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PubMed1983

Further mutagenicity studies on pesticides in bacterial reversion assay systems.

A total of 228 pesticides (88 insecticides, 60 fungicides, 62 herbicides, 12 plant-growth regulators, 3 metabolites and 3 other compounds) was tested for mutagenicity in bacterial reversion-assay systems with 5 strains (TA100, TA98, TA1535, TA1537 and TA1538) of Salmonella typhimurium and a strain (WP2 hcr) of Escherichia coli. 50 pesticides (25 insecticides, 20 fungicides, 3 herbicides, 1 plant-growth regulator and 1 other compound) were found to be mutagenic. 5 of them required metabolic activation (S9 mix) for their activities. Among various chemical groups, organic phosphates, halogenated alkanes and dithiocarbamates showed higher ratios of mutagens. Although 22 of the pesticides tested have been reported to be carcinogenic, 7 of them, i.e., captain, DBCP, EDB, EDC, ETU, HEH and nitrofen, were detected as mutagens in the present assay. Most of the other 15 non-mutagenic carcinogens were organochlorine pesticides such as alpha-BHC, chlorobenzilate, p,p'-DDT, dieldrin and quintozene.

Carcinogens↗
PubMed1983

Evaluation of FAO/WHO pesticide standards in relation to Polish and Honduran diets.

The FAO/WHO Codex Alimentarius Commission publishes a Guide to Codex Maximum Limits for Pesticide Residues (1978) which gives both acceptable daily intake (ADI) values and maximum residue limit (MRL) values for many pesticides in raw agricultural commodities (rac's) from crops on which their use is approved. ADI values are determined from animal toxicology data which given a no-observable-effect level (NOEL) and use of a safety factor. Specific MRL values are calculated from the ADI and a food factor (F), which is the decimal fraction of that rac in the assumed typical diet. One of the difficulties with this procedure is that dietary patterns differ substantially between countries. Whatever dietary pattern is assumed in calculation of the MRLs may be inappropriate for that country. Theoretical maximum residue intakes (TMRIs) were calculated from the Codex ADIs and MRLs using F values calculated from the national dietary patterns published separately in Poland and Honduras. The equation is TMRI = sigma MRLi X Fi X D, where D is the daily individual diet weight of rac's in kilograms for the particular country. The TMRI should be lower than the maximum permitted intake (MPI) calculated as MPI = ADI X 60, where the 60 is an arbitrary human body weight in kilograms. The TMRI exceeded the MPI for 16 of 33 pesticides used in Poland and for 10 of 20 used in Honduras. At the extreme, the Polish TMRI/MPI ratio for aldrin--dieldrin is 19.5 and 18.1 for fenithion; nine pesticides had ratios of 4.0 or higher.(ABSTRACT TRUNCATED AT 250 WORDS)

Animals↗
PubMed1984

Evaluation of pesticides which pose carcinogenicity potential in animal testing. I. Developing a tumor data evaluation system.

A modified-Squire carcinogen ranking system has been developed by the Worker Health and Safety Unit of the California Department of Food and Agriculture to deal with pesticides which pose carcinogenic potentials. For pesticide products that have been adequately tested with sufficient data for such evaluation, this system can provide an in-depth review which is necessary for the better understanding of a chemical under investigation. Only with such understanding can a product be placed in its proper perspective with respect to its carcinogenic potency. When applying this rather intensive tumor data evaluation system, a total scoring point and carcinogenicity categorization may be provided, which, in conjunction with human exposure information, may be adequate for regulatory decision making. Based upon the adequacy of tumor data, seven pesticides were investigated using the current tumor data evaluation system. These pesticides were chosen to demonstrate the stepwise evaluation procedure for carcinogenicity evaluation.

Animals↗
PubMed1989

Evaluation of the carcinogenic potential of pesticides. 1. Acifluorfen.

The Health Effects Division of the Office of Pesticide Programs evaluates the carcinogenic properties of pesticides by a consensus peer review process in which all available biological information on a compound is evaluated according to EPA's guidelines for cancer risk assessment. In many cases, pesticides are also evaluated by an external group of accomplished scientists who comprise the Agency's Scientific Advisory Panel. The herbicide acifluorfen was evaluated by these processes and was classified as a Category B2 (probable human) carcinogen based upon evidence of an increased incidence of malignant, or combined benign and malignant, tumors in multiple experiments involving two different strains of mice. The compound produced benign and malignant liver tumors in male and female B6C3F1 mice and in female CD1 mice. Stomach papillomas were also observed in male and female B6C3F1 mice. Acifluorfen was mutagenic in bacteria and yeast, but not in mammalian cell systems. In addition, acifluorfen is structurally related to eight other diphenyl ether pesticides, all of which evoke liver tumours in mice or rats. The data were found to be sufficient to quantify human risk to acifluorfen.

Animals↗
PubMed2004

Quantitative inter-specific chemical activity relationships of pesticides in the aquatic environment.

Inter-species correlations could be a useful tool for predicting toxicity and for establishing sensitivity ratios among species. In this paper, quantitative inter-specific chemical activity relationships (QICAR) for aquatic organisms were developed to verify if such an approach could be utilised for estimating toxicological data when no other information is available. Inter-specific toxicity relationships on fish, Daphnia and algae were performed for pesticides considering a large data set (more than 600 compounds) and grouping the data either on a functional (herbicides, fungicides and insecticides) or chemical class base. Good correlations were found between several fish species and they were improved by excluding, from the data set, highly specific compounds such as organophosphorus insecticides. Relationship between fish (rainbow trout) and Daphnia was significant for the whole data set, but clearly improves if congeneric classes of pesticides are considered. The most significant results were found for azoles (fungicides) and for all data set of pesticides with the exclusion of organophosphorus and carbamate insecticides. As expected, toxicity on algae does not correlate either with fish or with Daphnia on the whole data set, but excluding the classes acting specifically toward one organism (insecticides and several classes of herbicides), good relationships were found. The analysis of the data permits the conclusion that the specificity in the mode action of pesticides is the key parameter for expecting or not inter-specific relationships. By the relative specificity of action of a group of compounds towards two species, the probability of obtaining a QICAR for this group can be derived. In general, compounds acting with the same level of specificity towards two different species, have a higher probability of showing inter-specific relationships and the lower the specificity of the mode of action of the compounds (e.g. narcotics or less inert chemicals), then the stronger are the relationships.

Animals↗
PubMed2005

Application and validation of approaches for the predictive hazard assessment of realistic pesticide mixtures.

In freshwater systems located in agricultural areas, organisms are exposed to a multitude of toxicologically and structurally different pesticides. For regulatory purposes it is of major importance whether the combined hazard of these substances can be predictively assessed from the single substance toxicity. For artificially designed multi-component mixtures, it has been shown that the mixture toxicity can be predicted by concentration addition (CA) in case of similarly acting substances and by independent action (IA), if mixtures are composed of dissimilarly acting substances. This study aimed to analyse whether these concepts may also be used to predictively assess the toxicity of environmentally realistic mixtures. For this purpose a mixture of 25 pesticides, which reflects a realistic exposure scenario in field run-off water, was studied for its effects on the reproduction of the freshwater alga Scenedesmus vacuolatus. The toxicity of the tested mixtures showed a good predictability by CA. This is consistent with the finding that the toxicity was dominated by a group of similarly acting photosystem II inhibitors, although the mixture included substances with diverse and partly unknown mechanisms of action. IA slightly underestimated the actual mixture toxicity. However, the EC(50) values that can be derived from each prediction, according to CA respectively IA, only differed by a factor of 1.3. The finding of such a small difference is partly explainable by the fact that only few components dominate the mixture scenario in terms of so-called toxic units (TUs). This connection is established by developing an equation that allows to calculate the maximum possible ratio between corresponding predictions of effect concentrations by IA and CA for any given ratio of the TUs of mixture components, irrespective of their individual concentration-response functions and independent from their mechanisms of action. To evaluate whether small quantitative differences between EC(50) values predicted by CA and IA are an exception or rather the rule for agricultural exposure scenarios, this calculation was applied on an additional set of 18 pesticide exposure scenarios that were taken from the literature. For these scenarios, EC(50) values predicted by IA can never exceed those predicted by CA by more than a factor of 2.5. The findings of this study support the view that CA provides a precautious but not overprotective approach to the predictive hazard assessment of pesticide mixtures under realistic exposure scenarios, irrespective of the similarity or dissimilarity of their mechanisms of action.

Animals↗
PubMed2006

Relating olfactory neurotoxicity to altered olfactory-mediated behaviors in rainbow trout exposed to three currently-used pesticides.

Odor-evoked neurophysiological responses can form the basis for behavioral responses. Here we first characterized olfactory-mediated behavioral and neurophysiological responses of juvenile rainbow trout to the amino acid l-histidine, then looked at whether there were similar responses to the carbamate antisapstain IPBC and the herbicides atrazine and Roundup, and lastly explored how exposures to these pesticides modified the l-histidine responses. Trout were behaviorally attracted to 10(-7)M l-histidine (as assayed in a counter-current olfactometer), but this preference behavior switched to indifference with higher histidine concentrations. Neurophysiologically, the summed electrical responses of peripheral olfactory neurons, as measured using electro-olfactogram (EOG), was 0.843+/-0.252 mV to 10(-7)M l-histidine. Of the pesticides, only Roundup evoked EOGs, indicating the amino acid-based pesticide may have acted as an odorant, and generated a behavioral response: it was avoided at active ingredient [AI; glyphosate isopropyl amine] concentrations > or =10 mg/l. With 30 min pesticide exposures, 10(-7)M l-histidine preference behavior was eliminated following exposure to 1 microg/l IPBC and atrazine, and 100 microg/l AI Roundup. Similarly, 10(-7)M l-histidine-evoked EOGs were significantly reduced by exposure to 1 microg/l IPBC, 10 microg/l atrazine, and 100 microg/l AI Roundup. When combined together, the results demonstrate that typical preference behavior can be abolished when neurophysiological responses are reduced by >60% of control. This asymmetry in response thresholds suggests that behavioral responses may be more sensitive toxicological endpoints than neurophysiological responses.

Animals↗
PubMed2004

Influence of the application of sewage sludge on the degradation of pesticides in the soil.

A study was made of the influence of the application of sewage sludge on the degradation of pesticides in the soil. Two kinds of sludge were used, with different characteristics, one from an urban treatment plant and one from a food processing plant. Three organophosphorus insecticides, fenitrothion, diazinon and dimethoate, were studied. The relative importance was determined of the chemical and biological degradation processes, which involved experiments on soil and sterile soil samples. A comparative study was also made of the degradation of pesticide residues and the evolution of the microbial population. The application of sludge seems to have a complex effect on the degradation of pesticides, determined by the bioavailability and biodegradability of their active ingredient. The biodegradation of pesticide residues brings about alterations in the microorganism population of the soil.

Biodegradation, Environmental↗
PubMed2004

Determination of time-dependent partition coefficients for several pesticides using diffusion theory.

Diffusion-retarded partitioning of pesticides with aggregated soils results in a time-dependent partition coefficient (Kd') which is different at equilibrium from the partition coefficient derived from conventional 24-h batch studies (Kd) measured on dispersed soil. An experiment was undertaken to determine the importance of Kd' for the prediction of pesticide concentrations in solutions bathing artificial soil aggregates and to determine whether diffusion theory could accurately predict the concentrations. Two clay soils were mixed with polyacrylamide to create artificial aggregates of 0.8, 1.4 and 1.7 cm diameter when dry. After saturation, the aggregates were immersed in solutions containing isoproturon or a mixture of isoproturon, chlorotoluron and triasulfuron. The decline with time of the pesticide concentrations in the bathing solution was monitored and the results were compared with predictions from a diffusion-based model. The effective diffusion coefficients of the compounds were obtained by either fitting the non-linear diffusion model to the data (D(ef)) or by independent calculations based on the properties of the compounds and of the aggregates (D(ec)). The diffusion model was able to predict the temporal variation in pesticide concentrations in the bathing solution reasonably well whether D(ef) or D(ec) values were used. However, equilibrium concentrations in solution were sometimes overestimated due to increased sorption with time at the particle scale. Overall, the ratio between D(ef) and D(ec) ranged from 0.23 to 0.95 which was a reasonable variation when compared to the range of aggregate sizes used in the experiments and of the Kd values of the compounds.

Acrylic Resins↗
PubMed2005

Electrochemical detoxification of four phosphorothioate obsolete pesticides stocks.

The phosphorothioate pesticides are widely used for crop production and fruit tree treatment, but their disposal causes serious environmental problems. Four commercial phosphorothioate pesticides (Demeton-S-methyl, Metamidophos, Fenthion and Diazinon) were treated by an electrolysis system using Ti/Pt as anode and stainless steel 304 as cathode. A number of experiments were run in a laboratory scale pilot plant and the results are presented. For Fenthion the achieved reduction was over 60%, while for Demeton-S-methyl, Metamidophos and Diazinon was more than 50%. Diazinon had the lowest energy demand. The COD/BOD5 ratio was improved considerably after electrolysis for all four pesticides examined. As a conclusion, electrochemical oxidation could be used as a pretreatment method of the pesticides detoxification.

Electrochemistry↗
PubMed2005

Wet deposition of pesticides and nitrophenols at two sites in Denmark: measurements and contributions from regional sources.

The concentrations of selected pesticides, of some of their degradation products and nitrophenols in rain were measured at two stations in Denmark in the period January 2000-July 2001. Forty compounds were quantified at least at one station during at least one sampling period. Additionally 17 compounds could be detected but not quantified, and 22 compounds could not be detected at all. The highest depositions of pesticides were observed for pendimethalin and desethylterbuthylazine, which is a degradation product of terbuthylazine. The deposition of the nitrophenols 2,4-dinitrophenol, DNOC, 3-methyl-4-nitrophenol was much higher than that of pesticides. The deposition of 2,4-dinitrophenol was e.g. up to a factor of 40 higher than that of pendimethalin. Atrazine, chloridazon, 2,4-D, dieldrin, disulfoton, fenitrothion, isoproturon, lenacil, metazachlor and propachlor were found in precipitation, although these pesticides are not allowed in Denmark. It can therefore be concluded that they came from abroad and have been transported over at least 60-80 km. For some of these compounds the transport distance is much longer.

Chromatography, Liquid↗
PubMed2005

Screening 31 endocrine-disrupting pesticides in water and surface sediment samples from Beijing Guanting reservoir.

For screening 31 potential or suspected endocrine-disrupting pesticides in water and surface sediments, a multiresidue analysis method based on gas chromatography with electron capture detection (GC/ECD) was developed. Solid phase extraction (SPE) technology with Oasis HLB cartridge was also applied in sample extraction. The relevant mean recoveries were 70-103% and 71-103% for water and sediment, respectively. Relative standard deviations (RSD) are 2.0-7.0%, 4.0-8.0% for water and sediment, respectively. Thirty one pesticides (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH, hexachlorobenzene (HCB), aldrin, heptachlor, endosulfan I & II, p,p'-DDD, o,p'-DDT, p,p'-DDT, p,p'-DDE, endrin aldehyde, endosulfan sulphate, methoxychlor, hepachlor epoxide, alpha-chlordane, gamma-chlordane, dieldrin, endrin, dicofol, acetochlor, alachlor, metolachlor, chlorpyriphos, nitrofen, trifluralin, cypermethrin, fenvalerate, deltamethrin) in water and surface sediment samples from Beijing Guanting reservoir were analyzed. Concentrations of pesticides ranged from 7.59 to 36.0 ng g(-1) on a dry wt. basis for sediment samples, from 279.3 to 2740 ng l(-1) for pore waters and from 48.8 to 890 ng l(-1) for water samples, respectively, with a mean concentration of 10.7 ng g(-1) in sediment, 735 ng l(-1) in pore water and 295 ng l(-1) in water, respectively. The data obtained provides information on the levels and sources of endocrine-disrupting pesticides in Guanting reservoir. These results underscore the need to improved environmental protection measures in order to reduce the exposure of the population and aquatic biota to these endocrine-disrupting compounds.

China↗
PubMed2005

Pesticide removal from cotton farm tailwater by a pilot-scale ponded wetland.

A pilot-scale, ponded wetland consisting of an open pond and a vegetated pond in series was constructed on a cotton farm in northern New South Wales, Australia, and assessed for its potential to remove pesticides from irrigation tailwater. Ten incubation periods ranging from 7 to 13 days each were conducted over two cotton growing seasons to monitor removal of residues of four pesticides applied to the crop. Residue reductions ranging 22-53% and 32-90% were observed in the first and second seasons respectively. Average half-lives during this first season were calculated as 21.3 days for diuron, 25.4 days for fluometuron and 26.4 days for aldicarb over the entire wetland. During the second season of monitoring, pesticide half-lives were significantly reduced, with fluometuron exhibiting a half-life of 13.8 days, aldicarb 6.2 days and endosulfan 7.5 days in the open pond. Further significant reductions were observed in the vegetated pond and also following an algal bloom in the open pond, as a result of which aldicarb and endosulfan were no longer quantifiable. Partitioning onto sediment was found to be a considerable sink for the insecticide endosulfan. These results demonstrate that macrophytes and algae can reduce the persistence of pesticides in on-farm water and provide some data for modelling.

Agriculture↗
PubMed2005

Investigation of various physicochemical and environmental parameter influence on pesticide sorption to ditch bed substratum by means of experimental design.

Diffuse pollution by pesticide applied in rural catchments may contribute to alter water quality. Besides actions relative to the way the substances are introduced into the environment, it is also possible to limit the contamination by interfering on their transfer pathways from fields to the main river network. Especially, interface areas such as buffer strips or small ditches may play a major part in pesticide diffuse pollution decrease. In ditches a great variety of materials may act as sorbents for organic contaminants: grass, leaves, wood debris or sediments. In this study, laboratory experiments were designed to determine sorption characteristics for three herbicides with different physicochemical properties on sediment and leaves in decay commonly found in agricultural ditches. Sorption capacities were assessed for the herbicides isoproturon, diuron and diflufenican. Experimental design was carried out to investigate the effects of five parameters on herbicide sorption on sediment and dead leaves. These parameters have been chosen according to parallel field experiment needs. Thus, the influence of initial sorbent moisture, herbicide form, i.e. active substance or commercial formulation, water quality (tap or natural ditch water), bromide ions (used as conservative tracers) and solid/liquid ratio have been tested. Within the parameters investigated, pesticide formulation and solid/liquid ratio were the most important parameters affecting pesticide sorption on both ditch materials.

Absorption↗
PubMed2006

Study of the presence of pesticides in surface waters in the Ebro river basin (Spain).

This work studies the presence of a total number of 44 substances found in waters of the Ebro river basin (Spain), all included in the Pesticides Control Network, whose purpose is to monitor diffuse pollution of surface waters caused by pesticides contained in some of the dangerous substances lists established in existing legislation and their high degree of use in the basin. Most of the pesticide sampling points are located in the sections of river that receive run-off waters from various agricultural areas shortly before opening out onto the main river (the Ebro), in areas of special agricultural importance. Water samples are subjected to a solid-liquid extraction as a previous step to their analysis by GC/MS (gas chromatography/mass spectrometry). Pesticides most frequently found and in greater concentrations in the waters of the Ebro river basin are 3,4-dichloroaniline, molinate, desethylatrazine, dimetoate, simazine, atrazine, metolachlor and chlorpyrifos. There are certain compounds that are not detected or their concentrations are below the quantification limit, such as 4-isopropylaniline, ametryn, beta-HCH, delta-HCH, aldrin, isodrin, dieldrin, heptachlor epoxide, endosulfan and endosulfan-sulfate. Diuron appears at specific points in some of the stations.

Environmental Monitoring↗
PubMed2006

Antiandrogenic activity of pyrethroid pesticides and their metabolite in reporter gene assay.

Many pesticides possess hormonal activity and have thus been classified as endocrine disruptors. Pyrethroids are commonly used pesticides worldwide, but little has been done to characterize their antiandrogenic activity potential. We tested three frequently encountered pyrethroids (fenvalerate, cypermethrin, permethrin) and their metabolite 3-phenoxybenzoic acid (3-PBA) for antiandrogenic and androgenic activity using a human androgen receptor (AR) mediated luciferase reporter gene assay in CV-1 African green monkey kidney cell. The assay displayed appropriate response to the known AR agonist 5alpha-dihydrotestosterone and AR antagonist nilutamide and flutamide. At 0.1mM, all the three tested pyrethroids significantly suppressed the luciferase expression. Further, their metabolite 3-PBA also showed antagonist activity. None of the test chemicals showed androgenic activity. Through the antiandrogenic pathways, exposure to certain pyrethroids may contribute to the damage of reproductive system. In conclusion, pyrethroid pesticides can act as antiandrogen in vitro, and metabolizing to 3-PBA cannot eliminate the antagonist activity. This result provides useful information for risk assessment of pyrethroid pesticides.

Androgen Antagonists↗
PubMed2007

Human intake fractions of pesticides via greenhouse tomato consumption: comparing model estimates with measurements for Captan.

Human intake due to pesticide residues in food commodities can be much higher than those related to water consumption and air inhalation, stressing the importance to correctly estimate pesticide uptake into plants and predict subsequent intake by humans. We calculated the human intake fraction of captan via tomato consumption taking into account the time between pesticide application and harvest, the time between harvest and consumption, the absorption of spray deposit on plant surfaces, transfer properties through the cuticle, degradation inside the plant and loss due to food processing. Human population intake fractions due to ingestion were calculated for complete, washed and peeled tomatoes. The calculated intake fractions were compared with measurements derived from an experimental setup in a Mediterranean greenhouse. The fraction of captan applied in the greenhouse as plant treatment that eventually is ingested by the human population is on average 10(-2)-10(-5), depending on the time between pesticide application and ingestion of tomatoes and the processing step considered. Model and experimentally derived intake fractions deviated less than a factor of 2 for complete and washed tomatoes and a factor of 3 for peeled tomatoes. Intake fractions due to air inhalation and consumption of drinking water are expected to be significantly lower (5-9 orders of magnitude) than those induced by the intake of tomatoes in this case study.

Captan↗
PubMed2004

A new multi-residue method for analysis of pesticide residues in fruit and vegetables using liquid chromatography with tandem mass spectrometric detection.

A new multi-residue method for determination of pesticide residues in a wide variety of fruit and vegetables, using the National Food Administration (NFA) ethyl acetate extraction and determination by means of LC-MS/MS, is presented. The method includes pesticides normally detected by LC-UV or LC-fluorescence such as benzimidazoles, carbamates, N-methylcarbamates and organophosphorus compounds with an oxidisable sulphide group as well. After extraction with ethyl acetate, the extract is concentrated and an aliquot of the extract is evaporated to dryness and redissolved in methanol before injection on LC-MS/MS. The method has been validated for 57 different pesticides and metabolites. Representative species from different commodity groups were chosen as matrices in order to study the influence from different matrices on recoveries. The fortification levels studied were 0.01-0.5 mg kg(-1). Matrix effects were tested for all matrices by means of standard addition to blank extracts. The matrix effect, expressed as signal in solvent compared to signal in matrix, was in general found to be small. The obtained recoveries are, with a few exceptions, in the range 70-100%. The proposed method is quick and straightforward and no additional clean-up steps are needed. The method can be used for the analysis of all 57 pesticides in one single determination step at 0.01 mg kg(-1).

Chromatography, Liquid↗