新烟碱类农药在我国的登记现状及对蜜蜂的初级风险评估

调研已开发的包括吡虫啉、噻虫嗪、噻虫胺、啶虫脒、噻虫啉、呋虫胺、烯啶虫胺、环氧虫啶、氯噻啉、哌虫啶和氟啶虫胺腈在内的11种新烟碱类农药在我国的登记现状。根据已登记的新烟碱农药的使用方法,开展了不同暴露场景下蜜蜂的初级风险评估。结果表明,喷施场景下,吡虫啉、噻虫嗪、噻虫胺、烯啶虫胺、呋虫胺、氟啶虫胺腈和氯噻啉这7种新烟碱类农药在不同作物上使用对蜜蜂的风险商值均大于1,风险均不可接受;啶虫脒、哌虫啶和噻虫啉在所有登记作物上使用对蜜蜂的风险商值均小于1,风险可接受。土壤或种子处理场景下,除噻虫啉外,其余4种新烟碱类农药包括吡虫啉、噻虫胺、噻虫嗪和呋虫胺对蜜蜂的风险商值均大于1,风险均不可接受。评估结果可为新烟碱类农药在我国的登记管理提供科学参考。     

蔬菜水果中的新烟碱类农药残留量与人群摄食暴露健康风险评价

新烟碱类农药是目前被广泛用于农业中的一类作用独特、高效广谱的内吸性杀虫剂,它们在蔬菜水果中的残留对人体健康构成威胁。本研究目的是查明北京市场上蔬菜水果中不同新烟碱类农药的残留量,并对人群摄食暴露健康风险进行评估。从北京市场上采集49种蔬菜和24种水果,采用Qu ECh ERS–高效液相色谱串联质谱(HPLC-MS/MS)法测定蔬菜水果中9种新烟碱类农药的含量。利用测得数据和中国居民膳食结构调查资料,采用蒙特卡罗模拟方法计算了不同年龄段人群的日均经口摄入暴露量的概率分布,并采用商值法计算了新烟碱类农药的非致癌风险。结果显示新烟碱类农药普遍存在于北京市场上的蔬菜水果中。49种蔬菜样品中检出7种新烟碱类农药,其中吡虫啉、啶虫脒和噻虫嗪检出率均达100%,噻虫胺、烯啶虫胺、噻虫啉和呋虫胺的检出率分别为47%、14%、10%和4%。24种水果样品中检出5种新烟碱类农药,其中吡虫啉和啶虫脒的检出率均达100%,噻虫嗪、噻虫胺和噻虫啉的检出率分别为54%、13%和4%。不同新烟碱类农药在蔬菜水果中的含量范围为0.01 ng·g~(-1)~126 ng·g~(-1),均未超过我国食品安全国家标准或美国联邦管理条例中的限量值。小部分(约3%)人群因摄食蔬菜水果暴露于新烟碱类农药的非致癌风险商值大于0.1。新烟碱类农药在蔬菜水果中普遍存在,对人体健康有潜在的风险。     

新烟碱类杀虫剂对蜜蜂的急性毒性及风险评价

为新烟碱类杀虫剂合理使用提供科学依据,本研究采用饲喂法和点滴法测定了9种新烟碱类杀虫剂对蜜蜂的急性毒性效应,且根据风险商值法进行了风险评价,氟啶虫酰胺和吡蚜酮作为对照药剂。试验结果表明:6种新烟碱类杀虫剂(噻虫胺、呋虫胺、吡虫啉、烯啶虫胺、氟啶虫胺腈和噻虫嗪)对蜜蜂经口和接触毒性的48 h-LD50值为1.73×10-3(1.37×10-3~2.45×10-3)~35.3×10-2(30.5×10-2~41.4×10-2)μg·蜂-1,均属于高毒级;其次为氯噻啉,该药剂对蜜蜂经口和接触毒性的48 h-LD50值为56.4×10-2(40.9×10-2~95.5×10-2)和2.05(1.13~3.18)μg·蜂-1,分别为高毒和中毒;而啶虫脒和噻虫啉对蜜蜂经口和接触毒性的48 hLD50值为2.57(1.94~3.75)~9.85(8.23~11.6)μg·蜂-1,为中毒级。对照药剂氟啶虫酰胺和吡蚜酮对蜜蜂经口和接触毒性的48h-LD50值均100μg·蜂-1,为低毒级。风险评价结果表明:噻虫胺、呋虫胺、吡虫啉、噻虫嗪、氯噻啉、烯啶虫胺和氟啶虫胺腈对蜜蜂具有不可接受的风险,啶虫脒、噻虫啉和对照药剂氟啶虫酰胺、吡蚜酮对蜜蜂的风险可接受。因此,在害虫综合治理中,应谨慎使用新烟碱类杀虫剂,以免对蜜蜂产生严重的毒副作用。     

9种杀虫剂对中华大刀螂幼虫的毒性

螳螂是田间控制害虫种群增加的重要捕食性天敌之一。以中华大刀螂3龄幼虫(Paratenodera sinensis Saussure)为受试生物,利用9种常用杀虫剂配制成不同浓度梯度的药剂,通过喷雾法直接暴露,分别测定了LC50和死亡率来评价不同杀虫剂对中华大刀螂毒性和危害程度的影响。结果显示,9种杀虫剂对中华大刀螂幼虫的毒性(LC50值)差异很大,用药后24h的LC50在0.7182～347.7962mg·L-1之间,LC95在8.8057～1734.5650mg·L-1之间;用药后48h的LC50在0.3564～193.6887mg·L-1之间,LC95在3.8958～1548.3258mg·L-1之间;用药后72h的LC50在0.2232～115.3391mg·L-1之间,LC95在1.7730～530.6462mg·L-1之间。不同杀虫剂对中华大刀螂幼虫的毒性差异最高达到543.46倍。毒性大小依次为,高效氯氟氰菊酯﹥啶虫脒﹥联苯菊酯﹥毒死蜱﹥噻虫嗪﹥茚虫威﹥吡虫啉﹥阿维菌素﹥苏云金杆菌原粉(Bt)。根据田间推荐浓度处理的死亡率判断,毒死蜱、联苯菊酯、啶虫脒、高效氯氟氰菊酯为有害水平,Bt为中度有害水平,吡虫啉、茚虫威、噻虫嗪为微害水平,阿维菌素接近无害水平。根据LC50与田间推荐浓度的比值判断,阿维菌素、吡虫啉对螳螂种群数量不会产生太大影响;Bt、茚虫威和噻虫嗪对螳螂种群数量会产生一定危害;而毒死蜱、啶虫脒、联苯菊酯和高效氯氟氰菊酯将严重影响螳螂种群数量的稳定性。在24～72h范围内,不同杀虫剂LC50和LC95随施药时间的延长而降低,说明暴露时间越长毒性越大,危害程度也越大。建议在中华大刀螂生活范围内减少高效氯氟氰菊酯、联苯菊酯、啶虫脒和毒死蜱的施用,推荐杀虫剂田间使用量时,除考虑对防治对象的防效,还应考虑对天敌种群的危害,提高药剂使用安全性,保护天敌种群的稳定性。     

7种农药对管氏肿腿蜂的毒性及初级风险评价

为评估农药对寄生类自然天敌昆虫的安全性,选择管氏肿腿蜂(Scleroderma guani Xiao et Wu)作为受试生物,采用管测药膜法测定了3种杀虫剂、2种除草剂、2种杀菌剂对其致死效应,并根据田间推荐剂量计算暴露量,采用风险商值HQ对杀虫剂进行风险评估。结果显示,与空白对照比较,3种杀虫剂均具明显毒性作用,其中丁硫克百威、吡虫啉和呋虫胺对管氏肿腿蜂的24 h半致死量(24 h-LR50)分别为5.11、2.92和0.06 g a.i.·ha-1,农田内风险商值分别为60.23、16.64和3 105。除草剂和杀菌剂在3倍最大田间推荐剂量作用下,24 h管氏肿腿蜂死亡率均小于50%。上述结果表明,在田间推荐用量下,3种杀虫剂对管氏肿腿蜂的初级风险评价为存在高风险,建议进一步开展高级阶段风险评估或者采取合理的风险管理措施来降低风险;除草剂和杀菌剂对管氏肿腿蜂的风险可接受。     

16种农药对东亚小花蝽的生态风险评估

东亚小花蝽是我国北方林木、果园和农田的优势天敌昆虫。为评估常用化学农药对东亚小花蝽的毒害作用,首次测定了16种田间常用化学农药对东亚小花蝽的24 h急性接触毒性,并进行了生态风险评估。结果表明所试除草剂、杀菌剂和杀虫剂中的吡蚜酮对东亚小花蝽较为安全,3倍田间最高推荐剂量下的校正死亡率低于33.33%。阿维菌素、甲氨基阿维菌素苯甲酸盐、吡虫啉和啶虫脒对东亚小花蝽的半数致死浓度LC0分别为36.567、15.798、4.992和4.487 mg a.i.·L~(-1)5,农田内风险可接受。噻虫嗪、联苯菊酯和呋虫胺对东亚小花蝽的LC_(50)分别为0. 002、0. 080和0. 968 mg a. i.·L~(-1),农田内危害商值分别为3 976.36、69.03和16.93,在农田内对东亚小花蝽造成的风险均不可接受。本研究的结果有助于合理施用化学农药以保护和利用东亚小花蝽。     

常用杀菌剂对啶虫脒中华蜜蜂毒性潜在增效作用研究

啶虫脒对蜜蜂急性毒性较低,且允许在作物花期施用,而杀菌剂也是蜜源植物花期常用药剂。本文采用点滴法和摄入法测定了10种常用杀菌剂对啶虫脒中华蜜蜂毒性的潜在增效作用。结果表明,点滴田间实际暴露剂量的杀菌剂使啶虫脒对中华蜜蜂的毒性不同程度的增加。点滴杀菌剂和啶虫脒24 h、48 h后,咪鲜胺、丙环唑、腈菌唑、戊唑醇、苯醚甲环唑、嘧菌酯、己唑醇、吡唑醚菌酯、三唑酮、氟硅唑使啶虫脒毒性分别增加14.02、10.74、8.50、7.92、4.77、4.28、4.19、4.07、2.74、2.67倍和8.01、10.14、4.80、7.09、2.66、2.56、3.62、2.69、2.24、1.49倍。摄入田间实际暴露剂量的杀菌剂和啶虫脒混剂24 h、48 h后,啶虫脒对中华蜜蜂的毒性增加。其中,丙环唑、氟硅唑、苯醚甲环唑、嘧菌酯、咪鲜胺使啶虫脒的毒性分别增加3.62、2.46、2.10、1.98、1.56倍和2.07、2.81、2.20、2.58、2.23倍。因此蜜源植物花期应避免丙环唑、咪鲜胺、戊唑醇、腈菌唑与啶虫脒先后喷施或混合喷施,慎用己唑醇等其他6种杀菌剂,以防啶虫脒残留导致中华蜜蜂采集蜂中毒。     

杀虫剂对土壤温室气体排放的影响

在室内培养条件下,研究了在施用尿素的土壤（有效氮质量分数为200 mg·kg^-1）中分别添加不同剂量（在5、10和50 mg·kg^-1）的吡虫啉和毒死蜱2种杀虫剂时,杀虫剂对土壤温室气体CO2、N2O和CH4排放过程的影响。结果表明：和空白相比,施用尿素明显地增加了土壤中温室气体N2O和CO2的排放量,但对CH4的排放无明显影响。当施用5 mg·kg^-1吡虫啉时,土壤中N2O和CO2排放总量和尿素处理相比无明显差异,但吡虫啉用量上升至10和50 mg·kg^-1时则显著降低了温室气体N2O和CO2的排放量（P〈0.05）,N2O排放量分别降低了26.89%和53.10%,CO2排放量分别降低15.14%和13.79%。毒死蜱在5、10和50 mg·kg^-1三种用量时土壤的N2O排放量与尿素处理相比均无明显差异。毒死蜱在5和10 mg·kg^-1用量时则明显抑制了土壤CO2的排放（p〈0.05）,分别比尿素处理降低了19.88%和19.02%;用量上升到50 mg·kg^-1用量时,土壤的CO2排放量与尿素处理相比无差异。吡虫啉和毒死蜱对CH4排放量均没有明显影响。可见,杀虫剂施用明显影响到土壤温室气体的排放,但不同杀虫剂品种及其用量的效应也存在明显差异。     

吡虫啉对蜜蜂幼虫的室内毒性研究

吡虫啉是目前使用最广泛的新烟碱类农药,其不合理使用破坏蜜蜂的嗅觉记忆能力,影响采集行为,导致多种亚致死效应。利用室内人工饲养蜜蜂幼虫技术,选取意大利蜜蜂幼虫为研究对象,经3 d适应性饲养后,连续3 d喂食含不同浓度的吡虫啉日粮,测定蜜蜂幼虫的存活率、化蛹率和羽化率,评估吡虫啉对蜜蜂幼虫生长发育影响。结果表明,吡虫啉处理剂量为15ng·幼虫~(-1)时,并不影响蜜蜂幼虫存活率、化蛹率和羽化率;当处理剂量达到150 ng·幼虫~(-1)时,蜜蜂幼虫羽化率下降,但不影响蜜蜂幼虫的存活率和化蛹率;幼虫7 d半数致死剂量为2 300 ng·幼虫~(-1)。高剂量吡虫啉对蜜蜂幼虫存活率、化蛹率和羽化率均存在影响,处理剂量越高,存活率、化蛹率和羽化率越低,呈高度负相关(r=-0.99,-0.94,-0.89),同时蜜蜂幼虫的羽化时间延长。研究可为吡虫啉的合理使用提供科学参考。     

Terrestrial laserscanning of tidal flats—a case study in Jiangsu Province, China

Terrestrial laserscanning (TLS), also called ground-based LiDAR (Light Detection And Ranging) is a relatively new method which revolutionised geomorphological research in many domains. However, detailed studies of tidal flats by TLS have not been described in the literature yet. This study aims to fill this methodological gap by the application of TLS at two different locations on the coast of Jiangsu Province, Eastern China, and an assessment of the usability of this method for geomorphological research in such environments. The acquired point clouds are first processed to remove erroneous and noisy points. Subsequently, point clouds are computed to produce polygonal meshes and grid-based digital terrain model (DTM) more commonly used by the scientific community. The accuracy of the measurements is assessed by an analysis of elevation deviations for flat and horizontal concrete blocks. High quality point clouds with point densities of up to 4,000 points/m² were acquired for a distance of up to 200 m. The data allowed for the detection of small landforms such as tidal channels, creeks and ripples in centimetre and decimetre scale. The point clouds had an average error of approximately 3 mm, however for some few points errors of up to 1.8 cm were detected. Based on the results it can be concluded that TLS can be a useful additional method for geomorphological research on tidal flats due to its ability to describe the landforms from high density point clouds. Repeated scanning could therefore provide data to quantitatively and qualitatively describe geomorphological changes over wider areas and thereby improve the understanding of sedimentation and erosion on tidal flats.     

Gas chromatographic studies of chlorinated phenols,chlorinated anisoles,and chlorinated phenylacetates

The g.l.c. retention times of all chlorinated phenols, anisoles, and phenylacetates on different capillary columns are presented. The relative retention times of the chlorinated phenols are discussed with reference to their pK_a values and their toxicities.     

A preliminary assessment of levels of antifouling booster biocides in harbours and marinas of the island of Gran Canaria, using SPE-HPLC

An analytical procedure was developed to allow for the study of the levels of concentration of biocides in the various different ports on the island of Gran Canaria, The Canary Islands. The analytes studied were extracted from water samples using solid-phase extraction and then determined by high-performance liquid chromatography using a diode array detector. The relative standard deviations of the developed procedure were under 12%. Recoveries over 85% and limits of detection between 0.007 and 0.4 μg/L were obtained for all the analytes. The method was applied to the analysis of sea water samples from the ports and marinas on the island of Gran Canaria.     

南渡江农业土壤中农药分布特征与生态风险评估

为摸清稻菜轮作土壤中农药(CUPs)残留特征与生态风险,采集海南岛南渡江流域稻菜轮作系统168个土壤样品,利用QuEChERS-超高效液相色谱-串联质谱(UPLC-MS/MS)检测土壤中25种CUPs残留水平,结合土壤因子与作物类型分析CUPs残留关键影响因素,以风险熵法评估其生态风险.结果表明,∑25 CUPs处于0...     

Microbial degradation of two carbamate insecticides and their main metabolites in soil

Degradation studies in soil of the insecticides aldicarb and carbofuran and their metabolites (aldicarb sulfoxide, aldicarb sulfone; 3-ketocarbofuran and 3-hydroxycarbofuran) were carried out using laboratory systems under controlled conditions (temperature, water content, light). The insecticides were added to soil samples and subsamples of the soil were analyzed at different times to assess both the bacterial abundance and the concentration of the different chemicals. The epifluorescence direct count method was applied to the subsamples to estimate microorganism numbers (N/g soil). Untreated samples of soil were used as controls for evaluating the effects of the application of the insecticides on microbial abundance. Subsamples treated with the pesticides were analyzed using HPLC and the DT 50 s of the different compounds studied were calculated. The DT 50 values show that neither the parent compounds nor the transformation products have a high persistence in soil and there is a general increase in the concentration of microorganisms as the pesticides diminish.     

MICROBIAL DEGRADATION OF TWO CARBAMATE INSECTICIDES AND THEIR MAIN METABOLITES IN SOIL

Degradation studies in soil of the insecticides aldicarb and carbofuran and their metabolites (aldicarb sulfoxide, aldicarb sulfone; 3-ketocarbofuran and 3-hydroxycarbofuran) were carried out using laboratory systems under controlled conditions (temperature, water content, light). The insecticides were added to soil samples and subsamples of the soil were analyzed at different times to assess both the bacterial abundance and the concentration of the different chemicals. The epifluorescence direct count method was applied to the subsamples to estimate microorganism numbers (N/g soil). Untreated samples of soil were used as controls for evaluating the effects of the application of the insecticides on microbial abundance. Subsamples treated with the pesticides were analyzed using HPLC and the DT 50 s of the different compounds studied were calculated.

The DT 50 values show that neither the parent compounds nor the transformation products have a high persistence in soil and there is a general increase in the concentration of microorganisms as the pesticides diminish.     

3种农药及其复配剂对意大利工蜂的急性经口毒性

采用"小烧杯法"测定了3种农药及其复配剂对意大利工蜂的24 h、48 h急性经口毒性,根据我国《化学农药环境安全评价实验准则》中蜜蜂急性经口毒性划分等级可知,对意大利工蜂,35%精甲霜灵悬浮种衣剂属"低毒"级,25%噻虫嗪水分散粒剂属"高毒"级,25 g·L~(-1)咯菌腈悬浮种衣剂属"低毒",25%噻虫嗪-咯菌腈-精甲霜灵悬浮种衣剂也属"高毒"级。     

Retention of PCDDS and PCDFS in the liver of the rat and hamster after oral administration of a municipal incinerator fly ash extract

A single dose of an extract from 16 and 5 grams fly ash was administered orally to male rats and hamsters. In the rat 1,2,3,7,8‐PnCDD had the highest retention (41%) in the liver. The congener with the highest retention in the liver of the hamster was 2,3,4,7,8‐PnCDF (70.9%). In two oral multiple dose experiments with rats, highest liver retentions were found for 1,2,3,7,8‐PnCDD (51.7%) and 1,2,3,6,7,8‐HxCDD (59.8%). With the exception of 2,3,4,6,7‐PnCDF, all PCDDs and PCDFs retained in the liver of rat and hamster had a 2,3,7,8 chlorine substitution pattern. In both types of experiments with rats the retention of 2,3,7,8‐TCDF in the liver was very low, 1.1–2.8% of the total dose. In the liver of the hamster retention of 2,3,7,8‐TCDF was almost equal to that of 2,3,7,8‐TCDD, indicating that the hamster is probably metabolizing 2,3,7,8‐TCDF Jess efficiently than the rat. In all experiments 1,2,3,7,8‐PnCDD and 2,3,4,7,8‐PnCDF were retained in the liver more efficiently than 2,3,7,8‐TCDD. Based on first order pharmacokinetic calculations, it was found that the earlier published k_e value of 0.55 for 2,3,7,8‐TCDF in the liver of the rat was also applicable. Using the same calculations for 2,3,7,8‐TCDD (k_e = 0.029) a 30% difference was found between calculated and actual measurements, but calculated results were still within the 95% confidence limits of the actual measurements.     

Real-time monitoring of nanoparticle retention in porous media

Nanoparticles are not specifically targeted in conventional treatment schemes; consequently, typical wastewater treatment systems are ineffective for nanoparticles removal. With rapidly increasing concern over their health effects, improved understanding of nanoparticle transport and retention in porous media filters is critical because of its application in new wastewater treatment methods and for assessment of the fate of the discharged nanoparticles in soil. In this study, a unique and robust integrated method is developed and validated. Experimentally, this approach uses an on-line, real-time, and in situ method for measuring nanoparticle retention dynamics, eliminating the laborious and less accurate sampling and off-line analysis. The data analysis part is a process simulator which provides both kinetic properties of the retention process as well as the overall capacity and loading. This technique is validated by application to the transport and retention of TiO₂ nanoparticles in two vastly different porous filtration media—activated carbon and sand. TiO₂ retained concentrations ranged from 0.24 to 0.37 mg g^?1 for activated carbon and 0.01–0.014 mg g^?1 for sand. The integrated method presented here is useful for both comparison of the filtration effectiveness of various porous materials as well as for process optimization and scale-up for industrial applications.     

Synthesis of SnO2 quantum dots mediated by Camellia sinensis shoots for degradation of thiamethoxam

Abstract

A novel method of synthesis of tin dioxide quantum dots employing Camellia sinensis shoots as reducing agent and stabilizer is presented. The quantum dots were characterized by UV spectroscopy, X-Ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectroscopy and transmission electron microscopy. The crystalline tin dioxide quantum dots with an average size of 4.3?nm were of flake like morphology capped by phenolic compounds of Camellia sinensis. The quantum dots were employed for the photocatalytic degradation of thiamethoxam resulting in 57% degradation within 45 mins.