Pretreatment of heterocyclic pesticide wastewater using ultrasonic/ozone combined process

Ultrasonic/O3 combined process was employed to pretreat heterocyclic pesticide wastewater for increasing biodegradability and reducing biological toxicity. Influences of ultrasonic frequency, ultrasonic power, probe diameter, initial pH and O3 dosage on the COD removal were studied. The results showed that the ultrasonic/O3 process significantly improved the biodegradability and reduced the biological toxicity of the wastewater. The ratio of BOD5/COD was increased from 0.03 to 0.55 and the EC50 increased from 11% to 52% under ultrasonic/O3 treatment. Low ultrasonic frequency brought better COD removal. Initial pH was found to have a high influence on the COD removal and alkaline conditions were more favorable. The influences of ultrasonic power and probe diameter were small. With an increase in O3 dosage, COD removal was e ectively improved. The optimal operational parameters for the combined process on COD removal were ultrasonic frequency 20 kHz, initial pH 9.00, ultrasonic power 300Wand dosage of O3 454.8 mg/(L min), under which the e ciency of COD removal reached 67.2%.     

Photoelectrocatalytic degradation of high COD dipterex pesticide by using TiO2/Ni photo electrode

A TiO₂ thin film electrode deposited on porous nickel net (TiO₂/Ni) was prepared by the sol-gel method, and the surface morphology, crystal structure features and the grain size were characterized by Field emission scan electron microscopy (FESEM) and X-ray diffraction (XRD). The photoelectrocatalytic system was set up using a UV high-pressure mercury lamp as the light source, TiO₂ coated on foamed nickel as photo anode, Pt sheet as counter electrode and the pesticide dipterex in synthetic wastewater. Various factors that influence the photoelectrocatalytic decomposition of dipterex pesticide have been studied, such as degradation time, the type of electrolyte, current density, original pH value and different degradation methods. The prepared catalysts were employed to photoelectrocatalytically degrade the pesticide dipterex under UV irradiation, comparing the results with photocatalytic degradation and electrochemical oxidation. The results indicated that under the optimal conditions of 0.02 mol/L NaCl as the supporting electrolyte, current density = 2.5 mA/cm², pH 6.0 and dipterex pesticide 40 mg/L, and reaction time 2 hr, dipterex chemical oxygen demand (COD) removal rate and organophosphorous conversion of up to 82.6% and 83.5% were achieved, respectively. The method of photoelectrocatalytic degradation is more efficient than photocatalysis and electrochemical oxidation. The possible roles of the electrolytes on the reactions and probable mechanisms were also discussed.     

有机氯农药微生物降解技术研究进展

文章综述了有机氯农药的污染化学特征、环境介质中的分布水平、降解功能微生物的种类以及典型有机氯农药的降解途径等,并对有机氯农药微生物降解相关的酶和基因以及降解机理进行了重点讨论。参与有机氯农药微生物降解过程的酶主要有脱氯化氢酶、水解酶和脱氢酶三种,它们通过共代谢,中间协同代谢或矿化等作用完成降解过程。相关降解基因主要是Lin家族基因,包括LinA～LinJ的10个典型功能基因编码。微生物降解有机氯农药的机理主要包括矿化作用、共代谢作用、种间协同代谢作用、活化作用和间接作用等,其中矿化过程包括氧化、还原、水解、脱水、脱卤和裂解等生化反应。由于有机氯农药的持久性和广泛污染性,其降解机理及中间产物的类型、毒性以及新型降解菌的效能开发仍是该领域今后的研究重点。     

松涛水库水生生物农药污染水平及健康风险评价

在海南省松涛水库采集了鱼类和螺蛳共34个样品,利用气相色谱-质谱联用仪(GC-MS)检测样品中农药的浓度,并根据美国环境保护署(US EPA)的健康风险评价模型对松涛水库周围人群通过饮食途径摄入水生生物进行健康风险评价。结果表明,检测的29种农药,仅有7种在大部分样品中检出,分别为2,4-DDE、4,4-DDE、2,4-DDD、4,4-DDD、4,4-DDT、甲氧滴滴涕和甲基对硫磷,它们的平均含量(以湿重计)分别为0.32 ng·g~(~(-1))、3.68 ng·g~(~(-1))、0.17 ng·g~(~(-1))、1.33 ng·g~(~(-1))、0.90 ng·g~(~(-1))、1.34 ng·g~(~(-1))、0.32 ng·g~(~(-1))。鱼类肌肉以及螺蛳肉中农药的健康风险评价远远低于可承受水平,表明食用这些鱼类与螺蛳所造成的健康风险比较低。与其他研究相比,松涛水库的农药污染程度较轻。造成不同生物体间的农药含量差异的主要原因可能是牙叉库区的农药污染比南丰和番加库区的污染严重。     

我国重点流域地表水中29种农药污染及其生态风险评价

针对我国重点流域水体,包括长江流域、黄河流域、太湖流域、松花江流域、黑龙江流域、东江流域、南水北调中线和东线等,分析了29种农药(18种有机氯农药、6种有机磷农药、3种三嗪类农药、1种酰胺类和1种取代杂环类农药)在流域地表水中浓度,并使用风险商的方法进行了生态风险评价。结果显示,在27个采样点地表水样中一共检出9种农药,包括α-六六六、α-氯丹、γ-氯丹、西玛津、阿特拉津、乙草胺、扑草净、敌敌畏和噁草酮。其中,阿特拉津、乙草胺、扑草净、噁草酮和敌敌畏的检出率分别为100.0%,74.1%,59.3%,37.0%和33.3%;α-六六六、α-氯丹、γ-氯丹和西玛津均只有1~2个采样点检出。阿特拉津在各采样点浓度范围为7.0 ng·L-1~1 289.5 ng·L-1;乙草胺浓度范围为未检出(ND)~579.9 ng·L-1;扑草净浓度范围为ND~104.2 ng·L-1;噁草酮浓度范围为ND~32.6 ng·L-1;敌敌畏的浓度范围为ND~204.5 ng·L-1。研究发现,阿特拉津在太湖流域、黑龙江流域和松花江流域具有潜在生态风险;乙草胺在松花江流域有潜在生态风险;噁草酮在长江流域、太湖流域、松花江流域和黑龙江流域有潜在生态风险;敌敌畏在长江流域、黄河流域和东江流域具有潜在生态风险。上述4种需要重点关注的水体污染物中,仅阿特拉津和敌敌畏被列入地表水环境质量标准(GB3838-2002),但都没有保护水生生物或保护水生态的标准。     

珠江河口水体有机磷农药的含量与季节变化

定期采集珠江口地区3条河涌的水样,分析9种有机磷农药(OPPs)含量及其时空变化规律.监测期间,9种OPPs中有7种被检出,检出率由高到低依次为:甲拌磷(97.5%)、敌敌畏(80.0%)、乙拌磷(77.5%)、灭线磷(15.0%)、乐果(10.0%)、甲基对硫磷(5.0%)、毒死稗(5.0%).∑OPPs浓度为0.46~43.60μg/L,平均为7.25μg/L,与其他地区相比处于较高的污染水平.珠江口有机磷农药的污染状况受季节影响十分显著.从丰水期至枯水期,沙湾水道、蕉门水道、万顷沙∑OPPs均值分别从7.82μg/L降至2.24μg/L,10.58μg/L降至6.46μg/L,13.08μg/L降至3.32μg/L.3条水道水质受农田面积、种植类型等因素的影响,OPPs污染状况和组成有较大的差异.     

Agricultural chemical exposure in small farmers in Guyana

A study of self-reported injury from agricultural chemical exposure was conducted in farmers in rural Guyana. One hundred and ninety agricultural workers were studied, of which 167 (88%) were male. Morbidity from agricultural chemical exposure was common, with 87 farmers (46%) reporting having experienced at least one episode of illness after agricultural chemical exposure. Relatively few of the farmers sought medical assistance for their symptoms, with only 20 farmers (11%) visiting a local doctor and only two farmers (1%) reporting going to a hospital for treatment. Local farmer use of protective equipment was limited. Pyrethroids and herbicides paraquat and glyphosate were the most commonly used agricultural chemicals in the population studied. Data showed that exposure to agricultural chemicals remains frequent, with incidence of severe injury requiring less frequent medical attention.     

低温弱光条件下毒死蜱对黄瓜的毒性效应及油菜素内酯的调控作用

农药在使用中可能对农作物产生药害作用,而在低温弱光的亚适宜条件下,设施作物对农药暴露的应激响应可能具有特殊性。同时,作为一种新型植物激素,油菜素内酯在亚适宜条件下是否能够缓解农药的药害作用的研究有限。以典型的设施作物黄瓜为受试生物,通过人工气候箱模拟低温弱光的亚适宜条件,在毒死蜱(浓度分别为0.3和1mmol·L-1)暴露1、3和7d后,以实时荧光定量PCR对黄瓜叶片中光合作用基因(psaB、psbA和rbcL)、抗氧化系统相关基因(cAPX、DHAR、GR、CAT和GPX)、防御和应激相关基因(PAL、HPL、ADC和HSP70)的转录水平进行检测,阐明其毒性效应。并对比24-表油菜素内酯的预处理组,探讨油菜素内酯如何调控作物对农药胁迫的响应。结果表明,在低温弱光条件下,毒死蜱暴露抑制了黄瓜叶片中上述大部分基因的转录,而24-表油菜素内酯预处理后其转录水平显著上升,表明24-表油菜素内酯可有效且持续地缓解毒死蜱的药害效应。     

分散固相萃取-超高效液相色谱-串联质谱联用快速检测大豆及土壤中氟磺胺草醚残留

采用分散固相萃取(QuEChERS)样品前处理方法,建立了超高效液相色谱-串联质谱(UPLC-MS/MS)快速检测大豆和土壤中氟磺胺草醚的残留分析方法.大豆和土壤样品采用乙腈(含0.5%甲酸)提取,N-丙基乙二胺(PSA)或石墨化碳黑(GCB)净化,UPLC-MS/MS外标法检测定量.在0.005—0.5 mg.kg-1添加范围内,氟磺胺草醚在土壤、大豆和大豆植株中的平均回收率在79.4%—109.0%之间,变异系数在3.6%—10.1%之间.在山东、河南、吉林进行了氟磺胺草醚在大豆植株和土壤中的降解动态研究,结果表明,试验点中氟磺胺草醚在土壤中的降解半衰期为8.5—23.7 d;在大豆植株中的降解半衰期为2.7—9.8 d.     

氨基甲酸酯类农药对蛋白核小球藻联合毒性作用特点及机制

氨基甲酸酯类农药广泛应用于农业生产中,其在环境中的残留及其对非靶标生物的毒性作用引起关注。以5种氨基甲酸酯类农药包括残杀威、灭多威、抗蚜威、涕灭威和呋喃丹为研究对象,以蛋白核小球藻为受试生物,应用微板毒性分析法系统测定每种农药及其五元混合物对蛋白核小球藻在不同暴露时间(12、24、48、72和96 h)的生长抑制作用,并同步分析农药对蛋白核小球藻的生理特性如叶绿素含量、蛋白质含量、超氧化物歧化酶(SOD)活性和脂质过氧化物丙二醛(MDA)含量的影响。结果表明,5种农药对蛋白核小球藻的浓度-效应均具有明显的时间依赖性,农药抗蚜威在中低浓度促进绿藻生长,呈现非单调J型浓度-效应曲线(CRC)特征,其余4种农药的CRC呈现经典S型;以半数效应浓度的负对数(p EC50)为毒性大小指标,5种农药在96 h时毒性大小为:呋喃丹(p EC50=3.43)残杀威(p EC50=2.76)抗蚜威(p EC50=2.12)灭多威(p EC50=2.11)涕灭威(p EC50=1.89)。浓度为EC50的5种农药处理后的蛋白核小球藻中叶绿素和蛋白质含量随暴露时间的延长而减少,但不同农药处理的绿藻中叶绿素和蛋白质含量减少率随暴露时间延长变化趋势稍有不同; SOD酶活性随着暴露时间延长逐渐下降,MDA含量逐渐增加,这说明藻细胞受到破坏,脂质过氧化的损害程度超过细胞修复能力,SOD活性被抑制,细胞的抗氧化能力下降,藻细胞内的H2O2不断积累,导致MDA含量升高。五元混合物对蛋白核小球藻的毒性也具有一定的时间依赖性,并表现出刺激作用,即hormesis现象,且混合物毒性与组分浓度比具有良好的线性相关性;暴露于混合物的小球藻均在96 h出现了刺激效应,其叶绿素与蛋白质含量随暴露时间延长不断增加,SOD活性不断升高,MDA含量不断减少;五元混合物均在96 h呈现出拮抗作用,且与混合物的浓度和组分浓度比相关。