Perspectives of the chemical fate and toxicity of pesticides

Abstract

The wide‐spread use of pesticides in modern agriculture has created a need to investigate the chemical transformation of pesticides in plants and animals. This paper reviews the chemical and biochemical fate of various pesticides and other xenobiotics. Photochemical mechanisms appear to be the most common pathways for the abiotic transformation of these chemicals. Biotic transformation includes a large group of biochemical reactions which may result in either deactivation (detoxication) or activation (toxication) of bioactive compounds. The need for quality control in the production of pesticides is also discussed.     

Use of molecular and In Silico bioinformatic tools to investigate pesticide binding to insect (Lepidoptera) phenoloxidases (PO): Insights to toxicological aspects

In the present work, the promising bioinformatic tools, based on structure–affinity analysis, allowed to screen several pesticides supposed to bind to the insect immune Phenoloxidases (PO). First, the binding of aminoparathion, a reference compound, to the PO was structurally (3D) validated in accordance with previous reports. Second, using the same docking conditions, a range of pesticides was checked for their binding ability to the crystal 3D structure (PDB 3HSS) of the insect Manduca sexta (Lepidoptera) PO. The obtained data showed that many of the tested pesticides were able to bind, in silico, to M. sexta PO. The combination of in vitro (chemical and biochemical) and in silico (automated docking) approaches was found advantageous to elucidate the behavior of phenolic pesticides as substrate-analogues when binding to the active site of insect POs. Our findings emphasize new ecotoxicological aspects of pesticide residues in the agro-chemical and environmental circles.     

Environmental fate of rice paddy pesticides in a model ecosystem.

The distribution and metabolic fate of several rice paddy pesticides were evaluated in a modified model ecosystem. Among the three BHC isomers, beta-isomer was the most stable and bioconcentrated in all of the organisms. Alpha- and gamma-isomers were moderately persistent and degraded to some extent during the 33 day period. Disulfoton was relatively persistent due to the transformation to its oxidation products. Pyridaphenthion was fairly biodegradable. N-Phenyl maleic hydrazide derived from the hydrolysis of pyridaphenthion was not detected in the organisms though it was found in the aquarium water after 33 days. Cartap and edifenphos were considerably biodegradable, and the ratio of the conversion to water soluble metabolites was very high. There was a distinct difference in the persistence of Kitazin P and edifenphos in the aquarium water. It appeared that the hydrolysis rate of the pesticides affected their fate in the organisms. PCP appeared to be moderately biodegradable. CNP was considerably stable and stored in the organisms though the concentration in the aquarium water was relatively low. The persistence and distribution of the pesticides in the model ecosystem were dependent on their chemical structures. In spite of the limitation derived from short experimental period, the model ecosystem may be applicable for predicting the environmental fate of pesticides.     

Polar organic chemical integrative sampler (POCIS) uptake rates for 17 polar pesticides and degradation products: laboratory calibration

Polar organic chemical integrative samplers (POCIS) are useful for monitoring a wide range of chemicals, including polar pesticides, in water bodies. However, few calibration data are available, which limits the use of these samplers for time-weighted average concentration measurements in an aquatic medium. This work deals with the laboratory calibration of the pharmaceutical configuration of a polar organic chemical integrative sampler (pharm-POCIS) for calculating the sampling rates of 17 polar pesticides (1.15?≤?logK _ow?≤?3.71) commonly found in water. The experiment, conducted for 21 days in a continuous water flow-through exposure system, showed an integrative accumulation of all studied pesticides for 15 days. Three compounds (metalaxyl, azoxystrobine, and terbuthylazine) remained integrative for the 21-day experiment. The sampling rates measured ranged from 67.9 to 279 mL?day^?1 and increased with the hydrophobicity of the pesticides until reaching a plateau where no significant variation in sampling rate is observed when increasing the hydrophobicity.     

Changes in the chemical composition of water-extractable organic matter during composting: distribution between stable and labile organic matter pools

Aerobic decomposition and stabilization of organic matter during the composting of waste materials is primarily due to the biochemical transformation of water-soluble compounds in the liquid phase by the microbial biomass. For this reason water-soluble organic matter represents the most active fraction of compost, both biologically and chemically, and thus should directly reflect the biochemical alteration of organic matter. This work aims to elucidate the microbial-mediated processes responsible for the distribution of soluble organic matter between stable and labile pools with composting time. Accordingly, chemical analysis as well as UV absorption, and ¹H and ¹³C-NMR spectroscopy of samples collected during the industrial composting of urban waste revealed microbial induced transformation of water-extractable organic matter over time. The chemical composition changed from labile, hydrophilic, plant-derived organic compounds in the beginning to predominately stable, hydrophobic moieties comprising lignin-derived phenols and microbially-derived carbohydrates at later stages of composting.     

Assessment of pesticide residues in army cutworm moths (Euxoa auxiliaris) from the Greater Yellowstone Ecosystem and their potential consequences to foraging grizzly bears (Ursus arctos horribilis)

During summer, a grizzly bear (Ursus arctos horribilis) in the Greater Yellowstone Ecosystem (GYE) (USA) can excavate and consume millions of army cutworm moths (Euxoa auxiliaris) (ACMs) that aggregate in high elevation talus. Grizzly bears in the GYE were listed as threatened by the US Fish and Wildlife Service in 1975 and were proposed for delisting in 2005. However, questions remain about key bear foods. For example, ACMs are agricultural pests and concern exists about whether they contain pesticides that could be toxic to bears. Consequently, we investigated whether ACMs contain and transport pesticides to bear foraging sites and, if so, whether these levels could be toxic to bears. In 1999 we collected and analyzed ACMs from six bear foraging sites. ACMs were screened for 32 pesticides with gas chromatography with electron capture detection (GC-ECD). Because gas chromatography with tandem mass spectrometry (GC-MS/MS) can be more sensitive than GC-ECD for certain pesticides, we revisited one site in 2001 and analyzed these ACMs with GC-MS/MS. ACMs contained trace or undetectable levels of pesticides in 1999 and 2001, respectively. Based on chemical levels in ACMs and numbers of ACMs a bear can consume, we calculated the potential of chemicals to reach physiological toxicity. These calculations indicate bears do not consume physiologically toxic levels of pesticides and allay concerns they are at risk from pesticides transported by ACMs. If chemical control of ACMs changes in the future, screening new ACM samples taken from bear foraging sites may be warranted.     

Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine

The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol–water partition coefficient (log K_ow) 2.7–6.3 and water solubility 0.0002–142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log K_ow, water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.     

Mutagenicity evaluation of chemical pesticides

Abstract

Over the last few decades, the use of chemical pesticides has increased dramatically in the U.S. This relatively sudden increase greatly concerns the U.S. Environmental Protection Agency (EPA), since it has the responsibility for ensuring the safety of all pesticides used in the U.S. In response to this concern, EPA has established a review program, the Rebuttable Presumption Against Registration (RPAR), for periodically reassessing the mutagenic and carcinogenic potential of pesticide compounds.

This paper presents a review and evaluation of the data reported in the literature on six chemical pesticides suspect for mutagenic potential. The pesticide chemicals discussed are maleic hydrazide; rotenone; monuron; diallate; triallate, and benomyl.     

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.     

Contamination of vegetables of different seasons with organophosphorous pesticides and related health risk assessment in northern India

India is an agrarian country. The use of pesticides, herbicides and fungicides were introduced in India during the mid-sixties, which are now being used on a large scale and is a common feature of Indian agriculture. The main intention of the introduction of pesticides was to prevent and control insects, pests and diseases in the field crops. Initially the use of pesticides reduced pest attack and paved way for increasing the crop yield as expected. Simultaneously, increased use of chemical pesticides has resulted in contamination of environment and also caused many long-term affect on the society. In the present study an effort has been made to evaluate the residual concentration of selected organophosphorous pesticides (methyl parathion, chlorpyriphos and malathion) in vegetables grown in different seasons (summer, rainy and winter). Data obtained was then used for estimating the potential health risk associated with the exposure to these pesticides. The pesticides residue concentrations in vegetables of different season shows that the winter vegetables are the most contaminated followed by summer and rainy vegetables. The concentration of the various pesticides were well below the established tolerances but continuous consumption of such vegetables even with moderate contamination level can accumulate in the receptor's body and may prove fatal for human population in the long term. The analysis of health risk estimates indicated that chlorpyriphos and malathion did not poses a direct hazard, however, exposure to methyl parathion has been found to pose some risk to human health.     

Inhibition of plasma butyrylcholinesterase activity in the lizard Gallotia galloti palmae by pesticides: a field study

A field study was performed to evaluate the effect of exposure to organophosphorus (OP) and carbamate (CB) pesticides on the lizard Gallotia galloti palmae. Butyrylcholinesterase (BChE) activity was measured in the plasma of 420 lizards collected from agricultural and reference areas on the Island of La Palma (Canary Islands, Spain) in two sampling periods. Exposure to cholinesterase-inhibiting pesticides was evaluated by a statistical criterion based on a threshold value (two standard deviations below the mean enzyme activity) calculated for the reference group, and a chemical criterion based on the in vitro reactivation of BChE activity using pyridine-2-aldoxime methochloride (2-PAM) or after water dilution of the sample. Mean (+/- SD) BChE activity for lizards from agricultural areas was significantly lower (Fuencaliente site = 2.00 +/- 0.98 micromol min(-1) ml(-1), Tazacorte site = 2.88 +/- 1.08) than that for lizards from the reference areas (Los Llanos site = 3.06 +/- 1.17 micromol min(-1) ml(-1), Tigalate site = 3.96 +/- 1.62). According to the statistical criterion, the number of lizards with BChE depressed was higher at Fuencaliente (22% of males and 25.4% of females) than that sampled at Tazacorte (7.8% of males and 6.2% of females). According to the chemical criterion, Fuencaliente also yielded a higher number of individuals (112 males and 47 females) with BChE activity inhibited by both OP and CB pesticides. CBs appeared to be the pesticides most responsible for BChE inhibition because most of the samples showed reactivation of BChE activity after water treatment (63.3% from Fuencaliente and 29% from Tazacorte). We concluded that the use of reactivation techniques on plasma BChE activity is a better and more accurate method for assessing field exposure to OP/CB pesticides in this lizard species than making direct comparisons of enzyme activity levels between sampling areas.     

Applicability of polar organic compound integrative samplers for monitoring pesticides in groundwater

Polar organic chemical integrative samplers (POCISs) for the monitoring of polar pesticides in groundwater were tested on two sites in order to evaluate their applicability by comparison with the spot-sampling approach. This preliminary study shows that, as in surface water, POCIS is a useful tool, especially for the screening of substances at low concentration levels that are not detected by laboratory analysis of spot samples. For quantitative results, a rough estimation is obtained. The challenge is now to define the required water-flow conditions for a relevant quantification of pesticides in groundwater and to establish more representative sampling rates for groundwater.     

Absorption of current use pesticides by snapping turtle (Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle (Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC-MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.     

Passive sampling of selected pesticides in aquatic environment using polar organic chemical integrative samplers

Purpose  

Polar chemical integrative samplers (POCIS) were examined for their sampling efficiency of 12 pesticides and one metabolite commonly detected in surface waters. Laboratory-based calibration experiments of POCISs were conducted. The determined passive sampling rates were applied for the monitoring of pesticides levels in Lake Amvrakia, Western Greece. Spot sampling was also performed for comparison purposes.     

Legislative aspects of pesticide regulations

Abstract

This paper reviews the development of pesticides as an agricultural and health tool and discusses the national and international implications of pesticide regulation. The need for scientific input to the legislative and regulative processes is explained. Appropriate legislation and regulatory structures are presented. Finally, the need for international cooperation in the use and control of pesticides is analyzed.     

Monitoring of organochlorine pesticides residues in green mussels (Perna viridis) from the coastal area of Thailand

The utilization of organochlorine pesticides for pest control chemical has been of great interest on residue contamination from biological organisms in the environment. Green mussel (Perna viridis) samples were monitored as bioindicators for assessment of the water quality in coastal waters along the Gulf of Thailand. Thirty-six samples were collected from 12 stations during 1997-1999 and analysed for 26 organochlorine pesticide compounds. This paper focuses on the contamination of organochlorine pesticide residues in green mussel (P. viridis) during 1997-1999. The limit of detection of all organochlorine pesticides compounds was at the range of 0.1-8.3 ng g(-1) wet weight and recovery 75-95%. The concentration of organochlorine pesticides residues in green mussel was lower than the maximum residue limit for aquatic animals as recommended by the Ministry of Public Health of Thailand. The trend of organochlorine pesticide residue contamination in this area decreased from 1989 to 1999.     

农药对藻类的生态毒理学研究Ⅱ:毒性机理及其富集和降解

随着对农药污染认识的深入,农药对生态系统的初级生产者———藻类毒性以及毒性机制的研究不断增多。农药对藻类的毒性在于破坏藻类生物膜的结构和功能、影响藻类的光合作用、改变呼吸作用以及固氮作用,影响藻类的生理进程并改变其生化组分。开展农药对藻类毒性机理的研究,揭示农药结构—活性关系,对农药的研制和应用,评价农药的生态风险,减少农药对藻类的毒害是重要的。在自然环境中还发现藻能富集和降解农药。因此,对于这些藻来说,农药对藻类的毒害作用和藻类对农药的富集和降解作用可能同时存在。本文综述了农药对藻类的毒性机理以及藻类对农药的富集和降解作用。     

The Forum of the International HCH and Pesticides Association—a platform for international cooperation

The unsustainable life cycle management of pesticides in the last 60 years has created large pesticide stockpiles. The two major working areas of the International HCH and Pesticide Association (IHPA; www.ihpa.info) address a part of these legacies and are shortly introduced here: (1) The assessment and support of the management of the worlds single largest POPs stockpile: the globally dumped 4 to 7 million tonnes hexachlorocyclohexane (HCH) wastes from lindane production, and (2) the support for the management of the obsolete pesticides legacy in Eastern Europe, the Caucasus and Central Asia (EECCA) countries of ~240,000 t, leaving these pesticides in unregulated storages without adequate safety control being a huge risk to the environment and human health. The integrative approach IHPA takes—promoting international cooperation and the exchange of knowledge and experiences—is shortly explained. IHPA has developed various supporting tools for its work: the IHPA web page and newsletter informing on the threats and challenges, but also on the progresses of managing pesticide stockpiles; the joint GIZ-PAN-IHPA exhibition on awareness of the pesticide stockpile challenge; and the ‘International HCH and Pesticides Forum’ as most important tool to progress the integrative work and mission of IHPA. Finally, a summary of the 11th International HCH and Pesticides Forum held in Gabala, Azerbaijan is given which brought together more than 120 scientists, policy-makers, non-governmental and international organisations, industry and students from more than 40 countries to progress the obsolete pesticides and hazardous chemical waste challenge in EECCA countries. The event finished with adoption of ‘Gabala Declaration’, which aims to mobilise efforts of all stakeholders for prevention and elimination of POPs, obsolete pesticides, and hazardous chemical waste in the region.     

Sorption behaviour of acetochlor,atrazine, carbendazim,diazinon, imidacloprid and isoproturon on Hungarian agricultural soil

Laboratory studies were conducted to determine the sorption behaviour of six commonly used pesticides (acetochlor, atrazine, carbendazim, diazinon, imidacloprid and isoproturon) on Hungarian brown forest soil with clay alluviation (Luvisol) using the batch equilibrium technique. The sorption isotherms could be described by the Freundlich equation in non-linear form (n < 1) for all compounds, however in case of diazinon using the extended Freundlich equation proved to be a better approach. The adsorption constant related soil organic carbon content (Koc) calculated from Freundlich equation were 314 for acetochlor, 133 for atrazine, 2805 for carbendazim, 1589 for diazinon, 210 for imidacloprid and 174 for isoproturon. The octanol-water partition coefficients (Pow), which can be a useful parameter to predict of adsorption behaviour of a chemical on soil, and dissociation coefficients of these pesticides were calculated based on the chemical structure of them using a computerized expert system. The octanol-water partition coefficients were determined experimentally from high performance liquid chromatographic parameters as well. Good agreement was observed between experimental and the computer expert system estimated data. Computer estimated log Pow values ranged 0.5 and 3.86 for the examined pesticides, with imidacloprid and diazinon being the least and most hydrophobic respectively. Experimentally determined logPow ranged between 0.92 and 3.81 with the same tendency. It can be concluded that the Freundlich adsorption constants (Kf) are slightly related to the octanol-water partition coefficients of investigated chemicals, nevertheless no close correlation could be established because of the influence of further characteristics of solutes and soil.     

Uptake and Modeling of Pesticides by Roots and Shoots of Parrotfeather (Myriophyllum aquaticum) (5 pp)

Intention, Goal, Scope, Background Aquatic plants have a great potential to function as in situ, on-site biosinks and biofilters of pollutants. They are used for phytoremediation and phytotoxicity studies. Pesticide uptake studies are very important to predict contaminant accumulation, translocation, and transformation. There are a lot of models which have been developed for emergent plants, but there are not any existing models for submerged aquatic plants for assessing pesticide uptake. Objective In this study, uptake of selected pesticides in parrotfeather (Myriophyllum aquaticum) were studied and the results were modeled with the aid of Log Kow and the concentration of pesticides. At the end, the developed model was compared to other existing models. Methods The test was conducted with parrotfeather as a model plant. The bioassay and cultivation of this plant were examined. Pesticide uptake by roots and shoots was determined using 14C-radiolabeled materials. Results and Discussion The results were fitted with an equation that showed a relationship between uptake and lipophilicity of pesticides. The model was compared with other pesticide uptake models developed for other plants. Atrazine and cycloxidim were taken up more by roots than by shoots in comparison to other pesticides used. The total uptake, both in shoots and roots, was lower than for terbutryn and trifluralin. The best appropriate model was developed from the results against the other models seen in the literature. The concentration factors (Root Concentration Factor (RCF) and Submerged Shoot Concentration Factor (SSCF)) increased with a higher Kow of the substances. The Submerged Shoot Concentration Factor (SSCF) revealed a better relationship of the chemicals than did the Root Concentration Factor (RCF). Conclusions In this study, an uptake model was developed for rooted, submerged aquatic plants. Further studies are necessary to develop and compare models with different plants and pesticides. Recommendation and Outlook Such studies as this one may be extended to other environmental pollutants in the aquatic ecosystem and may be employed to evaluate the possibility of using different plants in phytoremediation studies.