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.

Spectroscopic Analysis of Organophosphorus Pesticides Using Colorimetric Reactions

The UV-Vis and infrared(IR)absorption spectra of organophosphorus(OP)pesticides have been studied.A correlation in spectra was developed to optimize the OP pesticides in the environments.The spectroscopic(UV-Vis and IR)spectrum of OP pesticides like methyl parathion,malathion and parathion has been interpreted in detail.A complete calculation of the normal frequencies and absolute intensities of UV-Vis and IR absorption bands are interpreted with the help of corresponding experimental data.In the colorimetric reactions,the bands appear at 2 077,1 637,1 455,1 015,655cm^(-1) for malathion;2 081,1 639,1 316,1 015,794,683cm^(-1) for parathion;2 078,1 632,1 032,794cm^(-1) for methyl parathion were used for quantitative or qualitative analysis.All these IR spectra were acquired by averaging 100 scans at a resolution of 4cm^(-1).It is determined experimentally in the region 200~450nm for UV-Vis absorption bands and in the region 400~4 000cm^(-1) for IR absorption bands.It is concluded that the mainly optically active groups(P—OH, C=O,P=O, C—O—C,P—O—C, P=S, —OH)present in pesticides which are responsible in change in significant data for quantitative and qualitative analysis.The various optical properties like wavelength,band energy,wave number,and frequency,also are calculated.

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.

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.

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.

High-Performance Liquid Chromatograph (HPLC) Equipped with a Neurophysiological Detector (NPD) as a Tool for Studying Olfactory System Intoxication by the Organophosphate (OP) Pesticide Diazinon and the Influence of OP Pesticides on Reproduction

A neurophysiological detector (NPD) is a hybridization of olfactory system neurons of the fish crucian carp, Carassius carassius L., with a computerized electronic device connected to a high-performance liquid chromatograph (HPLC). This system makes it possible to measure neurophysiological activities in the olfactory system of C. carassius L. after exposure of this fish to alarm pheromones. The construction of the system was presented for the first time at the 3rd International Symposium on Separation in Bio Sciences SBS 2003 in I. Brondz, et al., The Fish Olfactory System Used as an In-Line HPLC Neurophysiologic Detector NPD, 3rd Int. Symposium on Separation in Bio Sciences SBS 2003: A 100 Years of Chromatography, 13-18 May, Moscow, Russia, 2003, Abstract O- 27, p. 95. A complete paper was published in I. Brondz, et al., Neurophysiologic Detector (NPD)—A Selective and Sensitive Tool in High-Performance Liquid Chromatography, Chromatography B: Biomedical Sciences and Applications, Vol. 800, No. 1-2, 2004, pp. 41-47, and the hybridization of living cells with an electronic device has been discussed (I. Brondz, et al., International Scientific-Technical Conference Sensors Electronics and Microsystems Technology (SEMST-1), 1-5 June, (Odessa), Ukraine, 2004, Plenum Lecture, Abstract p. 17;I. Brondz, et al., The European Chemoreception Research Organization ECRO 2004 Congress, 12-15 September, (Dijon), France, 2004, Abstract P-3;and I. Brondz, et al., Biosensors as Electronic Compounds for Detector in the High-Performance Liquid Chromatography (HPLC), Electronic Components and Systems, Vol. 3, No. 103, 2006, pp. 25-27). In the present study, an HPLC equipped with an NPD was used to assess the influence of organophosphate (OP) pesticides on olfactory sensory nerves and the modification of nerve signals from the olfactory organ. The results show that exposure of the olfactory system to OP pesticides can lead to disruption of normal reflexes and to significant suppression of individual sexual activity and, as a result, to the suppression of a population.

巢湖沉积物OPs和SPs的生态风险评价

为了认识水生环境中当前使用的有机磷农药（OPs）和拟除虫菊酯杀虫剂（SPs）的赋存、来源和生态风险,文章利用固相萃取（solid-phase extraction,SPE）-气相色谱-质谱（gas chromatography-mass spectrometry,GC-MS）技术分析了巢湖表层沉积物中10种SPs和12种OPs的浓度,通过与国内外相关研究结果比较,明确了这些污染物在巢湖流域的污染现状,并结合物种敏感性分布模型（species sensitivity distribution,SSD）评价了表层沉积物中浓度较高的苄氯菊酯和敌敌畏生态风险。结果表明：巢湖表层沉积物中SPs和OPs质量比范围分别为0.08-2.95ng/g和0.09-1.72ng/g,并呈现出西半湖高、东半湖低的空间分布特点。其中苄氯菊酯和敌敌畏分别是SPs和OPs最重要的组成成分,占各自总质量比的44%和47%;与国内外其他地区表层沉积物中报道的数值比较,巢湖表层沉积物中SPs质量比处于较低水平。SSD模型评价结果显示巢湖表层沉积物中苄氯菊酯生态风险较低,但敌敌畏却存在极大的生态安全风险,因此需要采取相应的措施减小OPs对当地水生生态系统的影响。

Case Control Study of Impulsivity,Aggression,Pesticide Exposure and Suicide Attempts Using Pesticides among Farmers

A case-control study was conducted to investigate associations between organophosphate pesticide（OP）exposure,aggression,impulsivity,and attempted suicide.Questionnaires were used to collect information;impulsivity and aggression were measured by the Barratt Impulsivity Scale（BIS）and the Aggression Inventory（AI）.

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.

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.

3DRGO-NiFe2O4/NiO nanoparticles for fast and simple detection of organophosphorus pesticides

The residues of organophosphorus pesticide(OPs)on fruits and vegetables pose a threat to human health,so it is very meaningful to explore simple and fast detect methods for OPs residual.In this work,nickel ferrite/nickel oxide nanoparticles co-loaded three-dimensional reduced graphene oxide(3DRGONiFe2O4/NiO NPs),as a new low cost nanocomposite,was prepared.Based on its high performance mimetic peroxidase activity,a colorimetric method for the detection of OPs has been developed.Dichlorvos was chosen as model compounds to evaluate the detection performance.The detection linear range for dichlorvos is from 50μg/mL to 2.5×10^4μg/mL with a detection limit of 10μg/mL.Furthermore,a test paper can be developed based on the 3 DRGO-NiFe2O4/NiO NPs for visual detection of dichlorvos,and the image information of the paper sensor can be converted into digital signal and quantitative detection by a smartphone.Notably,this method can also be used to detect dichlorvos in real samples,including vegetables and fruits.Thus,the developed naked assay holds great potential in simple,inexpensive and rapid detection of OPs in fruit and vegetable samples.

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.

Identification of water-borne bacterial isolates for potential remediation of organophosphate contamination

Three water-borne bacterial isolates were collected from the Houston metropolitan area. Each isolate was capable of growing upon carbon limited media inoculated with the organophosphorus (OP) compound paraoxon. All isolates were able to efficiently metabolize paraoxon and, to a lesser degree, methyl parathion to p-nitrophenol. 16S rDNA genome sequencing with universal bacterial primers identified the isolates as species belonging to the genera Aeromonas, Steno- trophomonas, or Exiguobacterium. All screened isolates harbor organophosphorus degradation (opd) genes that are approximately 99% similar over approximately 660 base pairs sequenced to one first isolated from Sphingobium fuliginis ATCC 27551 (formerly Flavobacterium sp. ATCC 27551). Additionally, two isolates KKWT11, identified as a putative Senotro- phomonas maltophilia, and KKBO11, identified as a putative Exiguobacterium indicum, were found to possess genomic DNA that closely matched a metallo- beta-lactamase that has been reported to function as a methyl parathion degradation (mpd) gene suggesting that both of these strains are prime candidates for wastewater remediation of a broad range of OP compounds.

利用农业固体废弃物去除水环境中多环芳烃污染物和有机磷农药的研究进展

随着经济和人口的增长,环境污染特别是水环境污染日益加剧,对水生生物和人体健康皆造成了威胁。农业固体废弃物因成本低、吸附能力强、易修饰和操作简单,而成为一种有潜力的传统吸附剂替代品。本文以多环芳烃污染物(PAHs)和有机磷农药(OPs)为分析对象,就农业固体废弃物的性质、吸附机理、影响因素及其作为吸附剂对水环境中PAHs和OPs的吸附性能等方面进行综述,并对其应用进行了展望。

加压流体萃取-气相色谱-质谱法测定土壤和沉积物中32种有机磷类及8种拟除虫菊酯类农药残留

建立了加压流体萃取-气相色谱-质谱法测定土壤和沉积物中32种有机磷农药和8种拟除虫菊酯类农药的方法。选用正己烷/丙酮(体积比1∶1)混合溶液作为萃取溶剂,采用加压流体萃取仪对土壤和沉积物样品进行萃取,经石墨化炭黑固相萃取小柱净化后,内标法定量。实验结果表明,32种有机磷农药和8种拟除虫菊酯类农药在质量浓度10.0~100.0 mg·L^(-1)范围内线性关系良好,校准曲线中目标化合物相对响应因子的相对标准偏差均<20%,检出限为0.1~0.3 mg·kg^(-1),以空白样品为基体进行低、中、高三个浓度的加标回收试验,平均回收率分别为60.0%~100%、70.0%~90.0%、70.0%~104%,实验室内相对标准偏差(RSD)分别为:0.00%~13.0%、1.25%~15.3%、1.14%~19.1%。该方法具有操作简便、灵敏度高、精密度及准确性好等特点,可满足土壤和沉积物中32种有机磷农药和8种拟除虫菊酯类农药的分析要求。

The Mechanism of Organophosphorus Pesticide-Induced Inhihition of Cytolytic Activity of Killer Cells

The main toxicity of organophosphorus pesticides （OPs） is neurotoxicity, which is caused by the inhibition of acetylcholinesterase. OPs also affect immune responses including effects on antibody production, IL-2 production, T cell proliferation, decreasement of CD5 cells, and increasement of CD26 cells and autoantibodies. However, there have been few papers investigating the mechanism of OP-induced inhibition of cytolytic activity of killer cells. This study reviews the new mechanism of OP-induced inhibition of activities of natural killer （NK）, lymphokine-activated killer （LAK） and cytotoxic T lymphocytes （CTL）. NK, LAK and CTL induce cell death in tumor or virus-infected target cells by two main mechanisms. The first mechanism is direct release of cytolytic granules that contain perforin, granzymes, and granulysin by exocytosis to kill target cells, which is called the granule exocytosis pathway. The second mechanism is mediated by the Fas ligand （Fas-L）/Fas pathway. To date, it has been reported that OPs inhibit NK, LAK and CTL activities by at least the following three mechanisms： 1） OPs impair the granule exocytosis pathway of NK, LAK and CTL cells by inhibiting the activity of granzymes, and by decreasing the intracellular level of perforin, granzyme A and grannlysin, which was mediated by inducing degranulation of NK cells and by inhibiting the transcript of mRNA of perforin, granzyme A and granulysin; 2） OPs impair the FasL/Fas pathway of NK, LAK and CTL cells, as investigated by using perforin-knockout mice, in which the granule exocytosis pathway of NK cells does not function and only the FasL/Fas pathway remains functional; 3） OPs induce apoptosis of immune cells. Cellular ＆ Molecular Immunology. 2006;3（3）：171-178.

Determination of organophosphorus pesticide residues in vegetables by an enzyme inhibition method using α-naphthyl acetate esterase extracted from wheat flour

The widespread use of organophosphorus pesticides(OPs) poses a great threat to human health and has made the detection of OP residues in food an important task,especially in view of the fact that easy and rapid detection methods are needed.Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase(ANAE) in plants,in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour.The limits of detection(LODs) obtained for methamidophos,dichlorvos,phoxim,dimethoate,and malathion in lettuce samples with crude ANAE were 0.17,0.11,0.11,0.96,and 1.70 mg/kg,respectively.Based on the maximum residue limits(MRLs) for OPs in food stipulated by Chinese laws which are 0.05,0.20,0.05,1.00,and 8.00 mg/kg for methamidophos,dichlorvos,phoxim,dimethoate,and malathion,respectively,the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos,dimethoate,and malathion in lettuce,but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present.The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out.The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food.This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness,sensitivity,and convenience.

CVVHDF联合血液灌流对急性有机磷中毒患者肝肾功能及血清ChE水平的影响

目的研究连续性静脉-静脉透析滤过(continuous veno venous hemodia filtration,CVVHDF)联合血液灌流对急性有机磷中毒(acute organophosphorous pesticide poisoning,AOPP)患者肝肾功能及血清胆碱酯酶(cho⁃linesterase,ChE)水平的影响。方法回顾性分析2020年1月—2023年1月广西-东盟经济技术开发区人民医院收治的78例AOPP患者的临床资料,依据收治时间不同划分对照组与干预组,其中2020年1月—2021年7月收治的39例作为对照组,予以血液灌流治疗,同时予以患者洗胃、灌肠、同时补液维持体内电解质平衡与酸碱度平衡;2021年8月—2023年1月收治的39例作为干预组,在对照组基础上予以CVVHDF治疗。观察组患者血清中的谷丙转氨酶(alanine aminotransferase,ALT)、谷草转氨酶(aspartate aminotransferase,AST)、总胆红素(total bilirubin,TBiL)水平,以评估肝功能;分析血尿素氮(blood urea nitrogen,BUN)、血肌酐(serum cre⁃atinine,Scr)、尿酸,用以评价患者肾功能;于治疗前与治疗1 h、1 d、2 d、3 d后监测患者血清中ChE水平变化;并评价两组总疗效。结果治疗后,两组的ALT、AST、TBiL水平明显降低,且干预组降低程度高于对照组,差异有统计学意义(P均<0.05)。治疗后,两组血液BUN、Scr、尿酸水平明显降低,且干预组肾功能改善程度均优于对照组,差异有统计学意义(P均<0.05)。经过治疗1、2、3 d后,两组血清ChE水平明显升高,且干预组均高于对照组,差异有统计学意义(P均<0.05)。经过治疗后对照组的总有效率为74.36%,干预组的总有效率为92.31%,二者比较,差异有统计学意义(χ2=4.523,P<0.05)。结论CVVHDF联合血液灌流有助于提升患者血清ChE水平及肝肾功能,疗效明确。

固相微萃取/二氧化锡气体传感器联用技术对果蔬中有机磷农药残留的快速检测

研究了固相微萃取(SPME)和二氧化锡气体传感器的联用技术对果蔬中有机磷农药残留乐果、氧乐果、甲胺磷、乙酰甲胺磷、马拉硫磷、敌百虫等的快速检测。结果表明,在85℃下,解吸8min,二氧化锡气体传感器在2min内完成对有机磷农药残留的快速检测。零解吸时间测量的甲胺磷的动态响应曲线表明,SPME/二氧化锡气体传感器联用技术对分析SPME的解吸平衡非常有利。