Toxicity testing of pesticides in zebrafish—a systematic review on chemicals and associated toxicological endpoints

The use of zebrafish (Danio rerio) has arisen as a promising biological platform for toxicity testing of pesticides such as herbicides, insecticides, and fungicides. Therefore, it is relevant to assess the use of zebrafish in models of exposure to investigate the diversity of pesticide-associated toxicity endpoints which have been reported. Thus, this review aimed to assess the recent literature on the use of zebrafish in pesticide toxicity studies to capture data on the types of pesticide used, classes of pesticides, and zebrafish life stages associated with toxicity endpoints and phenotypic observations. A total of 352 articles published between September 2012 and May 2019 were curated. The results show an increased trend in the use of zebrafish for testing the toxicity of pesticides, with a great diversity of pesticides (203) and chemical classes (58) with different applications (41) being used. Furthermore, experimental outcomes could be clustered in 13 toxicity endpoints, mainly developmental toxicity, oxidative stress, and neurotoxicity. Organophosphorus, pyrethroid, azole, and triazine were the most studied classes of pesticides and associated with various toxicity endpoints. Studies frequently opted for early life stages (embryos and larvae). Although there is an evident lack of standardization of nomenclatures and phenotypic alterations, the information gathered here highlights associations between (classes of) pesticides and endpoints, which can be used to relate mechanisms of action specific to certain classes of chemicals.     

Obsolete pesticide storage sites and their POP release into the environment—an Armenian case study

Organochlorinated pesticides were widely applied in Armenia until the 1980s, like in all former Soviet Union republics. Subsequently, the problem of areas contaminated by organochlorinated pesticides emerged. Environmental, waste and food samples at one pesticide burial site (Nubarashen) and three former pesticide storage sites (Jrarat, Echmiadzin and Masis) were taken and analysed on the content of organochlorinated pesticides, polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls. Gradient sampling and diffusivity-based calculations provided information on the contamination release from the hot spots on a local scale. A risk analysis based on samples of locally produced food items characterised the impact of storage sites on the health of nearby residents. All four sites were found to be seriously contaminated. High pesticide levels and soil and air contamination gradients of several orders of magnitude were confirmed outside the fence of the Nubarashen burial site, confirming pesticide release. A storage in Jrarat, which was completely demolished in 1996 and contained numerous damaged bags with pure pesticides until 2011, was found to have polluted surrounding soils by wind dispersion of pesticide powders and air by significant evaporation of lindane and β-endosulfan during this period. Dichlorodiphenyltrichloroethane-contaminated eggs, sampled from hens roaming freely in the immediate surroundings of the Echmiadzin storage site, revealed a significant health risk for egg consumers above 1E-5. Although small in size and previously almost unknown to the public, storage sites like Echmiadzin, Masis and Jrarat were found to stock considerable amounts of obsolete pesticides and have a significant negative influence on the environment and human health. Multi-stakeholder cooperation proved to be successful in identifying such sites suspected to be significant sources of persistent organic pollutants.     

微生物降解拟除虫菊酯类农药残留的研究进展

随着拟除虫菊酯类农药使用量不断增加,产生的农药残留问题对生态环境和人类健康造成了危害.对降解拟除虫菊酯类农药的微生物种类、降解酶和降解机制及降解酶基因克隆和构建工程菌等方面进行综述,旨在为研究和开发微生物降解拟除虫菊酯类农药残留提供参考.     

The relationship between dermal pesticide exposure by fruit harvesters and dislodgeable foliar residues

Dermal pesticide exposure rates, expressed in mg/hr, by strawberry and blueberry harvesters and dislodgeable foliar pesticide residues were determined in 7 separate field experiments during 1981-1983 in California and Oregon. The pesticides which were studied included captan, vinclozolin, carbaryl, and methiocarb. A positive correlation between these two parameters was found and compared with literature values involving different pesticides and tree crops. The ratio between dermal exposure rate and dislodgeable foliar residues, the units of which are area/time, may have a possible use as an empirical factor for a first approximation of dermal exposure rates by fruit harvesters without the involvement of human subjects.     

Estimation of pyrethroid pesticide intake using regression modeling of food groups based on composite dietary samples

Population-based estimates of pesticide intake are needed to characterize exposure for particular demographic groups based on their dietary behaviors. Regression modeling performed on measurements of selected pesticides in composited duplicate diet samples allowed (1) estimation of pesticide intakes for a defined demographic community, and (2) comparison of dietary pesticide intakes between the composite and individual samples. Extant databases were useful for assigning individual samples to composites, but they could not provide the breadth of information needed to facilitate measurable levels in every composite. Composite sample measurements were found to be good predictors of pyrethroid pesticide levels in their individual sample constituents where sufficient measurements are available above the method detection limit. Statistical inference shows little evidence of differences between individual and composite measurements and suggests that regression modeling of food groups based on composite dietary samples may provide an effective tool for estimating dietary pesticide intake for a defined population.     

Contamination levels of selected organochlorine and organophosphate pesticides in the Selangor River, Malaysia between 2002 and 2003

In Malaysia, rivers are the main source of public water supplies. This study was conducted from 2002 to 2003 to determine the levels of selected organochlorine and organophosphate pesticides in the Selangor River in Malaysia. Surface water samples have been collected seasonally from nine sites along the river. A liquid-liquid extraction followed by gas chromatography-mass spectrometry technique was used to determine the trace levels of these pesticide residues. The organochlorine pesticides detected were lindane, heptachlor, endosulfan, dieldrin, endosulfan sulfate, o,p'-DDT, p,p'-DDT, o,p'-DDE and p,p'-DDE whereas for organophosphate pesticides, they were chlorpyrifos and diazinon. At the river upstream where a dam is located for public water supply, incidents of pesticide levels exceeding the European Economic Community Directive of water quality standards have occurred. Furthermore, the wetland ecosystems located at the downstream of the river which houses the fireflies community is being threatened by occasional pesticide levels above EPA limits for freshwater aquatic organisms. The occurrence of these residual pesticides in the Selangor River can be attributed to the intense agriculture and urban activity.     

Obsolete pesticides and application of colonizing plant species for remediation of contaminated soil in Kazakhstan

In Kazakhstan, there is a problem of finding ways to clean local sites contaminated with pesticides. In particular, such sites are the deserted and destroyed storehouses where these pesticides were stored; existing storehouses do not fulfill sanitary standards. Phytoremediation is one potential method for reducing risk from these pesticides. Genetic heterogeneity of populations of wild and weedy species growing on pesticide-contaminated soil provides a source of plant species tolerant to these conditions. These plant species may be useful for phytoremediation applications. In 2008–2009 and 2011, we surveyed substances stored in 80 former pesticide storehouses in Kazakhstan (Almaty oblast) to demonstrate an inventory process needed to understand the obsolete pesticide problem throughout the country, and observed a total of 354.7 t of obsolete pesticides. At the sites, we have found organochlorine pesticides residues in soil including metabolites of dichlorodiphenyltrichloroethane and isomers of hexachlorocyclohexane. Twenty-four of the storehouse sites showed pesticides concentrations in soil higher than maximum allowable concentration which is equal to 100 μg kg^?1 in Kazakhstan. Seventeen pesticide-tolerant wild plant species were selected from colonizing plants that grew into/near the former storehouse’s pesticides. The results have shown that colonizing plant annual and biannual species growing on soils polluted by pesticides possess ability to accumulate organochlorine pesticide residues and reduce pesticide concentrations in soil. Organochlorine pesticides taken up by the plants are distributed unevenly in different plant tissues. The main organ of organochlorine pesticide accumulation is the root system. The accumulation rate of organochlorine pesticides was found to be a specific characteristic of plant species and dependent on the degree of soil contamination. This information can be used for technology development of phytoremediation of pesticide-contaminated soils.     

Cross-sectional biomonitoring study of pesticide exposures in Queensland,Australia, using pooled urine samples

A range of pesticides are available in Australia for use in agricultural and domestic settings to control pests, including organophosphate and pyrethroid insecticides, herbicides, and insect repellents, such as N,N-diethyl-meta-toluamide (DEET). The aim of this study was to provide a cost-effective preliminary assessment of background exposure to a range of pesticides among a convenience sample of Australian residents. De-identified urine specimens stratified by age and sex were obtained from a community-based pathology laboratory and pooled (n = 24 pools of 100 specimens). Concentrations of urinary pesticide biomarkers were quantified using solid-phase extraction coupled with isotope dilution high-performance liquid chromatography–tandem mass spectrometry. Geometric mean biomarker concentrations ranged from <0.1 to 36.8 ng/mL for organophosphate insecticides, <0.1 to 5.5 ng/mL for pyrethroid insecticides, and <0.1 to 8.51 ng/mL for all other biomarkers with the exception of the DEET metabolite 3-diethylcarbamoyl benzoic acid (4.23 to 850 ng/mL). We observed no association between age and concentration for most biomarkers measured but noted a “U-shaped” trend for five organophosphate metabolites, with the highest concentrations observed in the youngest and oldest age strata, perhaps related to age-specific differences in behavior or physiology. The fact that concentrations of specific and non-specific metabolites of the organophosphate insecticide chlorpyrifos were higher than reported in USA and Canada may relate to differences in registered applications among countries. Additional biomonitoring programs of the general population and focusing on vulnerable populations would improve the exposure assessment and the monitoring of temporal exposure trends as usage patterns of pesticide products in Australia change over time.     

Accumulation levels and characteristics of some pesticides in human adipose tissue samples from Southeast China

This paper presents a comprehensive study of pesticide levels and bio-accumulation characteristics in human adipose tissues among residents of Southeast China. A large number of adipose samples (n = 633) were selected for 58 pesticides and were analyzed by high sensitive Gas Chromatography-Tandem Mass Spectrometry (GC-MS/MS). The results showed that POPs pesticides were frequently detected, including 2,4′-DDD, 2,4′-DDE, 2,4′-DDT, 4,4′-DDD, 4,4′-DDE, 4,4′-DDT, α-HCH, β-HCH, γ-HCH, δ-HCH, hexachlorobenzene (HCB), and mirex. Other detected pesticide species were dicofol, methamidophos and chlordimeform, which have rarely been reported. Comparing to different countries, the concentrations of total DDT and HCH in these three Chinese southeastern sites were in the middle range, whereas the HCB and mirex were in the lower end. A significant correlation was observed between region as well as age and POPs pesticide levels. Some pesticide residue levels were also found significantly correlated to occupation. However, there was no significant correlation between gender and pesticides. Meanwhile, it is interesting to find that mortality of malignant tumors tends to associate with the pesticides levels in human adipose tissue. More importantly, the measured data presented in this study provide realistic information which is useful for assessing human exposure to pesticides in the general population of Southeast China.     

Hair as a marker for pesticides exposure

Rats were orally treated with mixtures of chlorinated pesticides. Hair was collected and analyzed for pesticide residues over a period of up to four weeks. Quantitative and qualitative analysis of the recovered pesticides in hair were determined using gas chromatography with electron capture detector. Results suggest that hair can be used as a biomarker for the monitoring of organochlorinated pesticide residues at low parts per billion levels. Chlorinated pesticides were also detected in human hair of environmentally exposed and occupationally exposed individuals, which indicates that hair can be used for monitoring pesticides exposure.     

Characterization of distribution of pesticide residues in crop units

The characteristic features of distribution of pesticide residues in crop units and single sample increments were studied based on more than 19,000 residue concentrations measured in root vegetables, leafy vegetables, small-, medium- and large-size fruits representing 20 different crops and 46 pesticides. Log-normal, gamma and Weibull distributions were found to provide the best fit for the relative frequency distributions of individual residue data sets. The overall best fit was provided by lognormal distribution. The relative standard deviation of residues (CV) in various crops ranged from 15–170%. The 100–120 residue values being in one data set was too small to identify potential effects of various factors such as the chemical and physical properties of pesticides and the nature of crops. Therefore, the average of CV values, obtained from individual data sets, were calculated and considered to be the best estimate for the likely variability of unit crop residues for treated field (CV = 0.8) and market samples (CV = 1.1), respectively. The larger variation of residues in market samples was attributed to the potential mixing of lots and varying proportion of non-detects. The expectable average variability of residues in composited samples can be calculated from the typical values taking into account the sample size.     

Pesticide residues in freshwater and marine zooplankton: a review

A review of the scientific literature on pesticide residues in freshwater and marine zooplankton indicates that despite the great number of pesticides in current use, only residues of the persistent organochlorine insecticides, many of which have been restricted or removed from general use in North America, have been determined. Much of this information is outdated. In addition, with the exception of the Great Lakes on which limited information is available, reports on residues in freshwater zooplankton are rare. Information on residues of the newer, less persistent but heavily used pesticides is lacking. As an alternative to field sampling and chemical analysis of endemic populations of zooplankton, scientists have modeled the bioaccumulation of pesticides in zooplankton using either laboratory microcosms or mathematical equations. However, the extent and importance of trophic transfer to higher food levels through this intermediary group of organisms is still controversial. In addition, the relationship between accumulation of pesticides and toxicity to zooplankton remains unresolved.     

In-residence,multiple route exposures to chlorpyrifos and diazinon estimated by indirect method models

One of the objectives of the National Human Exposure Assessment Survey (NHEXAS) is to estimate exposures to several pollutants in multiple media and determine their distributions for the population of Arizona. This paper presents modeling methods used to estimate exposure distributions of chlorpyrifos and diazinon in the residential microenvironment using the database generated in Arizona (NHEXAS-AZ). A four-stage probability sampling design was used for sample selection. Exposures to pesticides were estimated using the indirect method of exposure calculation by combining measured concentrations of the two pesticides in multiple media with questionnaire information such as time subjects spent indoors, dietary and non-dietary items they consumed, and areas they touched. Most distributions of in-residence exposure to chlorpyrifos and diazinon were log-normal or nearly log-normal. Exposures to chlorpyrifos and diazinon vary by pesticide and route as well as by various demographic characteristics of the subjects. Comparisons of exposure to pesticides were investigated among subgroups of demographic categories, including gender, age, minority status, education, family income, household dwelling type, year the dwelling was built, pesticide use, and carpeted areas within dwellings. Residents with large carpeted areas within their dwellings have higher exposures to both pesticides for all routes than those in less carpet-covered areas. Depending on the route, several other determinants of exposure to pesticides were identified, but a clear pattern could not be established regarding the exposure differences between several subpopulation groups.     

Effect of organophosphorus (dimethoate) and pyrethroid (deltamethrin) pesticides on semen characteristics in rabbits

The present study was undertaken to determine the effect of chronic treatment with two sublethal doses of Dimethoate (organo-phosphorus) or Deltamethrin (pyrethroid) on body weight and semen characteristics in adult male rabbits. Pesticide treatment resulted in a decline in body weight, libido, ejaculate volume, sperm concentration and semen initial fructose; and an increase in abnormal and dead sperm and methylene blue reduction time. In this regard Dimethoate showed greater effects than Deltamethrin. The hazardous effect of these pesticides on semen quality continued during the post-treatment period, and was dose-dependent. This deleterious effect on sperm formation together with the decline in libido suggest a decrease in testosterone secretion by pesticide treatment.     

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.     

室内空气中的化学农药及其检测技术

室内空气中化学农药之所以存在 ,主要因为我们在杀灭室内蚊、蝇、蚤、蚂蚁、蟑螂及老鼠时 ,使用了含化学农药的杀虫剂。目前 ,我国市场上流通的含有化学农药的杀虫剂商品近 1 0 0 0种 ,但从农药的有效成分来看 ,大约有 60余种。它们多属拟除虫菊酯类农药 ,占总数的 50 % ;此外还有氨基甲酸酯类、有机磷类农药等。本文重点介绍室内空气中化学农药的捕集及检测技术     

Ecological risk of pesticide residues in the British Columbia environment: 1973–2012

An updated ecological risk assessment was conducted to re-evaluate and review the overall risk of pesticide residues to certain aquatic life. The focus was the impact on offsite non-target, freshwater organisms of pesticide operational sprays in British Columbia from 1973 until 2012. The values of risk quotients for pesticides of selected indicator organisms were determined to measure the effect. When compared with organophosphorus, carbamate, and other miscellaneous pesticides, this risk assessment analysis suggests that the historical use of persistent and highly toxic organochlorine pesticides posed, and continue to pose, a deleterious ecological risk. The risk is both short-term acute and long-term sub-acute, chronic toxicity to offsite, non-target aquatic invertebrates and juvenile salmonid fish. Data indicated that these organisms were, and remain, subjected to harmful effects of pesticide residues to varying degrees. Most vulnerable were, and also are, benthic organisms inhabiting bottom sediments. This substrate is the natural sink for persistent pesticide residues, predominantly organochlorine pesticides from historical use, as well as dioxins, furans, and polycyclic aromatic hydrocarbons from wood preservatives, and other sources. Environment Canada's main aquatic protection strategy was a 10 metre no-treatment buffer zone, augmented with an additional appropriate setback along shorelines of fishery and wildlife resource-sensitive water bodies. This study discusses why this guideline was necessary, useful and effective, but was only partially successful. The physical-chemical properties of pesticide residues, from either an individual compound or different compounds in combination, also influence the nature of biological impacts on non-target, aquatic organisms. Few studies have been conducted in British Columbia aquatic environments to investigate the significance of this aspect.     

Estimation of measurement uncertainty associated to the determination of pesticide residues: a case study

In the analytical analysis the measurement uncertainty is a quantitative indicator of the confidence describing the range around a reported or experimental result within which the true value can be expected. Several approaches can be used to estimate the measurement uncertainty associated to the analysis of pesticide residues: a) the top-down, the estimation can be referred to default values; b) the bottom-up the estimation is related to the uncertainty sources. Concerning the bottom-up approach, the following contributions have been investigated: weight of sample, calibration solutions, final volume of sample and intermediate repeatability studies. The commodity/residue combination selected in this study was celery/tau-fluvalinate pesticide. Tau-fluvalinate is a broad-spectrum insecticide in the pyrethroid class of pesticides. The Maximum Residue Limit (MRL) of tau-fluvalinate in celery has been set at 0.01 mg/kg. The tau- Fluvalinate showed two chromatographic peaks. Since the individual standards are not available, the two peaks were integrated separately and the instrumental responses were added. The total residue was calculated on the basis of resulted peaks. The present work aims to compare the uncertainty estimated by experimental data using repeated analysis (n = 12) of a real sample and a spiked sample. The relative expanded uncertainty for two data set, incurred and spiked, was 22 % and 20 %, respectively. No differences were observed from repeated determinations of real samples and spiked samples.     

Pesticide distribution in an agricultural environment in Argentina

An assessment of the off-site migration of pesticides from agricultural activity into the environment in the Neuquen River Valley was performed. The aim of this study was to evaluate the distribution of pesticides in several compartments of a small agricultural sub-catchment. Soil, surface water, shallow groundwater and drift deposition were analyzed for pesticide residues. Results showed the presence of some pesticide residues in soil, surface water and shallow groundwater compartments. The highest detection frequencies in water (surface and subsurface) were found for azinphos-methyl and chlorpyrifos (>70%). In terms of concentration, the highest levels were observed in shallow groundwater for azinphos methyl (22.5 μg/L) and carbaryl (45.7 μg/L). In the soil, even before the application period had started, accumulation of residues was present. These residues increased during the period studied. Spray drift during pesticide application was found to be a significant pathway for the migration of pesticide residues in surface water, while leaching and preferential flows were the main transport routes contributing to subsurface contamination.     

Formaldehyde Concentrations in Wisconsin Mobile Homes

Mobile homes utilize a class of prefabricate construction techniques which rely greatly upon the use of particle board and hardwood plywood paneling for structural components. This has resulted In household sources which may emit formaldehyde into the home, since urea-formaldehyde resins are used as the bonding agent in most pressed wood stocks. A series of 137 mobile home households was investigated to determine indoor formaldehyde exposure concentrations. Homes were selected based on the estimated age of the construction components. Homes were studied serially for a nine-month period, with formaldehyde samples obtained on a monthly basis using a modified NIOSH chromotropic acid procedure. Formaldehyde concentrations were found to range from less than 0.10 ppm to 2.84 ppm. The median exposure concentration was 0.39 ppm. Analysis of variance was performed on each home to discern visit and room measurement effects. Eighty-nine percent of the homes exhibited no measurement placement effects, while only 10 percent failed to demonstrate between-visit variance effects. Regression models were constructed to predict household formaldehyde concentrations. Concentrations exhibited an inverse relationship with the age of the construction materials. A weighted least squares regression model of log of home age predicting temperature-corrected log formaldehyde explained 82 percent of the formaldehyde variation.