compounds were applied on each plate to verify the proper elution and detection conditions. The Rf values varied in the different elution systems. The best separation (widest Rf range) was achieved with silica gel (SG)--ethyl acetate (0.05-0.7), SG--benzene, (0.02-0.7) and reverse phase RP-18 F-254S layer with acetone: methanol: water/30:30:30 (v/v) (0.1-0.8). The relative standard deviation of Rf values (CV(Rf)) within laboratory reproducibility was generally less than 20%, except below 0.2 Rf, where the CVRf rapidly increased with decreasing Rf values. The fungi spore inhibition, chloroplast inhibition, and enzyme inhibition were found most suitable for detection of pesticides primarily for confirming their identity or screening for known substances. Their use for determination of pesticide residues in samples of unknown origin is not recommended.

Chromatography, Thin Layer↗

Bioaccumulation studies of organochlorinated pesticides in tissues of Cyprinus carpio.

Freshwater fish Cyprinus carpio was selected for the study of bioaccumulation of organochlorinated pesticides in tissues like gills, muscle, intestine, kidney, and liver in a continuous fed system. The pesticides used were Aldrin, Dieldrin, BHC, and DDT. The bioaccumulation of Dieldrin was maximum of 85.0 microg g(-1) wet weight in liver tissue while minimum of 7.30 microg g(-1) wet weight for DDT at 30 days exposure time. Bioconcentration factor (BCF) has followed the same trend in liver tissue for Dieldrin and DDT. The rate of bioaccumulation was found to be maximum of 4.3879 microg g(-1) wet weight in liver tissue and minimum of 0.0021 microg g(-1) wet weight in gill tissue for 30 days exposure. As evidenced by the increasing values of BCF, pesticide uptake also showed increased trend with the increase in exposure time. A high correlation coefficient ranging between 0.7247 and 0.9616 between the pesticide concentration and exposure time was observed. Based on actual BCF values, log Kow were calculated and the values are well within the reported values of 6.5 indicating efficient relationship between BCF and log Kow because beyond the 6.5 the bioconcentration levels off.

Aldrin↗

Chlorinated pesticides (2,4-D and DDT) biodegradation at high concentrations using immobilized Pseudomonas fluorescens.

Degradation of two chlorinated pesticides (2,4-D and DDT) using a 54-mL glass column packed with tezontle (a low-cost basaltic scoria) was tested. Bacteria were cultured in YPG (yeast, peptone, and glucose) liquid medium at 32 degrees C. The rich medium was pumped during 24 h through the column to inoculate it. Later, the wasted medium was discharged and the pesticide added. Optical densities, TOC, and pesticide concentration were determined. Pesticide removals for 2,4-D (with initial concentration between 100 and 500 mg/L) were about 99%. DDT removal (at initial concentration of up to 150 mg/L) was as high as 55-99%. TOC removals for 2,4-D was in the 36-87% interval, whereas for DDT they were as high as 36-78%.

2,4-Dichlorophenoxyacetic Acid↗

Neurodegenerative diseases and exposure to pesticides in the elderly.

The authors investigated the hypothesis that exposure to pesticides could be related to central nervous system disorders in a prospective cohort study of 1,507 French elderly (1992-1998). Lower cognitive performance was observed in subjects who had been occupationally exposed to pesticides. In men, the relative risks of developing Parkinson's disease and Alzheimer's disease for occupational exposure assessed by a job exposure matrix were 5.63 (95% confidence interval: 1.47, 21.58) and 2.39 (95% confidence interval: 1.02, 5.63), respectively, after confounding factors were taken into account. No association was found with having a primary job in agriculture or with environmental pesticide exposure, nor was an association found in women. These results suggest the presence of neurologic impairments in elderly persons who were exposed occupationally to pesticides.

Aged↗

Solid-phase extraction method for the quantitative analysis of organochlorine pesticides in wildlife urine.

A gas chromatographic method for the analysis of nine organochlorine pesticides in wildlife urine is described. Reversed-phase solid-phase extraction is utilized to extract the organochlorine pesticides from urine. The pesticides are recovered by elution with hexane-ethyl ether (1:1) and quantified by gas chromatography with electron-capture detection. Method detection limits range from 1.4 to 2.7 micrograms/L. Mean recoveries for all pesticides are 90.6%.

Animals↗