Effects of cyclodextrins on hydrolysis of malathion

Cyclodextrins （CDs）, with hydrophobic interior cavity and hydrophilic external surface, are capable of accelerating or inhibiting chemical degradation of organophosphorus pesticides through forming inclusion complexes between CDs and pesticides. This work evaluated the effects of CDs on hydrolysis of malathion in an attempt to assess their potential application in environmental approach. β-CD and its two derivatives, randomly methylated β-CD （RAMEB） and hydroxypropyl β-CD （HP-β-CD）, were tested. It was found that RAMEB could inhibit the hydrolysis of malathion, and this was the function of pH and temperature, the inhibitory effects increase with increasing concentration of RAMEB and elevating temperature between 15 and 35℃. On the other hand, β-CD and HP-β-CD have little or no stabilizing effects on malathion at all pH and temperature studied, except that the large concentration of β-CD and HP- β-CD can mildly reduce hydrolysis of malathion. Both 2 mol/L and 5 mol/L urea increase the inhibitory effects of RAMEB on hydrolysis of malathion at 25℃, oH 9.0.     

马拉硫磷及其水解产物对圆瘤浮萍的生长抑制及氧化损伤作用

为了探讨马拉硫磷和主要水解产物对圆瘤浮萍的生长抑制作用及可能的氧化损伤机制,采用静态培养法,研究不同浓度的马拉硫磷及其水解产物二甲基二硫代磷酸酯(DMDTP)、二甲基硫代磷酸酯(DMTP)、二甲基磷酸酯(DMP)对圆瘤浮萍生长、叶绿素含量、叶绿体活性、超氧化物歧化酶(SOD)、过氧化物酶(POD)和过氧化氢酶(CAT)活性及丙二醛(MDA)含量的影响。结果表明,暴露7 d后,浓度为100 mg a.i.·L-1处理下的浮萍叶状体生长量与空白对照组无显著性差异;DMDTP、DMTP和DMP对圆瘤浮萍叶状体生长量的半数抑制浓度(7 d-IC50)分别为52.9、45.5和98.0 mg a.i.·L-1。随着试验液中DMDTP、DMTP和DMP浓度的升高,圆瘤浮萍叶绿素含量均明显降低,叶绿体活性则分别表现为诱导-抑制、抑制和抑制效应。在DMDTP、DMTP和DMP胁迫下,脂质过氧化产物丙二醛(MDA)含量明显增加;圆瘤浮萍体内的抗氧化酶系统均受到影响。总体表现为随着DMDTP浓度的增加,SOD活性先降低后升高;DMTP和DMP胁迫下,SOD活性呈现先降后升再降的趋势;POD和CAT活性则随3种水解产物浓度的增加呈现先升后降趋势;这表明抗氧化酶系统对外部胁迫的应答很复杂。马拉硫磷对圆瘤浮萍的毒性较小,其水解产物DMDTP、DMTP和DMP均对圆瘤浮萍的生长产生一定的毒性作用。在实际生产中,应多加关注马拉硫磷水解产物对环境生物的风险评估。     

A field study on residues of four insecticides used in strawberry protection

Abstract

In 1986 strawberry plots were treated with dimethoate, malathion, permethrin and cypermethrin at 80% bloom of primary flowers. In 1987 the plots were sprayed with dimethoate, malathion and permethrin at 30% bloom. Residue analysis of these insecticides on the flowers were analyzed using solvent extraction and gas liquid chromatography. Residue analysis at 0 to 18 days on flowers and fruit showed an exponential decrease. Organophosphates tended to degrade more quickly than synthetic pyrethroids. The results are discussed in the context of an integrated pest management program.     

4种人工湿地基质对马拉硫磷的吸附特性

通过基质对马拉硫磷的等温吸附和吸附动力学实验,研究天然土壤、煤渣、沸石、砾石对马拉硫磷的吸附特性,为人工湿地处理含马拉硫磷废水提供理论依据.结果表明:马拉硫磷浓度为2.25 ～ 90 mg/L条件下,Langmuir和Freundlich方程均能较好地拟合4种基质对马拉硫磷的等温吸附过程,并且Freundlich方程的拟合效果要好于Langmuir方程.马拉硫磷的理论饱和吸附量大小依次为天然土壤(9.9304 mg/g)＞煤渣(1.6173 mg/g)＞沸石(0.6039 mg/g)＞砾石(0.3965 mg/g).4种基质对马拉硫磷的缓冲能力大小依次为天然土壤＞煤渣＞沸石＞砾石,即当进水马拉硫磷浓度波动较大时,作为湿地基质天然土壤使人工湿地系统维持稳定出水水质的能力最强.马拉硫磷浓度为4.5 mg/L条件下,吸附动力学模型Elovich方程能较好地拟合4种基质对马拉硫磷的吸附动力学特征,说明4种基质对马拉硫磷的吸附是表面吸附和内部扩散吸附共同作用的结果.因此,天然土壤和煤渣适宜作为处理含马拉硫磷废水的人工湿地基质.     

利用多物种净水监测仪在线监测水体抗生素药物及有机磷农药

通过多物种净水监测仪(Multispecies Freshwater Biomonitor,MFB)监测斑马鱼在抗生素药物(恩诺沙星、磺胺嘧啶)和有机磷农药(乐果、马拉磷硫)暴露下的行为强度变化,以验证其作为监测水体环境中抗生素类药物和有机磷农药生物指标的可行性.结果表明,恩诺沙星、磺胺嘧啶对斑马鱼没有急性毒性,乐果、马拉硫磷对斑马鱼的LC50-96值(96h半致死浓度)分别是61、5.4mg.L?1.斑马鱼对环境变化的行为反应快速且敏感,随着药物浓度的增加,斑马鱼行为变化的强度增大,反应时间缩短,且行为强度的变化符合环境压力模型(Stepwise Stress Model,SSM).斑马鱼行为的改变与一般急性毒性实验结果有相关性,可以作为对抗生素和有机磷农药污染水质早期预警的生物在线监测指标.     

Sublethal contaminant exposure alters behavior in a common insect: Important implications for trophic transfer

This study examined the effects of sub-lethal exposure of the ubiquitous pesticide malathion on the behavior of the model orthopteran species, the house cricket (Acheta domesticus). Increasing concentrations of malathion caused male crickets to increase periods of non-directional movement, such as twitching and grooming, directional movement, and to seek out shelter less. These are all behavioral alterations that may increase the cricket's chances of being preyed upon, and thus have the potential for serious ecological consequences through trophic transfer. This study also revealed that female crickets appeared to be less affected by malathion than their male conspecifics, indicating a potential sex-bias in both susceptibility and possible predator attack.     

Highly sensitive and selective determination of malathion in vegetable extracts by an electrochemical sensor based on Cu-metal organic framework

Abstract

This article demonstrates the first application of a copper-based porous coordination polymer (BTCA-P-Cu-CP) as a carbon paste electrode (CPE) modifier for the detection of malathion. The electrochemical behavior of BTCA-P-Cu-CP/CPE was explored using cyclic voltammetry (CV) while chrono-amperometry methods were applied for the analytical evaluation of the sensor performance. Under optimized conditions, the developed sensor exhibited high reproducibility, stability, and wide dynamic range (0.6–24?nM) with the limits of detection and sensitivity equal to 0.17?nM and 5.7 µAnMcm^?1, respectively, based on inhibition signal measurement. Furthermore, the presence of common coexisting interfering species showed a minor change in signals (<4.4%). The developed sensor has been applied in the determination of malathion in spiked vegetable extracts. It exhibited promising results in term of fast and sensitive determination of malathion in real samples at trace level with recoveries of 91.0 to 104.4%. (RSDs < 5%, n?=?3). A comparison of the two studied techniques showed that the HPLC technique is unable to detect malathion when the concentration is lower than 1.8?µM while 0.006 µM is detected with appropriate RSDs 0.2–5.2% (n?=?3) by amperometric method. Due to the high sensitivity and selectivity, this new electrochemical sensor will be useful for monitoring trace malathion in real samples.     

Malathion-induced sublethal toxicity on the intestine of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

Does malaoxon play a role in the geno- and cytotoxic effects of malathion on human choriocarcinoma cells?

This investigation was undertaken to elucidate whether the active metabolite of malathion, malaoxon, has any role in exerting cyto- and genotoxic effects for human choriocarcinoma (JAR) cell line which is an acceptable model for human placental cells. Gas chromatography-mass spectrometry (GC-MS) analysis were separately performed on the cell compartment and supernatant cell culture medium after subjecting the cell line to different malathion concentrations (10–400 μg/mL) and for various incubation periods (0.5 to 24 hours). GC-MS analysis showed that the sonication performed for the disruption of the cells did not cause the chemical change of malathion. The uptake of malathion by the cells was relatively fast. However, the presence of malaoxon, even in trace amounts, could not be confirmed either in samples originating from disrupted cells or in the cell culture medium. Although the hydrolysis of malaoxon occurred in the culture medium, this degradation process could not be counted as a reason for the absence of malaoxon. Since both malathion and malaoxon standard compounds could be accurately detected and distinguished by the applied liquid-liquid extraction and GC-MS methods, one can conclude that, in the case of JAR cells, the parent compound, (i.e. malathion itself) is responsible for the observed in vitro cyto- and genotoxic effects. Our results indicate that the direct toxicity of malathion contributes to the complications of pregnancy observed for environmental malathion exposure.     

淡水鱼脑AChE的动力学特性及抗抑制性

用PEG2000双水相萃取、DEAE-Sephadex A-50和SephadexG-200方法分离提纯麦穗鱼(Pseudorasbora parva)、金鱼(Carassius auratus)和虹鳟鱼(Salmo gairdneri)脑乙酰胆碱酯酶(AChE),比较这3种淡水鱼脑AChE纯酶液与粗酶液的动力学特性、抗抑制性及其种类之间的差异.结果表明,这3种鱼脑AChE的性质在种类间的差异要远远小于其在粗酶状态时酶活性的差异,由此得出AChE性质在种类间的差异并非影响这3种淡水鱼脑AChE活性差异的主要因素;由AChE抗抑制试验结果可知,这3种鱼脑AChE粗酶液对经溴水氧化后的马拉硫磷和三唑硫磷的敏感性及种间的差异都远大于纯酶液.