Comparative study of accessibility of distinctive pesticides

Interactions of micro-contaminants with soil may play a crucial role in their environmental fate and possible harmful effects. Major goals of our investigations were to model the availability of widely used pesticides and characterize adsorption capabilities of distinctive soil types by the accomplishment of extensive comparative studies and application of several extraction methods. Environmental and biological relevance of these examinations is enhanced by the fact that intrinsic features and specific details of pesticide accessibility have not been revealed so far by a comparative approach. Five different experimental methods were assessed for modelling accessibility of five selected pesticides. The applied models for regaining the pesticides showed diverse efficiency in extraction capability in cases of the different soil types (sandy, brown forest and alluvial soils). The amounts of the obtained pesticides were determined by using gas-chromatography coupled to mass spectrometry (GC-MS) and high pressure liquid chromatography coupled to mass spectrometry (HPLC-MS). Accessibility of pesticides was also compared in cases of sterilized and real soil samples in order to estimate the extent of the influence of microflora. Aqueous extraction solvents proved to be suitable for accurate assessment of the accessible amounts of pesticides, as their effectivity was at least as high as that of the applied organic solvents. In our studies pesticide-soil interactions have comprehensively been characterized, and possible influences of environmental factors on the accessibility have also been revealed. Our study might be regarded as a tentative approach to model some significant circumstances playing key roles in pesticides' possible bioavailability.     

Occurrence of pesticides and polychlorinated biphenyls in water of the Nile river at the estuaries of Rosetta and Damiatta branches,north of delta,Egypt

Abstract

A study was conducted from summer 1995 to summer 1997 to assess the seasonal occurrence of pesticide residues and other organic contaminants, polychlorinated biphenyls (PCBs), in water at the estuaries of Rosetta and Damiatta branches of the Nile river. The results indicated that organochlorine compounds (OCs) including HCB, lindane, p,p‘‐DDE, p,p‘DDD, p,p‘‐DDT, aroclor 1254 and aroclor 1260 were present in all the water samples at concentration levels ranging between 0.195–0.240, 0.286–0.352, 0.035–0.067, 0.019–0.033, 0.024–0.031, 0.390–0.70 and 0.166–0.330 μg/l, respectively. The levels of these compounds were higher in water of Damiatta branch than those found in water of Rosetta branch. Aldrin, dieldrin and endrin were not detected in all water samples. Only 4 compounds from 36 organophosphorus insecticides, fungicides and s‐triazine herbicides tested were detected in water samples collected during summer and autumn seasons from Rosetta branch. The concentration levels of these detected compounds, dimethoate, malathion, captan, and ametryne, ranged from 0.011 to 0.340 μg/l, respectively. Similar compounds during the same seasons as found in water of Rosetta branch were also detected in water of Damiatta branch except ametryne. The levels of the detected compounds (dimethoate, malathion and captan) ranged between 0.030 and 0.330 μg/l. The levels of detected organophosphorus insecticides, fungicides and s‐triazine herbicides were in the order: dimethoate > malathion > captan > ametryne.     

Photocatalytic Degradation of an Organophosphorus Pesticide Phosalone in Aqueous Suspensions of Titanium Dioxide

Abstract

The present work deals with photocatalytic degradation of an organophosphorus pesticide, phosalone, in water in the presence of TiO₂ particles under UV light illumination (1000 W). The influence of the basic photocatalytic parameters such as pH of the solution, amount of TiO₂, irradiation time, stirring rate, and distance from UV source, on the photodegradation efficiency of phosalone was investigated. The degradation rate of phosalone was not high when the photolysis was carried out in the absence of TiO₂ and it was negligible in the absence of UV light. The half-life (DT₅₀) of a 20 ppm aqueous solution of phosalone was 15 min in optimized conditions. The plot of lnC (phosalone) vs. time was linear, suggesting first order reaction (K = 0.0532 min^?1). The half-life time of photomineralization in the concentration range of 7.5–20 ppm was 13.02 min. The efficiency of the method was also determined by measuring the reduction of Chemical Oxygen Demand (COD). During the mineralization under optimized conditions, COD decreased by more than 45% at irradiation time of 15 min. The photodegradation of phosalone was enhanced by addition of proper amount of hydrogen peroxide (150 ppm).     

Organochlorine pesticide residues in sediments from the Uganda side of Lake Victoria

Organochlorine (OC) residues were analysed in 117 sediment samples collected from four bays of the Uganda side of Lake Victoria. The sediments were collected with a corer at a depth of 0-20 cm, and extracted for OC residues using a solid dispersion method. The extracts were cleaned using gel permeation chromatography and analysed for pesticide residues using a gas chromatograph (GC) equipped with an electron capture detector. The results were confirmed using a GC equipped with a mass spectrometer (MS). A total of 16 OC residues, most of them persistent organic pollutants (POPs) were identified and quantified. The OC residue levels were expressed on an oven dry weight (d.w.) basis. Endosulphan sulphate, in the range of 0.82-5.62 μg kg⁻¹d.w., was the most frequently detected residue. Aldrin and dieldrin were in the ranges of 0.22-15.96 and 0.94-7.18 μg kg⁻¹d.w., respectively. DDT and its metabolites lay between 0.11-3.59 for p,p′-DDE, 0.38-4.02 for p,p′-DDD, 0.04-1.46 for p,p′-DDT, 0.07-2.72 for o,p′-DDE and 0.01-1.63 μg kg⁻¹d.w. for o,p′-DDT. The levels of γ-HCH varied from 0.05 to 5.48 μg kg⁻¹d.w. Heptachlor was detected only once at a level of 0.81 μg kg⁻¹d.w., while its photo-oxidation product, heptachlor epoxide, ranged between non-detectable (ND) to 3.19 μg kg⁻¹d.w. Chlordane ranged from ND to 0.76 μg kg⁻¹d.w. Based on the threshold effect concentration (TEC) for fresh water ecosystems, aldrin and dieldrin were the only OCs that seemed to be a threat to the lake environment.     

Modelling effects of chemical exposure on birds wintering in agricultural landscapes: The western burrowing owl (Athene cunicularia hypugaea) as a case study

We describe an ecotoxicological model that simulates the sublethal and lethal effects of chronic, low-level, chemical exposure on birds wintering in agricultural landscapes. Previous models estimating the impact on wildlife of chemicals used in agro-ecosystems typically have not included the variety of pathways, including both dermal and oral, by which individuals are exposed. The present model contains four submodels simulating (1) foraging behavior of individual birds, (2) chemical applications to crops, (3) transfers of chemicals among soil, insects, and small mammals, and (4) transfers of chemicals to birds via ingestion and dermal exposure. We demonstrate use of the model by simulating the impacts of a variety of commonly used herbicides, insecticides, growth regulators, and defoliants on western burrowing owls (Athene cunicularia hypugaea) that winter in agricultural landscapes in southern Texas, United States. The model generated reasonable movement patterns for each chemical through soil, water, insects, and rodents, as well as into the owl via consumption and dermal absorption. Sensitivity analysis suggested model predictions were sensitive to uncertainty associated with estimates of chemical half-lives in birds, soil, and prey, sensitive to parameters associated with estimating dermal exposure, and relatively insensitive to uncertainty associated with details of chemical application procedures (timing of application, amount of drift). Nonetheless, the general trends in chemical accumulations and the relative impacts of the various chemicals were robust to these parameter changes. Simulation results suggested that insecticides posed a greater potential risk to owls of both sublethal and lethal effects than do herbicides, defoliants, and growth regulators under crop scenarios typical of southern Texas, and that use of multiple indicators, or endpoints provided a more accurate assessment of risk due to agricultural chemical exposure. The model should prove useful in helping prioritize the chemicals and transfer pathways targeted in future studies and also, as these new data become available, in assessing the relative danger to other birds of exposure to different types of agricultural chemicals.     

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.     

Dermal exposure to pesticides modifies antioxidant enzymes in tissues of rats

Abstract

Superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX) activities were determined in rat tissues after dermal exposure to pesticides. Two experiments were conducted in male SD rats, 190–210 g body weight. Acephate (ACP), methamidophos (MAP) and nicotine (NIC) were dissolved either individually or together in 0.25 mL of 50% ethanol, which contained: AP=12.6 or MAP 1.3 or NIC= 9.6 mg; EXP 1 ‐ individual pesticide exposure; 64 rats, 16/group; EXP 2 ‐ mixture of AP+MAP+NIC at levels of IX, 2X, 3X; 48 rats, 12/group; 0.25 mL of solution or ethanol (Controls) was applied to 25 mm² area of shaved skin 3 times a week. Half the rats were terminated after 4 weeks and the rest after 4 weeks of stopping exposure. Single pesticides decreased erythrocyte (RBC) SOD by 17 % after exposure and in the NIC group after post exposure (P#0.05). Increasing concentrations of AP+MAP+NIC mixture elevated RBC SOD by 22 % in the 2X and 3X groups and CAT by 13 % in the 3X group (P#0.05); post exposure increased RBC SOD by 2–3 fold and CAT activity by 13 % in all 3 groups. Liver GPX increased by 30–40 % and CAT decreased by 12 % in all exposed and post exposed groups (P#0.05). The results suggest that dermal exposure to mixtures of pesticides can selectively induce SOD, CAT and GPX activities in RBC and liver.     

Persistent organic pollutants associated to water fluxes and sedimentary processes in the Colorado River delta, Baja California, México

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were studied in sediment cores from two distinctive modern channels of the Colorado River (CR) delta. Their abundance and temporal changes are associated with flood-flows from the CR across the USA-Mexico border. The CR channel is directly exposed to river flood-flows while the Hardy River (HR) is a local channel derived mainly from agricultural runoff, geothermal effluents, and treated urban wastewater. Different headwater compositions and degrees of exposure to flood-flows appear to be the factors controlling the composition of persistent organic pollutants (POPs). Enrichment of OCPs (46 ng g⁻¹ dwt in HR and 4.37 ng g⁻¹ dwt in CR) occurred during or a few years after flooding. PCB-138 (4.2 ng g⁻¹ dwt) is enriched in HR suggesting its origin in dielectric oils from the geothermal power plant. PCB-28 (2.1 ng g⁻¹ dwt) in CR may be related with atmospheric input and/or re-deposition of upstream sediments. In surficial sediments (0-3 cm), only HR exceeds international sediment quality guidelines (4,4′-DDE = 8.16 ng g⁻¹ dwt and ΣDDT = 8.34 ng g⁻¹ dwt).     

Application of various methods to determine the lipophilicity parameters of the selected urea pesticides as predictors of their bioaccumulation

Different lipophilicity procedures including a newly developed (based on O?cik's equation) was applied in order to compare various urea pesticides with herbicidal and also insecticidal activity, such as monolinuron, chlorotoluron, diuron, isoproturon, linuron, dimefuron, diflubenzuron, teflubenzuron and lufenuron. Lipophilicity parameters (R_MWS and R_MW0) of nine examined pesticides were determined on the chromatographic plates RP-8F₂₅₄ with the use of methanol–water as a mobile phase_. Similarity analysis enabled to group all examined pesticides depending on their lipophilic character and allowed to perform a more objective comparison of different lipophilicity parameters obtained for investigated compounds by means of thin-layer chromatography and by the use of computational methods. It was stated that with the number of fluorine in examined pesticides, the lipophilic character of insecticides and also their tendency to bioaccumulation in the living systems increases noticeably. The results of this work confirmed that a new procedure for determining the lipophilicity parameter (R_MW0) by O?cik's equation could be a suitable tool in the prediction of pesticide bioaccumulation in living system and may be used as an indicator in design of new urea pesticides, which will be safe for humans and the environment.