The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

Predicting the aquatic risk of realistic pesticide mixtures to species assemblages in Portuguese river basins

Although pesticide regulatory tools are mainly based on individual substances, aquatic ecosystems are usually exposed to multiple pesticides from their use on the variety of crops within the catchment of a river. This study estimated the impact of measured pesticide mixtures in surface waters from 2002 and 2008 within three important Portuguese river basins (‘Mondego’, ‘Sado’ and ‘Tejo’) on primary producers, arthropods and fish by toxic pressure calculation. Species sensitivity distributions (SSDs), in combination with mixture toxicity models, were applied. Considering the differences in the responses of the taxonomic groups as well as in the pesticide exposures that these organisms experience, variable acute multi-substance potentially affected fractions (msPAFs) were obtained. The median msPAF for primary producers and arthropods in surface waters of all river basins exceeded 5%, the cut-off value used in the prospective SSD approach for deriving individual environmental quality standards. A ranking procedure identified various photosystem II inhibiting herbicides, with oxadiazon having the relatively largest toxic effects on primary producers, while the organophosphorus insecticides, chlorfenvinphos and chlorpyrifos, and the organochloride endosulfan had the largest effects on arthropods and fish, respectively. These results ensure compliance with European legislation with regard to ecological risk assessment and management of pesticides in surface waters.     

The impact of pesticides on oxidative stress level in human organism and their activity as an endocrine disruptor

Pesticides cause serious environmental and health problems both to humans and animals. The aim of this review is to discuss selected herbicides and fungicides regarding their mode of action and their influence on basic oxidative stress parameters and endocrine disruption properties tested in selected cell cultures in vitro. Because of numerous difficulties which animal studies are subject to, cell cultures are an excellent experimental model reflecting human exposure to different pesticides through all relevant routes. This experimental model can be used to monitor aggregate and cumulative pesticide exposures.     

Characterisation of FOGs in grease trap waste from the processing of chickens in Thailand

Industrial firms that kill and process chickens generate wastewater that contains fat, oil, and grease (FOG). The FOGs are located in the fatty waste that is collected by floatation in grease traps. Chemical and physical characterisation of FOGs would provide useful information that would help in the development of methods designed to decrease the extent of pollution caused by disposal of the waste and to utilise commercially some of its lipid constituents. Employing these methods would enhance the profitability and competitive potential of these commercial organisations. Samples of grease trap waste from 14 firms in central Thailand have been examined. Due to the very different schemes of waste management employed by these firms, the physical appearance of their fatty wastes showed considerable variation. The chemical and physical properties of the FOGs present in these wastes showed considerable variation also. Large amounts of free fatty acids (10–70% as oleic acid) were detected in most of the 14 wastes and palmitic, cis-9-oleic, cis,cis-9,12-linoleic, stearic, and palmitoleic acids were the predominant species of free and esterified acids. Most of the FOGs were solid at temperatures below 40 °C. Many of them contained traces of heavy metals (Cu and Pb) and some contained traces of the pesticides dimethoate and cypermethrin. The content of these potentially hazardous substances would have to be considered very carefully before discarding the fatty wastes and during the development of methods designed to isolate their potentially profitable lipid constituents.     

Comprehensive estimate of the theoretical maximum daily intake of pesticide residues for chronic dietary risk assessment in Argentina

A chronic dietary risk assessment for pesticide residues was conducted for four age groups of the Argentinian population following the procedure recommended by the WHO. The National Theoretical Maximum Daily Intake (NTMDI) for 308 pesticides was calculated for the first time, using the Maximum Residue Limits (MRLs) from several Argentinean regulations and food consumption data from a comprehensive National Nutrition and Health Survey. The risk was estimated by comparing the TMDI with the Acceptable Daily Intakes (ADI) identified by various sources. Furthermore, for each of the compounds with a TMDI >65% of the ADI, a probabilistic analysis was conducted to quantify the probability of exceeding the ADI. In this study 27, 22, 10, and 6 active ingredients (a.i.) were estimated to exceed the 100% of the ADI for the different population groups: 6–23 month-old children, 2–5 year-old children, pregnant women, and 10–49 year-old women, respectively. Some of these ADI-exceeding compounds (carbofuran, diazinon, dichlorvos, dimethoate, oxydemeton-methyl and methyl bromide) were found in all four of these groups. Milk, apples, potatoes, and tomatoes were the foods that contributed most to the intake of these pesticides. The study is of primary importance for the improvement of risk assessment, regulations, and monitoring activities.     

Impact of European legislation on marketed pesticides — A view from the standpoint of health impact assessment studies

The very significant impact of European legislation (Directive 91/414/EEC) on the authorization of plant protection products is reviewed herein, which has resulted in withdrawal of 704 active substances (AS) out of 889 assessed so far. The list of currently approved 276 AS includes 194 AS “existing” in the market before 1993 and 82 “new” AS introduced during the last 15 years. Results of toxicity characterization of the approved AS are also summarized, utilizing several well-known databases. Although significant data gaps exist for a rather large part of the approved AS, it is found that 84 AS are positive for at least one health effect (after chronic and/or acute exposure) including carcinogenicity, reproductive and neuro-developmental disorders, as well as endocrine disruption. The toxicity characterization results of this study are compared to those of recent assessments by other organizations (KemI, the Swedish Chemicals Agency, and the Pesticide Safety Directorate of the UK), where interpretation and use is made of AS “cut-off” criteria foreseen in new EU legislation. These studies report a comparatively smaller AS number with positive toxicity characterization. The possibility of some additional AS withdrawal in the near future, combined with the rather small rate of new AS introduction (approx. 5 per year) suggest that the list of approved AS over the next 10–15 years may not change very drastically. Consideration of the above trends is necessary and instructive in evaluating results of existing health impact assessment (HIA) studies, as well as in planning new ones. Due to the very drastic change in the number and type of marketed AS, that took place within the past 8–9 years, it is suggested that new HIA studies (based on epidemiological data after year 2000) should focus on a rather short time frame and, therefore, on appropriate cohort groups, e.g. young children. For the same reason, results of epidemiological studies of the past (involving banned AS) should be carefully interpreted and used with caution.     

QSAR trout toxicity models on aromatic pesticides

The pesticides originally designed to kill target organisms are dangerous for many other wild species. Since they are applied directly to the environment, they can easily reach the water basins and the topsoil. A dataset of 125 aromatic pesticides with well-expressed aquatic toxicity towards trout was subjected to quantitative structure activity relationships (QSAR) analysis aimed to establish the relationship between their molecular structure and biological activity. A literature data for LC₅₀ concentration killing 50% of fish was used. In addition to the standard 2D-QSAR analysis, a comparative molecular field analysis (CoMFA) analysis considering the electrostatic and steric properties of the molecules was also performed. The CoMFA analysis helped the recognition of the steric interactions as playing an important role for aquatic toxicity. In addition, the transport properties and the stability of the compounds studied were also identified as important for their biological activity.     

Transfer of pesticides to the brew during mate drinking process and their relationship with physicochemical properties

In order to evaluate the extraction of pesticide residues that are transferred to the brew during mate drinking process of P.U.1 yerba mate leaves (Ilex paraguariensis), a special device to simulate the way in which mate is drunk in Uruguay was developed. The transfer to the brew of 12 organophosphates, 5 synthethic pyrethroids and one organochlorine pesticide from spiked samples was studied. The relationship between the transfer data thus obtained and physicochemical properties like water solubility (Ws), octanol-water coefficient (Kow) and Henry's constant (H) was evaluated. The extractability of the pesticide residues from yerba mate can be correlated with log Ws and log Kow. These transfer values allowed the calculation of ARLs (acceptable residue level) for the pesticides following Food and Agriculture Organization (FAO), World Health Organizaion (WHO) guidelines. These results can help the future establishment of maximum residue levels (MRLs)     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

Pesticide residue dynamics in passion fruits: Comparing field trial and modelling results

We evaluated the exposure to pesticides from the consumption of passion fruits and subsequent human health risks by combining several methods: (i) experimental field studies including the determination of pesticide residues in/on passion fruits, (ii) dynamic plant uptake modelling, and (iii) human health risk assessment concepts. Eight commonly used pesticides were applied onto passion fruits cultivated in Colombia. Pesticide concentrations were measured periodically (between application and harvest) in whole fruits and fruit pulp. Measured concentrations were compared with predicted residues calculated with a dynamic and crop-specific pesticide uptake model, namely dynamiCROP. The model accounts for the time between pesticide application and harvest, the time between harvest and consumption, the amount of spray deposition on plant surfaces, uptake processes, dilution due to crop growth, degradation in plant components, and reduction due to food processing (peeling). Measured and modelled residues correspond well (r² = 0.88-0.99), with all predictions falling within the 90% confidence interval of the measured values. A mean error of 43% over all studied pesticides was observed between model estimates and measurements. The fraction of pesticide applied during cultivation that is eventually ingested by humans is on average 10⁻⁴-10⁻⁶, depending on the time period between application and ingestion and the processing step considered. Model calculations and intake fractions via fruit consumption based on experimental data corresponded well for all pesticides with a deviation of less than a factor of 2. Pesticide residues in fruits measured at recommended harvest dates were all below European Maximum Residue Limits (MRLs) and therefore do not indicate any violation of international regulatory thresholds.