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Surface-enhanced Raman spectroscopy spectra of dimethoate and phosmet pesticides were recorded using a Klarite substrate. Significant enhancements were achieved with dimethoate over a concentration range of 0.5–10 µg mL−1 and phosmet over a concentration range of 0.1–10 µg mL−1. The best prediction model for dimethoate pesticide was achieved with a correlation coefficient of 0.940 and a root mean square error of prediction of 0.864 µg mL−1, with the first derivative and standard normalized variate data preprocessing, and the best prediction model of phosmet pesticide was achieved with a correlation coefficient of 0.949 and a root mean square error of prediction of 0.741 µg mL−1 with the first derivative data preprocessing. Our study shows that pesticides, including dimethoate and phosmet, could be quantitatively measured at as low as 0.5 µg mL−1 level using surface-enhanced Raman technology coupled with a Klarite substrate and the results indicated that surface-enhanced Raman spectroscopy with a Klarite substrate has potential for the analysis of dimethoate and phosmet residues. [ABSTRACT FROM AUTHOR]

The potential dermal and respiratory exposure and risk assessments for an applicator were performed with chromafenozide in rice fields in Korea. Three experienced farmers of approximately the same height (168–170 cm) and weight (65–73 kg) were employed to perform the experiment. Dermal patches, gloves, socks, and masks were used to monitor the potential dermal exposure (PDE), and personal air samplers with XAD-2 resins were used to monitor the potential inhalation exposure. During the mixing/loading process of chromafenozide (2.5%, EC), the average hand exposure amount was 3.7 mg and the ratio to the applied amount was 1.85 ×10−2%. For spraying process, the potential dermal exposure amount was 98.3 (74.5–112.8) mg, corresponding to 0.492% of the total exposure amount. The major exposure parts were thigh (0.37%) and shin (0.10%), and the left body (55.0%) was more than that of the right body (45.0%). The inhalation exposure amount was only 39.9 mg. For risk assessment, the mean of PDE (384.0 mg/day) and the mean of absorbable quantity of exposure (3.99 mg/day) were calculated. The value of margin of safety (MOS) ranged from 1.12 to 1.69, all MOS were >1, indicating the exposure level of chromafenozide was safe during application in rice fields. [ABSTRACT FROM PUBLISHER]

1,1,1-Trichloro-2,2-bi(4-chlorophenyl)ethane (DDT) pesticide that has been extensively used in agriculture in China in the last century, and even now, has been banned from all purposes. The disposal of obsolete DDT pesticide has been an urgent task for the Chinese government. In order to evaluate the feasibility of co-processing DDT in the current new style dry-process rotary kiln with a precalciner as the feeding point, the destruction efficiency (DE) of DDTs (includingp,p′-DDT,o,p′-DDT,p,p′-DDE andp,p′-DDD), proportion of DDTs in the combustion residue and exhaust gas, and the release of chlorine were studied under different operating conditions of temperature, oxygen content and gas retention time in the laboratory. The DE of DDTs exceeded 99% when the temperature was over 800 °C with enough oxygen. As the temperature increased from 600 °C to 1200 °C, the proportion ofp,p′-DDD increased andp,p′-DDT decreased but still the main effective component remained in the combustion residue. In the exhaust gas, the most dominant phenomenon was the rapid increase inp,p′-DDE concentration as the temperature increased. The release of chlorine reached a peak between 800 °C and 900 °C. It was found that the oxygen content had a positive correlation with the process of dechlorination. The proportion ofp,p′-DDE increased as the oxygen content was increased in the exhaust gas. The gas retention time had almost no influenced on the DE of DDTs, but affected the degradation extent of DDTs in the gas phase. These experiments showed that co-processing of obsolete DDT pesticide in cement kiln precalciners is feasible. [ABSTRACT FROM PUBLISHER]

Contamination of drinking water sources with agrochemical residues became a major concern in the twenty-first century. Coagulation–flocculation is the most widely used water-treatment process, but the efficiency to remove pesticides and other organic pollutants are limited compared to adsorption process. Thus, simultaneous action of adsorption on normal bentonite or organo-modified montmorillonite clays [modified with octadecylamine (ODA-M) and octadecylamine + aminopropyltriethoxysilane (ODAAPS-M)] followed by coagulation–flocculation by alum and poly aluminium chloride has been evaluated for removal of 10 different pesticides, namely atrazine, lindane, metribuzin, aldrin, chlorpyriphos, pendimethalin, α-endosulphan, β-endosulphan,p, p′-DDT, cypermethrin and two of its metabolites, endosulphan sulphate andp, p′-DDE, from water. The coagulation without integration of adsorption was less effective (removal % varies from 12 to 49) than the adsorption–coagulation integrated system (removal % varies from 71 to 100). Further, coagulation integrated with adsorption was more effective when organically modified montmorillonite was used as adsorbent compared to normal bentonite. The removal efficiency of organic clay depends upon the concentration of pesticides, doses of clay minerals, and efficiency was more for ODAAPS-M as compared to ODA-M. The combination of ODAAPS-M-clay with coagulants was also used efficiently for the removal of pesticides from natural and fortified natural water collected and the results exhibit the usefulness of this remediation technique for application in water decontamination and in treatment of industrial and agricultural waste waters. [ABSTRACT FROM PUBLISHER]

The 2010 4-yearly national survey of pesticides in groundwater included 162 wells. The aims of the survey were to update the national overview of pesticides in New Zealand's groundwater systems, to investigate temporal variation in pesticide concentrations between surveys, and to identify environmental factors associated with pesticide contamination. Pesticides were detected in 38 wells (23%), with two or more pesticides detected in 15 wells (9%). Pesticides were measured in wells in nine of the 14 regions sampled. One well showed a dieldrin concentration greater than the maximum acceptable value for drinking water. A total of 22 different pesticides were detected. Herbicides were the most common pesticide group detected. Levels of only three of the 66 pesticide detections exceeded 1 mg/m3. Comparisons with earlier surveys indicate that a similar percentage of wells had detectable pesticides in the last four surveys once correction for variable detection limits was made. [ABSTRACT FROM PUBLISHER]

Background. Pesticide self-poisoning causes one third of global suicides. Sri Lanka halved its suicide rate by banning WHO Class I organophosphorus (OP) insecticides and then endosulfan. However, poisoning with Class II toxicity OPs, particularly dimethoate and fenthion, remains a problem. We aimed to determine the effect and feasibility of a ban of the two insecticides in one Sri Lankan district. Methods. Sale was banned in June 2003 in most of Polonnaruwa District, but not Anuradhapura District. Admissions with pesticide poisoning to the district general hospitals was prospectively recorded from 2002. Results. Hospital admissions for dimethoate and fenthion poisoning fell by 43% after the ban in Polonnaruwa, while increasing by 23% in Anuradhapura. The pesticide case fatality fell from 14.4% to 9.0% in Polonnaruwa (odds ratio [OR] 0.59, 95% confidence interval [CI] 0.41-0.84) and 11.3% to 10.6% in Anuradhapura (OR 0.93, 95%CI 0.70-1.25; p == 0.051). This reduction was not sustained, with case fatality in Polonnaruwa rising to 12.1% in 2006-2007. Further data analysis indicated that the fall in case fatality had actually been due to a coincidental reduction in case fatality for pesticide poisoning overall, in particular for paraquat poisoning. Conclusions. We found that the insecticides could be effectively banned from agricultural practice, as shown by the fall in hospital admissions, with few negative consequences. However, the ban had only a minor effect on pesticide poisoning deaths because it was too narrow. A study assessing the agricultural and health effects of a more comprehensive ban of highly toxic pesticides is necessary to determine the balance between increased costs of agriculture and reduced health care costs and fewer deaths. [ABSTRACT FROM AUTHOR]

Non-persistent pesticides, such as organophosphorous (OP) insecticides have been extensively used in Mexico, and becoming a public health problem. This review presents data of OP use and related toxicity from epidemiological and experimental studies conducted in Mexico. Studies in agricultural workers from several regions of the country reported moderate to severe cholinergic symptoms, including decreased acetylcholinesterase (AChE) activity (the main acute OP toxic effect that causes an over accumulation of the neurotransmitter acetylcholine), revealing the potential risk of intoxication of Mexican farmers. OP exposure in occupational settings has been associated with decreased semen quality, sperm DNA damage and as endocrine disrupter, particularly in agricultural workers. Alterations in female reproductive function have also been observed, as well as adverse effects on embryo development by prenatal exposure in agricultural communities. This illustrates that OP exposure represents a risk for reproduction and offspring well-being in Mexico. The genotoxic effects of this group of pesticides in somatic and sperm cells are also documented. Lastly, we present data about gene-environmental interactions regarding OP metabolizing enzymes, such as paraoxonase-1 (PON1) and its role in modulating their toxicity, particularly on semen quality and sperm DNA integrity. In summary, readers will see the important health problems associated with OP exposure in Mexican populations, thereby the need of capacitation programs to communicate farmers the proper handling of agrochemicals to prevent their toxic effects and of more well designed human studies to support data of the current situation of workers and communities dedicated to agriculture activities. [ABSTRACT FROM AUTHOR]

A method for the detection and quantification of 16 pesticides: flufenoxuron, fenoxycarb, dimethomorph, acetamiprid, imidacloprid, lufenuron, thiacloprid, thiabendazole, thiophanate-methyl, spinosad, fenbutatin oxide, methoxyfenozide, oxamyl, clothianidin, thiamethoxam and carbendazim has been developed based on high-performance liquid chromatography-mass spectrometry. Pesticide residues were extracted from the samples according to the QuEChERS method which stands for quick, esay, cheap, effective, rugged and safe. Homogenised analytical portions (10 g ± 0.1) of samples of peppers were spiked at two levels (10 and 100 μg Kg-1) with a small volume of an appropriate standard mixture solution containing each pesticide. Analyses were performed using electrospray ionization (ESI) and a MSD trap system. Chromatography separation was achieved using a ZORBAX SB-C18 3.5 μm particle size analytical column, 2.1 × 50 mm from Agilent, with gradient elution at a flow-rate of 0.4 mL/min with mobile phases: waters-0.1 % HCOOH-5 mM HCOONH4 and MeOH-5 mM HCOONH4. The method has been validated based on the SANCO European Guidelines. Under the optimized conditions the recoveries (n = 7) were in the range 70-110 % with satisfactory precision (CV ≤ 20 %). A linear dynamic range was obtained over a range of concentrations from 10 to 100 μg Kg-1 for each of the analytes, with correlation coefficients >0.997. [ABSTRACT FROM AUTHOR]

This investigation was under taken to evaluate the groundwater resources contamination due to intensive agricultural practices (particularly greenhouses). The study-area is located in the coastal area of the Ragusa province (South-East Sicily), where numerous existing greenhouses may cause the contamination of groundwater systems (unconfined and confined aquifers) beneath the cropped land. The pollution risk is mainly related with the seepage process of macro-elements nitrogen (N), phosphorus (P), potassium (K), held in the irrigation water and the massive use of fertilizers and pesticides, that may pass through the unsaturated zone of the soil profile. Moreover, the area is characterized by the presence of several wells (about 15 wells/km2) for agricultural use that cause the aquifer overexploitation and the consequent risk of seawater intrusion. The agriculture practices adopted in the study area (irrigation volumes, fertilizer concentrations, use of pesticides...) were monitored since February 2009; moreover, the pollution risk of the aquifers was evaluated through the analysis of groundwater water samples collected (monthly) in the monitoring wells; in particular, nitrogen compounds, soluble phosphorous (PO4--), potassium, as well as the main pesticides commonly used in the study area, were measured.The results show that electrical conductivity and chloride concentration values can cause reduction of production and leaf damage problems, respectively, for most of the monitored farm systems. The high nitrogen compounds concentrations observed in the monitored wells can cause health and environmental problems. Moreover high pesticide contamination of groundwater was found in two of the five monitored wells. [ABSTRACT FROM AUTHOR]

The most important factor affecting efficacy and drift of pesticide applications is the droplet spectrum. To measure pesticide drift, researchers utilize fluorescent tracers to rapidly quantify spray deposition. Although fluorescent tracers have been used for more than 50 years, no experiments have been performed on the effect they have on the properties of pesticide formulations (density and viscosity) or droplet spectrum, which affect the drift of pesticides. Therefore, we examined the effect of an oil- and water-based tracer on the volume median diameter (VMD), viscosity, and density of oil- and water-based pesticide formulations. In addition, we experimentally fit and demonstrate the utility of using distributions to characterize pesticide droplet spectra. The addition of tracers to both water- and oil-based formulations did not significantly alter the VMD, viscosity, and density. Lognormal distributions provided the best fit for the water- and oil-based formulations with and without tracer. Our results demonstrated that the addition of oil- and water-based tracers do not significantly alter pesticide formulations properties and droplet spectrum, and most likely do not alter the movement of pesticide droplets in the environment. [ABSTRACT FROM AUTHOR]

Gas chromatography with nitrogen phosphorus detector (GC-NPD)was applied to the simultaneous determination of 15 organophosphorus and 6 organonitrogen pesticides residues in Angelica sinensis. The pesticides were extracted by microwave-assisted extraction (MAE) and ultrasound-assisted extraction (UAE) techniques, respectively. The experimental variables were optimized through orthogonal array experimental design. Cleanup of extracts was performed with column chromatography using florisil and neutral aluminum as the sorbents. The determination of pesticides in the final extracts was carried out by GC-NPD. Under optimized conditions, the average recoveries obtained from MAE and UAE are in the range of 75.1-129% and 70.6-129%, respectively, and the relative standard deviations of MAE and UAE were 3.1-10.6% and 1.0-17.8%, respectively. [ABSTRACT FROM AUTHOR]

A multiresidue method was developed and optimized for the identification/quantification of organochlorine pesticides (OCPs) and pyrethroids (PYRs) in beef meat samples. Samples extraction was performed by an automated solvent extractor and the extracts were cleaned-up by a tandem-cartridge system consisting of an Extrelut NT3 combined with a Sep-Pack C18 cartridge and a florisil minicartridge. Analysis was finally carried out by gas chromatography coupled with quadrupole mass spectrometry (GC/MS). The performance of the method was investigated in terms of linearity, accuracy, precision, detection limit (LOD) and quantification limit (LOQ). Good linearity was obtained, with correlation coefficients (r2) higher than 0.98. Mean recoveries were found in the ranges 70-110 % and 84-99 % for the investigated OCPs and PYRs, respectively, with the exception of extremely volatile hexachlorobenzene (HCB). RSD% turned out to range from 2 to 15 %. LOQ values were in the range 0.005-0.1 mg/kg for either class of compounds. The method developed was successfully tested on 50 commercial beef meat samples from the market area of Rome (Italy), proving to be a useful tool in routine multiresidue analysis of OCPs and PYRs for monitoring purposes. None of the compounds of interest were observed above their respective LOQ. [ABSTRACT FROM AUTHOR]

A series of novel N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were synthesized as potential new agents to control pests. Their structures were confirmed on the basis of IR, NMR and elemental analyses. Six new N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were prepared by reduction of corresponding Schiff bases using sodium borohydride in 80-87 % yields. These compounds were tested for their antifungal activity against two pathogenic fungi viz., Rhizoctonia bataticola ITCC 0482 and Sclerotium rolfsii ITCC 5226 and for insecticidal activity against insects of stored grain pest Callosobruchus analis. Fungicidal bioassay revealed that compound N-Decyl-N-[1-(2-hydroxyphenyl)ethyl]amine, was highly effective against R. bataticola (ED50 6.86 mg L-1) which was comparable with that of commercial fungicide hexaconazole (ED50 6.35 mg L-1). Also compounds N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine, N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine and N-Nonyl-N-[1-(2-hydroxyphenyl)ethyl]amine displayed promising fungitoxicity against same pathogen. However, compound N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine was also found to be effective against S. rolfsii (ED50 4.92 mg L-1 as against 1.27 mg L-1 for hexaconazole). Compound N-Hexyl-N-[1-(2-hydroxyphenyl)ethyl]amine was most effective as insecticide followed by compound N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine. LC50 values for these compounds were 155.0 and 275.0 mg L-1 respectively as against 36.70 mg L-1 for commercial insecticide dichlorovos. The results obtained from bioassays indicate that this class of compounds can be utilized for the design of new substances endowed with pesticidal activities. [ABSTRACT FROM AUTHOR]

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method. [ABSTRACT FROM AUTHOR]

The impact of pesticides, namely thiobencarb (TBC), molinate (MOL) and chlorpyrifos (CPF), on soil microbial processes was studied in two Australian soils. Substrate induced respiration (SIR), substrate induced nitrification (SIN) and phosphatases and chitinase enzymatic activities were assessed during a 30-day microcosm study. The pesticides were applied to soils at recommended rates either alone, or as binary mixtures with TBC. Soil samples were sampled at 5, 15 and 30 days after pesticide treatments. Substrate induced respiration was only transiently affected by pesticides in both soils. In contrast, the process of indigenous nitrification was affected by the presence of pesticides in both soils, especially when the pesticides were applied as binary mixtures. Substrate induced nitrification increased with pesticides in the Griffith soil (except with MOL+TBC after 5 days) whereas SIN values were non-significantly different to the control on the Coleambally soil. The binary mixtures of pesticides with TBC resulted in a decrease in SIN in both soils, but the effects disappeared within 30 days. The enzymatic activities were not consistently affected by pesticides, and varied with the soil and pesticides studied. This study showed that, when applied at recommended application rates, TBC, MOL, and CPF (individually or as binary mixtures), had little or only transitory effects on the functional endpoints studied. However, further investigations are needed to assess the effect on microbial densities and community structure despite the low disturbance to the functions noted in this work. [ABSTRACT FROM AUTHOR]

Lindane (1α, 2α, 3β, 4α, 5α, 6β-hexachloro cyclohexane), methyl parathion (O,O-dimethyl-O-4-nitrophenyl phosphorothioate) and dichlorvos (2,2-dichlorovinyl-O-O-dimethyl phosphate) are removed from water individually and as a mixture by photo degradation using suspended and immobilized forms of TiO2 (Degussa P-25). Studies were conducted to optimize the coating thickness of immobilized photo catalyst. The rate of degradation of pesticides was compared in both suspended and immobilized TiO2 systems. Degradation studies of mixed pesticides were carried out with low concentrations (1.0 and 2.5 mg/L) of pesticides. Only three intermediate byproducts such as methyl paraoxon, O,O,O-trimethyl phosphonic thionate and p-nitrophenol were observed during the methyl parathion degradation in suspended, immobilized TiO2 systems and mixed pesticides degradation studies. At the end of the reaction methyl parathion and its by-products were completely degraded. During lindane degradation hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene, 1-hydroxy 2,3,4,5,6-chlorocyclohexane, 1-hydroxy 2,3,4,5,6-chlorobenzene, pentachloro cyclopentadiene, 1,2,3,4,5-hydroxy cyclopentene and 1,2,3-hydroxy cyclobutane were identified in suspended and immobilized TiO2 systems, whereas only hexachloro cyclohexane, pentachloro cyclohexane, hexachloro benzene and pentachloro cyclopentadiene were observed during mixed pesticides degradation. No intermediate by-product was observed during the photo degradation of dichlorvos. Langmuir-Hinshelwood pseudo first order kinetic equation showed that there was not much change in the rates of degradation in both suspended and immobilized TiO2 systems irrespective of the pesticide. During mixed pesticides degradation, the degradation pattern was not similar to that of single pesticide. [ABSTRACT FROM AUTHOR]

A new method for monitoring Pseudomonas aeruginosa growth with dimethoate (DMA) as sole carbon using the series piezoelectric quartz crystal (SPQC) and high-performance liquid chromatography (HPLC) was described. Compared with the general methods, SPQC gives real-time, multidimensional information. The determination limit of HPLC was 1.08 ng. A combined novel response model for Pseudomonas aeruginosa degrading DMA was derived. By fitting DMA reducing data, the value of the reduction rate constant (k) was obtained and in line with the actual trend. The proposed kinetic model was successfully applied to Pseudomonas aeruginosa degrading DMA. [ABSTRACT FROM AUTHOR]

The occurrence of organophosphorus pesticide (OPs) and their metabolite residues was investigated in 167 samples of Greek virgin olive oil during a 2-year (2004-2005) sampling campaign. A total of 30.5% of samples contained detectable residues, although only one sample contained dimethoate residues above the maximum residue limit. Among the seven detected OPs, fenthion and fenthion sulfoxide residues were detected in 10.8 and 14.4% of the samples, respectively, at levels of 0.003-0.61 mg kg-1. Dimethoate was detected in 10.2% of the samples at 0.003-0.057 mg kg-1. The acute dietary risk assessment was undertaken by determining the national estimated short-term intake (NESTI); for chronic dietary risk assessment, the national theoretical maximum daily intake (NTMDI) and national estimated daily intake (NEDI) were calculated. The estimated intakes (NESTI and NEDI) of each pesticide were <7 and <0.86% of the corresponding acute reference doses (ARfDs) and acceptable daily intakes (ADIs), respectively. A cumulative risk assessment was performed using the hazard index (HI) and toxicity equivalence factor (TEF), taking into account that OPs share the same toxicological mechanism. The determined HI and TEF values were found to represent only a small portion of the respective ADIs or ARfDs. These results indicate that there is neither acute nor chronic risk for the Greek population through olive oil consumption. [ABSTRACT FROM AUTHOR]

Two treatments to control the olive pest Prays oleae Bern. were compared in a 2-year study at five different olive-growing sites. In one treatment the pesticide dimethoate was sprayed, and in the second treatment ethylene was applied to olive trees in the form of ethrel (2-chloroethyl-phosphonic acid). In 2005 and 2006 the ethylene treatment provided a mean benefit of 340 Euros per hectare, whereas in the dimethoate treatment there were losses of 100 Euros per hectare. We conclude that treatments with dimethoate, the most widely used pesticide in southern Spain, are undesirable, reducing both the activity and killing efficiency of indigenous predators of P. oleae, mainly the green lacewing Chrysoperla carnea (Stephens) (Neuroptera: Chrysopidae), compared to control and ethylene-treated trees. [ABSTRACT FROM AUTHOR]

A novel chemiluminescence method for the quantitative assay of the organophosphorus pesticide chlorpyrifos in vegetable samples is presented. The determination is based on the reaction of chlorpyrifos with luminol-H2O2 in alkaline medium with sodium chloride being enhancer. Under the optimum conditions, the increased CL intensity was proportional with the concentration of chlorpyrifos in the range of 1.0 × 10-8 g ∙ ml-1 - 1.0 × 10-6 g ∙ ml-1 and the detection limit was 3.5 × 10-9 g ∙ ml-1 (3σ). The relative standard is less than 3.9% for 5.0 × 10-7 g ∙ ml-1 chlorpyrifos (n = 7). This method has been successfully applied to the determination of chlorpyrifos residue in vegetable sample. Further study was focused on the mechanism of chlorpyrifos and the possible mechanism was proposed. [ABSTRACT FROM AUTHOR]

Monosodium methanearsonate (MSMA), an arsenic-based pesticide, has been used since the mid 1980s in attempts to suppress mountain pine beetle (Dendroctonus ponderosae) outbreaks in British Columbia, Canada. It was previously shown that cavity nesting forest birds forage and breed in MSMA-treated pine stands. The present study was designed to investigate the effects of ecologically relevant oral exposure to MSMA, including tissue distribution, growth parameters, and general health, including survival and immune function, of a model passerine, the zebra finch (Taeniopygia guttata). Nestling finches were orally dosed for 20 d from hatching to fledging with 4, 8, 12, 24, 36, or 72 μg/g bw/d of monomethylarsonic acid (MMA(V), which corresponds to MSMA at physiological pH). Preliminary trials showed complete mortality at 36 and 72 μg/g bw/d, and repeat trials also resulted in high mortality at 24 μg/g bw/d. Surviving nestlings showed dose-dependent trends in accumulation of arsenic in blood and specific tissues, and decreased tarsi and wing cord length upon fledging. There were no observed effects of dosing on measured immune function (phytohemagglutinin [PHA], hematocrit, and leukocrit). The data obtained suggest that passerine nestlings may be at risk of mortality and reduced growth due to exposure to MSMA under current environmental conditions. [ABSTRACT FROM AUTHOR]

Linking biomarker data to pharmacokinetic (PK) models permits comparison of absorbed dose with a toxicological benchmark, which is an important step to understanding the health implications of pesticide exposure. The purpose of this analysis was to evaluate the feasibility of reconstructing the absorbed dose of two pesticides using PK models developed from biomarker data in a study of occupational application of these compounds. Twenty-four-hour urine samples were collected from farmers 24 h before through 96 h after a typical application of chlorpyrifos or 2,4-D. PK models were used to link the amounts found in urine samples to absorbed dose. Modeled total body dose estimates (in micrograms) were compared to measured dose from time 0-96 h. Despite the complexities surrounding the interpretation of biomonitoring data from a field setting, the models developed as part of this analysis accurately estimated the absorbed dose of 2,4-D and chlorpyrifos when collection of urine samples was largely complete. Over half of the farmers were excluded from modeling due to suspected noncompliance with urine collection or confounding exposure events, which highlights the importance of these issues for designing and interpreting biomonitoring data in future studies. Further evaluation of PK models in scenarios using single void samples is warranted for improving field-based dose assessments. [ABSTRACT FROM AUTHOR]

Arguing that the 2006 Environmental Protection Agency (EPA) human-subjects rule allows use of unethical third-party research (on pregnant women and children) in setting pesticide regulations, this article first (a) provides a brief history of U.S. pesticide regulation, particularly regarding childhood safety. Next it (b) outlines ethical and scientific loopholes in the 2006 EPA rule; (c) shows how the Human Subjects Review Board, mandated by the 2006 rule, has been implemented in flawed ways; and (d) illustrates that one source of problems with the rule may be influence by those with conflicts of interest. [ABSTRACT FROM AUTHOR]

The aim of this study was to evaluate the soil microbial characteristics in historically heavy-metal polluted soil, which was also affected by organic co-contaminants, 2,4-dichlorophenol or pentachlorophenol, which often occur due to the conventional use of pesticides. It was observed that the normalized microbial biomass (microbial biomass per unit soil organic C) of the contaminated soil was very low, less than 1% in both non-planted and ryegrass planted soil, and showed a decreasing trend with the treatment of organic co-contaminants. The microbial biomass and substrate-induced respiration (SIR) in the ryegrass planted soil were much larger, as compared with the non-planted soil with or without organic pollutants. The different resistant bacterial community and its physiological diversity in the rhizosphere further suggested that the effect of vegetation on microbial activity was not just a general increase in the mass or activity of pre-existing microorganisms, but rather acted selectively on microbial growth so that the relative abundance of different microbial groups in soil was changed. In sum, high concentrations of organic co-contaminants, especially pentachlorophenol (PCP), could strengthen the deterioration of microbial ecology. The adverse effect of heavy metal-organic pollutants on the soil microbial biomass and activity might be the reason for the slow degradation of PCP that has high chlorinated and high toxicity. Vegetation might be the efficient way to assist in improving and restoring the utilization of agricultural ecosystems. The beneficial microbial effect of vegetation could cause the rapid dissipation of 2,4-dichlorophenol (2,4-DCP) that has less chlorinated and less toxicity in the planted soils. [ABSTRACT FROM AUTHOR]

This study was conducted to determine the significance of bromacil transport as a function of water and carbon content in soils and to explore the implications of neglecting sorption when making assessments of travel time of bromacil through the vadose zone. Equilibrium batch sorption tests were performed for loamy sand and sandy soil added with four different levels of powdered activated carbon (PAC) content (0, 0.01, 0.05, and 0.1%). Column experiments were also conducted at various water and carbon contents under steady-state flow conditions. The first set of column experiments was conducted in loamy sand containing 1.5% organic carbon under three different water contents (0.23, 0.32, and 0.41) to measure breakthrough curves (BTCs) of bromide and bromacil injected as a square pulse. In the second set of column experiments, BTCs of bromide and bromacil injected as a front were measured in saturated sandy columns at the four different PAC levels given above. Column breakthrough data were analyzed with both equilibrium and nonequilibrium (two-site) convection-dispersion equation (CDE) models to determine transport and sorption parameters under various water and carbon contents. Analysis with batch data indicated that neglect of the partition-related term in the calculation of solute velocity may lead to erroneous estimation of travel time of bromacil, i.e. an overestimation of the solute velocity by a factor of R. The column experiments showed that arrival time of the bromacil peak was larger than that of the bromide peak in soils, indicating that transport of bromacil was retarded relative to bromide in the observed conditions. Extent of bromacil retardation (R) increased with decreasing water content and increasing PAC content, supporting the importance of retardation in the estimation of travel time of bromacil even at small amounts of organic carbon for soils with lower water content. [ABSTRACT FROM AUTHOR]

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO3 and 30 g anhydrous Na2SO4 with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO4 and primary secondary amine (PSA) sorbent. 14C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method. [ABSTRACT FROM AUTHOR]

The behavior of an amperometric organic-phase biosensor consisting of a gold electrode modified first with a mercaptobenzothiazole self-assembled monolayer, followed by electropolymerization of polyaniline in which acetylcholinesterase as enzyme was immobilized, has been developed and evaluated for organophosphorous pesticide detection. The voltammetric results have shown that the formal potential shifts anodically as the Au/MBT/PANI/AChE/PVAc thick-film biosensor responded to acetylthiocholine substrate addition under anaerobic conditions in selected organic solvent media containing 2% v/v 0.05 M phosphate buffer, 0.1 M KCl (pH 7.2) solution. Detection limits in the order of 0.147 ppb for diazinon and 0.172 ppb for fenthion in acetone-saline phosphate buffer solution, and 0.180 ppb for diazinon and 0.194 ppb for fenthion in ethanol-saline phosphate buffer solution has been achieved. [ABSTRACT FROM AUTHOR]

The contents of 16 organochlorine pesticides (OCPs) and six so-called indicator polychlorinated biphenyls (PCBs) were determined in the surface zone (0-5 cm) of soil and sediment samples, taken from different locations in the city of Novi Sad, capitol of Vojvodina Province (North of the Serbia) covering residential and commercial area, recreational and arable zone. The total organochlorine pesticides concentration in soil varied from 2.63 to 31.78 ng g-1 dry weight, while the level in sediment was 10.35 ng g-1 dry weight. Maximum content of identified individual organochlorine pesticide in soil samples was 10.40 ng g-1 dry weight for p, p-DDE in the market garden and 6.31 ng g-1 dry weight for p, p'-DDT in sediment of the Danube River, although their application is restricted in Serbia. Some of investigated PCBs were identified only in the soil samples from a park-school backyard in the city downtown (0.32 ng g-1 dry weight) and market garden (0.22 ng g-1 dry weight), and also in sediment sample from left bank of the Danube River (0.41 ng g-1 dry weight). Data of the OCPs and PCBs present in this study were compared with the ones found for soils and river sediments throughout the world, and with limit values set by soil and sediment quality guidelines. Also, correlation between the levels of certain pesticides and soil characteristics (organic matter, pH and clay content) was investigated. [ABSTRACT FROM AUTHOR]

Use of synthetic pesticides has resulted into health hazards, ecological imbalance, resistance in pests and environmental pollution.[1] Neem oil is natural pesticide and has excellent insecticidal properties. Hence, attempts are being made to develop neem oil emulsions to be used as pesticide. Surfactants like castor‐oil based, nonyl phenol‐based, sodium lauryl sulphate, and calcium alkyl benzene sulphonate were tried to develop stable emulsions. Neem extract based emulsifiable concentrates were prepared by using methanol. Stability of emulsion as a function of type of surfactants, hydrophile‐lipophile balance (HLB) of surfactants and hardness of water was studied. Larvasidal effects of emulsions and emulsifiable concentrates were examined. Laboratory experiments have shown effectiveness of these emulsions and emulsifiable concentrates as pesticide. [ABSTRACT FROM AUTHOR]

Cyclodextrins (CDs) possess a hydrophilic external surface and a hydrophobic cavity. They are thus highly soluble and, in the meantime, effectively form inclusion complexes with hydrophobic organic compounds to enhance their solubilities. In this study, the complexation between modified β -CDs and the herbicide diclofop-methyl (DM), (2-(4-(2,4-dichlorophenoxy)-phenoxy) propionate), was investigated. The complexation was confirmed by the shifts in the wavelengths of maximum ultra violet (UV) absorption and fluorescence excitation/emission. The deuterium isotope effects indicate that in the presence of β -CDs the solubility of DM was lower while that of diclofop was higher in D 2 O than in H 2 O, suggesting the primary role of hydrophobic interactions in complexation. The solubility of DM was enhanced in the presence of β -CDs, the extent of which depended on the modification of β -CDs. The complexation reduced the hydrolysis of DM and hence increased its stability. The small inconsistency in the power of β -CDs between hydrolysis retardation and solubilization suggests that hydrolysis was affected by the properties of β -CDs and the configuration of DM in the complexes. Use of β -CDs may thus result in the mobilization of soil DM. Properly modified β -CDs may be utilized as formulation additives for improved delivery of DM and for enhanced environmental remediation. [ABSTRACT FROM AUTHOR]

Thirty-one thermodynamical and quantum-chemical descriptors were used to characterize all 209 chloro trans -azobenzenes (C t -ABs, PC t -ABs) in terms of their environmental stability and specific dioxin-like toxicity. Some of the PC t -ABs are produced as a by-side impurity during the manufacture of 3,4-dichloroaniline (DCA) and its derivatives and thus can be found in technical products of certain chloroaniline herbicides. A prepared basic thermodynamic and quantum-chemical property data matrix of PC t -ABs was interpreted using Principal Component Analysis (PCA). The PCA of the thermodynamic and quantum-chemical data matrix created a three-dimensional model that explained 78% (68% + 6% + 4%) of the total variance in the data set. The loading plot shows that the first Principal Component (PC) is influenced by variables describing molecular weight, polarizability and lipophilicity. The second PC was strongly influenced by the most positive partial charge on atoms and the most negative partial charge on atoms. The third PC depends on energy of the highest occupied molecular orbital. Next, factors extracted from PCA were used for selection of a representative set of eight trans -chloroazobenzene congeners, which seemed in the best way reflect a diverse property of all 209 PC t -ABs. [ABSTRACT FROM AUTHOR]

Pesticides in stream flow from the 142 ha Colworth catchment in Bedfordshire, UK were monitored from October 1999 to December 2000. About 47% of the catchment is tile-drained and different pesticides and cropping patterns have recently been evaluated in terms of their effect on nutrient and pesticide losses to the stream. The data from Colworth were used to test soil and water assessment tool (SWAT) 2000 predictions of pesticide concentrations at the catchment outlet. A sound model set-up to carry out pesticide modelling was created by means of hydrological modelling with proper simulation of crop growth and evapotranspiration. The pesticides terbuthylazine, terbutryn, cyanazine and bentazone were modelled. There was close agreement between SWAT-predicted pesticide concentration values and observations. Scenario trials were conducted to explore management options for reducing pesticide loads arriving at the catchment outlet. The results obtained indicate that SWAT can be used as a tool to understand pesticide behavior at the catchment scale. [ABSTRACT FROM AUTHOR]

Pesticides and polychlorinated biphenyls (PCBs) are found in various parts of the environment in quite small concentrations, but they accumulate and thus become a threat to the health and life of humans and animals. Humans, who are at the very top of the food chain, are the most vulnerable to the harmful effects of these compounds. An awareness of the dangers carried by ongoing pollution of the environment with these compounds, together with modern precautionary means should reduce the risk of poisoning among people--and the risk of irreversible damage being done to the natural environment--to an absolute minimum. The necessity to assay these compounds in various parts of the environment, and above all in food, is unquestionable as long as the awareness of these substances among people remains small. The variety of matrices in which pesticides and PCBs occur, and of their physical and chemical properties, requires the use of many methods for preparing samples for analyses and assaying. Selection of appropriate conditions of analysis determines the credibility of the end results. [ABSTRACT FROM AUTHOR]

A dipstick assay for the simultaneous determination of atrazine and carbaryl in vegetable samples was developed. The analytical method involved a fast extraction procedure followed by a multi-strip membrane test. The assay took 10 min, with a detection limit (naked eye) of 10 and 200 µg l -1 for atrazine and carbaryl, respectively. The cross-reactivities to related compounds tested were negligible except for propazine. Quantification of the pesticides was carried out by measuring the dot colour with a spectrophotometer. IC 50 values (inhibition constant at 50% of the maximum binding) of 2.04 μg l -1 for atrazine and 92.8 μg l -1 for carbaryl were achieved by this approach. Vegetable samples were extracted with MeOH. The proposed methodology was used to analyse atrazine and carbaryl and check for compliance with European Union maximum residue levels for vegetables. Recoveries (75-105%) were in agreement with those obtained by GC/MS or HPLC. Standard curves using 25% methanol/75% TBS were used for food sample assays using a multi-analyte dipstick. IC 50 values were 9.2 μg kg -1 for atrazine and 179.2 μg kg -1 for cabaryl. [ABSTRACT FROM AUTHOR]

The article discusses an evaluation made by Health Hazard Evaluation Program upon a request of a health and safety manager at a government agency who was concerned with potential exposures when employees manually applied pesticides into rivers to control sea lamprey larvae. Recommendations included enclosing pesticide transfer and mixing equipment, installing washing stations for employees to clean their boots and personal protective equipment (PPE) and washing hands and feet with clean water.