Pesticide soil contamination mainly affects earthworm male reproductive parameters

Aim: To explore the effect of exposure to commercial Parathion~ (Pc) on the reproductive parameters (sperm and cocoon production and genotoxicity on male germ cells), the survival, the body weight and the gross anatomical changes in Eiseniafoetida. Methods: Three doses of Pc(1478, 739 and 444 mg/kg of soil) and three time intervals of exposure (5, 15 and 30 days) were used. Results: All treated animals were affected. An acute genotoxic effect, revealed by DNA fragmentation (comet assay), was seen by 5 days. Alterations in reproductive parameters were conspicuous in regard to the number of sperm, cocoons and worms born, and the histological observation of the gonads and seminal receptacles. In addition, the body weight and survival rate were decreased. Neuromuscular function was also affected. Conclusion: Earthworms are suitable bioindicators of chemical contamination of the soil, their advantage being their easy and economical handling

Development and Prospect of Rare Earth Functional Biomaterials for Agriculture in China

The development and prospect of rare earth functional biomaterials (REFB) was discussed. From 1979 to 1985, the simple REFB (salts) has been developed, and the fundamental research including forms, effects, toxicity, conversion in soil, and analysis methods had been finished. Then, the RE feed additive materials had been developed, and the fundamental research had also been finished. In 1990s, new REFB including RE phosphate fertilizer additive, RE conversional agricultural film additive, RE water-retraining reagent and RE seed coating reagent had been developed out rapidly. They were extended to 1.36 million hectares and big benefit had been got during the last three years. Recently, it was found that RE has some function of antagonizing heavy metals and degradating organophosphors pesticide, so the REFB will be studied as a focus once more, and will become one of the important methods of guaranteeing food security in the future.

Hydrolysis Activities of Resins of Complexes Made from Polysaccharides and Ce^(4+)

Resins of complexes made from agarose-Ce4+ (RCA-Ce) and chitosan-Ce4+ (RCC-Ce) were prepared. Hydrolysis rates of methamidophos, omethoate and chlorpyrifos treated by RCA-Ce were 32.39%, 27.12% and 46.62%, respectively, those of chlorpyrifos and methamidophos in mung bean sprout juice 38.28% and 35.45%, and that of chlorpyrifos in tea extract 59.76%. Hydrolysis rates of protein in tea extract treated by RCA-Ce increased by 86.46%. RCC-Ce could be employed in the apple juice production. The contents of methamidophos and parathion-methyl in the juice treated by RCC-Ce decreased 58.76% and 71.92%. Furthermore, RCC-Ce was used to clarification for beer by the ways of a column. RCC-Ce could hydrolyze sensitive protein and increase contents of free amino acid in the beer. Therefore, the beer treated by RCC-Ce could stay oxidation and aging procedure due to some metal ions being absorbed by RCC-Ce.

Degradation of Extraction from Seaweed and Its Complex with Rare Earths for Organophosphorous Pesticides

On the basis of several experiments carried out in China, it was proved that both seaweed liquid fertilizer and rare earth （RE） could promote the growth of crops and increase their yield. The effects of extraction from seaweed and its complex with RE on the degradation of organophosphorous pesticides and the yield of vegetables were investigated. The resuits showed that the extract and its complex with RE could degrade organophosphorous pesticides in neutral solvent. The residues of the pesticides treated by the extract decreased by 96.88 %, 52.30%, 49.52%, and 22.88 %, respectively, for chlorpyrifos, dichlorvos, omethoate, and dimethoate, and those by the complex decreased by 95.99%, 54.23%, 48.79%, and 25.66%, respectively, when compared with the control. The residues of chlorpyrifos and dimethoate in spinach sprayed with the complex were decreased by 90.64% and 76.56%, respectively, compared with those in spinach from control plots when the interval between spraying and sampling was 8 d. The fresh weight of brassica chinensis and cabbage increased by 28.62% and 18.72%, and their dry weight increased by 44.49% and 14.74%, respectively, compared with those of the controls. The chlorpyrifos and dimethoate residues in brasscia chinese were decreased by 36.36% and 50.00%, respectively, and their rate of decrease in cabbage was 40.00% and 75.00%, respectively, on 5th day after spraying with the complex, when compared with those in the vegetable from control. These results suggest that this complex can increase the agricultural productivity and reduce the use of pesticide residues in the production of vegetables.

Acute effects of chlorpyryphos-ethyl and secondary treated effluents on acetylcholinesterase and butyrylcholinesterase activities in Carcinus maenas

The acute effects of commercial formulation of chlorpyrifos-ethyl （Dursban ） and the secondary treated industrial/urban effluent （STIUE） exposure on acetylcholinesterase （ACHE） and butyrylcholinesterase （BuChE） activities in hepatopancreas and gills of Mediterranean crab Carcinus maenas were investigated. After 2 d of exposure to chlorpyriphos-ethyl, the AChE activity was inhibited in both organs at concentrations of 3.12 and 7.82 μg/L, whereas the BuCHE was inhibited only at higher concentration 7.82 μg/L of commercial preparation Dursban~. The exposure of crabs to Dursban （3.12 μg/L） showed a significant decrement of ACHE activity at 24 and 48 h, whereas the BuChE was inhibited only after 24 h and no inhibition for both enzymes was observed after 72 h. Moreover, a significant repression of AChE activity was observed in both organs of C. maenas exposed to 5% of STIUE. Our experiments indicated that the measurement of AChE activity in gills and hepatopancreas of C. maenas would be useful biomarker of organophosphorous （OP） and of neurotoxic effects of STIUE in Tunisia.

Determination of Omethoateby Cathodically SweepingOscillopolarography

Determination of omethoate by cathodically sweeping oscillopolarography is described. The product of the alkaline hydrolysis exhibited a sensitive second derivative wave at ?0.50 V (vs. SCE) in a 1.0 ×10?5mol/L sodium dodecylbenzene sulfonate (SDBS)+0.1 mol/L HAc-NaAc (pH 4.0) buffer. The peak current was linearly proportional to the concentration of omethoate in the range from 6.4×10?7 to 5.1×10?5 mol/L. The detection limit is 2.0×10?7 mol/L with the relative standard derivation (RSD) of 3.5%. The hydrolysis procedure and the electrode reaction were studied by voltammetry.

Sperm quality in mice acutely treated with parathion

Aim: To investigate the toxic effect of a single injection of the organophosphorous agropesticide, parathion, on sper-matogenesis in immature male mice. Methods: Seven-day old mice received a single injection of parathion intraperi-toneally at a dose of 1/3 LD_50. The epididymal sperm count, sperm morphology and chromatin thermal stability wereanalyzed 28 and 50 days after injection. Results: Sperm counts were decreased and teratozoospermia and thermal de-naturation of DNA increased after parathion injection. Sperm parameters were changed to a greater extent in younger an-imals, denoting a higher lability of spermatogenic process at its beginning. The damages could recover a long time afterparathion administration. Conclusion: Organophosphorous agropesticides are testicular toxicants, eliciting reversiblecytotoxic and cytogenetic alterations in germ cells.

Electrochemical Assay of Effects of Organophosphate Poisoning on Acetylcholinesterase from Pheretima via 2,6-Dimethyl-p-benzoquinone

Electroanalytical techniques could be a reliable and promising alternative to classical and sophisticated methods because of their simplicity（small and portable）,easy use,the ability to deliver fast response with high sensitivity and selectivity.A square wave voltammetric method was developed for the assessment of organophosphorus（OPs） compound impact on acetylcholinesterase（AChE） of Pheretima with 2,6-dimethyl-p-benzoquinone（2,6DMBQ） as a redox indicator.The substrate of acetylthiocholine is hydrolyzed by AChE and the produced thiocholine reacts with 2,6-DMBQ to give an obvious shift of electrochemical signal.The reduction peak of 2,6-DMBQ is located at around 0.18 V which is far away from the oxidation potential of possible interference components often present in biosample.The decreased rate of reduction current was related with the activity of AChE.The inhibition of parathion-methyl on AChE was assessed.The inhibiton rate of OPs on AChE activity increased quickly during the first 10 min inhibition,and after that the value of inhibition rate approached to be constant.AChE lost almost 29.3% of activity after 10 min incubation with 1 μg/mL parathion-methyl and 67.5% of activity with 10 μg/mL parathion-methyl,while the activity that corresponds to 40 μg/mL parathion-methyl was nearly completely inhibited（94.9%）.Compared to cyclic voltammetry and amperometry,Square wave voltammetry（SWV） method is a high sensitive electroanalysis with fast scan-rate（only several seconds for one signal value） which is useful to prevent the electrodes from possible fouling or passivation.This method can be employed to assess the inhibition of organophosphate on AChE and investigate OPs impact on environmental animals.

Study of the Adsorption Efficiency of an Eco-Friendly Carbohydrate Polymer for Contaminated Aqueous Solution by Organophosphorus Pesticide

The removal of pesticide (ethoprophos) from aqueous solution using a natural biosorbent such as chitosan (CH) prepared from a biopolymer waste obtained from marine industry was studied. The Fourier Transform Infrared Spectroscopy (FTIR), Scanning electron microscopy (SEM), and X-ray diffraction spectroscopy (XRD) were used to study the structure of the adsorbent. The biosorption studies were carried out under various parameters, such as biosorbent dose, initial pesticide concentration and contact time. The experimental results show that the removal percentage of ethoprophos increased from 85.693% to 89.234%, as adsorbent dose (CH) increased from 0.02 to 0.1 g/100ml. The equilibrium uptake was increased with an increase in the initial pesticide concentration in solution. Biosorption kinetic data were fitted well with the pseudo-second order kinetic model. The experimental isotherms data were analyzed using Freundlich, Langmuir, Temkin and Dubinin-Radushkevich (D-R) isotherm equations. The best fit was obtained by Freundlich isotherm with high correlation coefficients. That the value of energy calculated from the D-R isotherm was 5.56 KJ/mol suggests the adsorption of ethoprophos on Chitosan is physical. All the results indicating CH was chosen as low-cost biosorbent could be applied for the removal of organophosphorous pesticide from aqueous solutions.

Influence of Co-Solvent on the Extraction Behaviour of Uranium and Thorium Nitrates with Organophosphorous Compounds

Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical carbon dioxide (Sc-CO2) modified with various organophosphorous compounds such as dialkylalkyl phosphonates, trialkyl phosphates and trialkyl phosphine oxides in the presence of co-solvents such as methanol, dichlormethane and n-hexane. The influence of ligand and co-solvent on the extraction of the metal nitrates was studied in detail. These studies have established that co-solvent plays an important role in the extraction as well as fractionation of uranium and thorium nitrates. Polar co-solvent, methanol provided faster extraction without fractionation whereas the non-polar solvent, e.g. n-hexane provided some fractionation of metal nitrates though the extraction kinetics was slower.

Ultrastructure of mouse teratozoospermia induced by parathion

Male fertility has been correlated to sperm counts,motility and morphology. Wyrobek et al (1983),evaluating changes in sperm morphology caused bychemicals (including some pesticides) found that analysisof teratozoospermia is a useful tool to asses testiculartoxicants. In view of their wide agricultural use and scarcereproductive information available regarding organo-

Impact of organophosphorous pesticide exposure on semen quality of Chinese peasants

Aim: To investigate the impact of organophosphorous pesticide exposure and other risk factors on the semen quality of Chinese peasants. Method: Questionnaire investigation, external genital examination and laboratory examination were conducted on 322 male peasants, including the exposed and the control groups of 161 subjects each. Results: Multivariate analysis showed that the educational level and the years of alcohol drinking influenced the semen volume. Compared with subjects of primary school education or lower, those with junior high school education had a higher semen volume (OR=1.961). Proportion of subjects with higher semen volume decreased with increased years of alcohol drinking (OR=0.962). Organophosphorous pesticide exposure decreased the number of forward progression sperm (OR=0.528), the sperm density (OR=0.266), the sperm viability (OR=0.398) and the percentage of normal morphology sperm (OR=0.281). A possible relationship was present between the season of semen collection and the number of forward progression sperm, sperm viability and percentage of normal morphology sperm. Compared with the summer data, the above three indices were higher in winter (OR being 2. 272, 4.060 and 5.249, respectively). Conclusion: Exposure to organophosphorous pesticide could damage the semen quality of the peasants. Education and alcohol drinking also affect the semen quality.

Synthesis,GC-EIMS,~1H NMR,^(13)C NMR,Mechanistic and Thermal Studies of o-Xylylene-α,α'-bis (triphenylphosphinebromide)

Organophosphorous compounds containing phosphorus as an integral part have been widely used in industry, organic synthesis and optoelectronics, o-Xylylene-a,a＇-bis（triphenylphosphinebromide）（OXBTPPB） is a facile reagent to convert o-quinones（e.g., 9,10-phenanthrenequinone） into polycyclic aromatic hydrocarbons（PAHs）. Herein lies an improved synthetic route to OXBTPPB. The resultant was carefully characterized with GC-EIMS, ^1H NMR, ^13C NMR, spectroscopic techniques. The EIMS shows characteristic peaks at m/z=262.4, 183.3, 108.2, 77.1 attributed to the [C18H15P]^＋, [C12H8P]^＋, [C6H8P]^＋, [C6H5]^＋ ions, respectively. The ^1H and ^13C NMR spectrum shows well resolved peaks and all the hydrogens and carbons were well-assigned via a combined study of ^1H-^1H COSY, HMBC, and HMQC experiments. The mechanism for the formation of OXBTPPB was proposed based on literature and obtained experimental data. Meanwhile, the thermal stability of OXBTPPB was evaluated with TGA analysis, and an onset decomposition temperature（Td） was recorded at 323.6 ℃.

Determination of Isocarbophos by Cathodically Sweeping Oscilliopolarography

Determination of isocarbophos by cathodically sweeping oscilliopolarography is described. In a 1.0×10?5 mol/L sodium dodecylbenzene sulfonate (SDS)+0.1 mol/L HAC-NaAC (pH=4.0) buffer medium, isocarbophos and its alkaline hydrolysate exhibited sensitive second derivative wave at ?0.50 V and ?0.48 V respectively. The peak current was linearly proportional to the concentration of isocarbophos in the range of 5.40×10?6?1.05×10?4 mol/L by detecting isocarbophos directly. The detection limit was 3.60×10?6 mol/L with the relative standard derivation (RSD) of 7.3%. By employing an alkaline hydrolysis, the peak current was linearly proportional to the concentration of isocarbophos in the range from 7.70×10?7 mol/L to 1.24×10?4 mol/L, and the detection limit was 5.80×10?7 mol/L with RSD of 3.1%. The hydrolysis procedure and the electrode reaction were studied by voltammetry.

Impact of Organophosphorous Pesticide Exposure on Semen Quality

Objective To investigate the impact of organophorous pesticide exposure on semen quality and other risk factors of semen quality Method Questionnaire investigation, external genital examination and laboratory examination of semen quality were conducted on 322 subjects, who were divided into exposed and control group, each consisting of 161 subjects. Results Multivariate analysis showed that educational level and years of alcohol drinking had effect on semen volume. Compared with subjects with primary school education or lower, those with junior high school education had higher value of semen volume(OR=1.961). Proportion of subjects with high semen volume decreased with the increasing years of alcohol drinking (OR=0.962). Organophosphorous pesticide exposure could result in the decline of the number of sperms with progressive forward progression (OR=0.528), figure of semen density (OR=0.266), semen viability (OR=0.398) and percentage of normal sperm morphology (OR=0.281). There are possible relationships between the season of semen collection and the number of sperms with progressive forward progression, semen viability and percentage of normal sperm morphology . Compared to summer, values of the above three indices would be higher in winter (OR was 2.272, 4.060 and 5.249, respectively). Conclusion Exposure to organophosphorous pesticide could result in the deterioration of semen quality of the peasants.

Prevalence of Organophosphorous Pesticide Residues in Pumpkin, Spinach and Sorrel Leaves Grown in Akwanga, Nasarawa State, Nigeria

Three green leafy vegetable samples of pumpkin leaves, spinach leaves, and sorrel leaves were collected from three different locations in a farm in Akwanga and were tested for the presence of organophosphorus (OP) compounds. The concentrations of all the pesticide residues in the vegetable samples were determined using gas chromatography with mass spectrometry (GC-MS). The organophosphorus pesticides detected include carbaryl (0.052 mg/kg) in pumpkin, this is below European maximum residues limit (EU MRL) of 0.1 mg/kg, Dimethoate was found in pumpkin (0.165 mg/kg), spinach (0.103 mg/kg) and sorrel (0.250 mg/kg) all above the EU MRL of 0.05 mg/kg. Dichlofenthion was detected in pumpkin (0.308 mg/kg), pirimiphos methyl was detected in pumpkin and spinach (0.428 mg/kg and 0.149 mg/kg respectively), all these were below the EU MRL of 0.5 mg/kg. Chlorpyrifos was found in spinach (0.230 mg/kg) and sorrel (0.192 mg/kg) only spinach was above the EU MRL of 0.2 mg/kg. The pesticide residue Bromophosethyl was detected in all vegetables, pumpkin leaves (0.501 mg/kg), sorrel (1.571 mg/kg) and spinach (7.981 mg/kg) all above the EU MRL of 0.5 mg/kg. The remaining pesticides detected were all below their EU MRL value;these are Ethion found in spinach (0.167 mg/kg), Methyl Parathion in spinach (0.103 mg/kg) and sorrel (0.335 mg/kg). The levels of some of the organophosphorus pesticide residues found in vegetables were above the maximum residue limits (MRLs) set by the European Union. This calls for laws to regulate the use and circulation of such chemicals. Based on the observation made in these studies, it is proposed that more extensive monitoring investigation covering all vegetables part in Akwanga Nasarawa state be carried out to find the exact position of pesticide residues.

Immobilization of acetylcholinesterase on one-dimensional gold nanoparticles for detection of organophosphorous insecticides

This paper reports a simple method for immobilization of acetylcholinesterase (AChE) on one-dimensional (1D) gold (Au) nanoparticles for detection of organophosphorous (OP) insecticides. 1D Au nanoparticles were prepared by electrodeposition in the pores of an alumina template which was subsequently removed by 2.0 M NaOH solution. They were characterized by XRD and FESEM. The immobilized AChE retained its biological activity and catalyzed the hydrolysis of acetylthiocholine to form thiocholine, which was subsequently oxidized to produce detectable signals. Based on the inhibition toward the enzymatic activity of AChE by OP insecticides, sensitive detection of methamidophos (an OP insecticide) was performed. Under optimal conditions, the sensors could be used for the determination of methamidophos ranging from 0.004 to 24 μg/mL with the detection limit of 0.001 μg/mL. The developed OP insecticide biosensors exhibited satisfactory stability and reproducibility. This work demonstrated that 1D Au nanoparticles could serve as an ideal carrier for immobilization of AChE to fabricate the corresponding biosensor.

Rapid Detection of Irreversible Acetylcholineasterase Inhibitor by Mass Spectrometry Assay

Here we developed a rapid method to detect acetylcholinesterase （ACHE） activity by matrix-assisted laser de- sorption/ionization Fourier transform mass spectrometry （MALDI-FTMS） for screening irreversible AChE inhibi- tors. Due to its good salt-tolerance and low sample consumption, MALDI-FTMS could facilitate rapid detection, especially detection in real application. AChE activity was determined through calculating abundance of substrate and product in mass spectrometry. By this approach, we investigated the relation of organophosphorous （OP） con- centrations and AChE inhibition. Shown in different inhibition curves from different OP pesticides, enzyme inhibi- tions still kept good correlation with concentration of OPs. Finally, this AChE-inhibited method was applied to screen whole bloods of four decedents and discuss their death reason. In contrast to healthy persons, three of dece- dents showed low AChE activity, and probably died for irreversible AChE inhibitors. Through the following de- tecting in GC-MS/MS, the possible death reason of these three decedents was confirmed, and another decedent actually died for sumicidin, a non-AChE inhibitor. It demonstrated that screening irreversible AChE inhibitors by detecting enzyme activity in MALDI-FTMS provided fast and accurate analysis results and excluded another toxicants not functioning on ACHE. This method offered alternative choices for indicating the existence of enzyme inhibitors.