Evaluation of the impact of matrix effects in LC/MS measurement on the accurate quantification of neonicotinoid pesticides in food by isotope-dilution mass spectrometry

The use of isotope-labeled internal standards is the most widely accepted approach to overcome the matrix effects on quantification of pesticides in food by LC/MS. We evaluated the impact of the matrix effects on quantification of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam, in food by using deuterated internal standards. The calibration curves for each pesticide were obtained by using matrix-free and matrix-matched calibration solutions with blank brown rice, carrot, and green onion extracts. For brown rice and carrot, the matrix effects were not observed. In contrast, the slopes of calibration curves for each pesticide were influenced by presence of green onion extracts in calibration solutions (variability of the slopes was 4–9%), because the ratios of peak area for native pesticide to those for internal standards were influenced by matrix. The spike-and-recovery test with green onion was also performed. The analytical values obtained by using matrix-free calibration solution were biased from the spiked concentration, whereas those obtained by using matrix-matched calibration solution were comparable to the spiked concentration. These results indicate that matrix-matched calibration solution should be used for accurate quantification of neonicotinoid pesticides in food by LC/MS using deuterated internal standards.     

外源褪黑素对As3+胁迫下水稻种子萌发的影响

研究添加外源褪黑素对As³⁺胁迫下水稻种子萌发及生理指标的影响。结果表明添加外源褪黑素能促进As³⁺下水稻种子的萌发,提高水稻的发芽势和发芽率,促进水稻幼苗的生长。当As³⁺浓度为100 μmol L^-1时,添加100 μmol L^-1褪黑素使水稻种子发芽率和总根长比对照分别提高57.1%和50.0%。添加褪黑素能显著提高As³⁺胁迫下水稻幼苗中抗氧化酶系统过氧化氢酶(CAT)、过氧化物酶(POD)活性和超氧化物歧化酶(SOD)的活性,并降低水稻幼芽中丙二醛(MDA)的含量。当As³⁺浓度为100 μmol L^-1时,添加50 μmol L^-1和100 μmol L^-1褪黑素导致水稻幼芽中POD活性比对照处理分别提高57.5%和114.8%,CAT活性提高29.4%和53.8%,SOD活性提高31.5%和56.0%,丙二醛含量比对照处理降低16.5%和31.9%。添加褪黑素也能显著提高As³⁺胁迫下水稻的根系活力,当As³⁺浓度为100 μmol L^-1时,50、100 μmol L^-1褪黑素处理后根系活力比对照分别提高42.4%和124.1%。说明添加外源褪黑素可缓解As³⁺胁迫对水稻的脂质过氧化损害,有效降低As对水稻内膜的破坏,显著缓解As污染对水稻的毒害作用。     

外源Mo降低As(III)和As(V)对水稻的毒性及As的积累

通过溶液培养试验,研究外源添加Mo对2种价态砷(As(III)和As(V))胁迫下水稻吸收积累Mo和As的影响。结果表明,这2种价态的As对水稻生长均有抑制作用,As(III)比As(V)对水稻毒害更明显,添加Mo可缓解As对水稻的毒害。As添加可影响水稻根系和茎叶对Mo的吸收积累,但是不同价态As对Mo积累量的影响不一致。同时,Mo的添加也可以显著地降低水稻根系和茎叶对2个价态As的吸收积累。在100 μmol?L^-1 As(III)处理下,添加0.1和0.5 mg?L^-1的Mo可导致水稻根系As积累量分别比对照处理降低38.8%和52.8%,茎叶As积累量分别降低5.1%和10.6%;当As(V)浓度为100 μmol?L^-1时,添加0.1和0.5 mg?L^-1的Mo可导致水稻根系As积累量分别比对照处理降低15.4%和62.4%,茎叶As积累量分别降低11.9%和23.7%。Mo的添加还能显著地降低2种价态As在水稻根系和茎叶中的富集系数。因此,通过施用适量的Mo肥可以用来防治农田As污染,降低As对人体健康的危害。     

禾草灵对水稻生长和典型土壤酶活性的影响

禾草灵是一种广泛使用的除草剂,在土壤中大量残留,对非靶标生物产生危害。为探究除草剂对环境生物的毒性作用,本研究模拟水稻自然生长的环境,评估禾草灵对水稻及土壤微生物的影响。研究结果表明,低浓度禾草灵(200μg·L-1)处理4d对土壤微生物量没有显著影响(P0.05);8 d时,水稻生长没有明显变化,但土壤微生物量较对照组显著升高(P0.05)。高浓度禾草灵(1 000μg·L-1)处理4 d后,土壤脲酶、酸性磷酸酶和过氧化氢酶的活性显著下降(P0.05),下降幅度分别为8.9%,16.6%和10.2%;处理8 d后,水稻幼苗鲜重显著降低(P0.05),叶绿素a和叶绿素b含量分别下降了13.5%和13.3%。本研究证实高浓度的禾草灵残留会对植物和土壤微生物产生不良的影响。     

外源Mo降低As(Ⅲ)和As(Ⅴ)对水稻的毒性及As的积累

通过溶液培养试验,研究外源添加Mo对2种价态砷(As(Ⅲ)和As(Ⅴ))胁迫下水稻吸收积累Mo和As的影响。结果表明,这2种价态的As对水稻生长均有抑制作用,As(Ⅲ)比As(Ⅴ)对水稻毒害更明显,添加Mo可缓解As对水稻的毒害。As添加可影响水稻根系和茎叶对Mo的吸收积累,但是不同价态As对Mo积累量的影响不一致。同时,Mo的添加也可以显著地降低水稻根系和茎叶对2个价态As的吸收积累。在100μmol·L~(-1)As(Ⅲ)处理下,添加0.1和0.5 mg·L~(-1)的Mo可导致水稻根系As积累量分别比对照处理降低38.8%和52.8%,茎叶As积累量分别降低5.1%和10.6%;当As(V)浓度为100μmol·L~(-1)时,添加0.1和0.5 mg·L~(-1)的Mo可导致水稻根系As积累量分别比对照处理降低15.4%和62.4%,茎叶As积累量分别降低11.9%和23.7%。Mo的添加还能显著地降低2种价态As在水稻根系和茎叶中的富集系数。因此,通过施用适量的Mo肥可以用来防治农田As污染,降低As对人体健康的危害。     

Use pattern of pesticides and their predicted mobility into shallow groundwater and surface water bodies of paddy lands in Mahaweli river basin in Sri Lanka

Pesticides applied on agricultural lands reach groundwater by leaching, and move to offsite water bodies by direct runoff, erosion and spray drift. Therefore, an assessment of the mobility of pesticides in water resources is important to safeguard such resources. Mobility of pesticides on agricultural lands of Mahaweli river basin in Sri Lanka has not been reported to date. In this context, the mobility potential of 32 pesticides on surface water and groundwater was assessed by widely used pesticide risk indicators, such as Attenuation Factor (AF) index and the Pesticide Impact Rating Index (PIRI) with some modifications. Four surface water bodies having greater than 20% land use of the catchment under agriculture, and shallow groundwater table at 3.0 m depth were selected for the risk assessment. According to AF, carbofuran, quinclorac and thiamethoxam are three most leachable pesticides having AF values 1.44 × 10^?2, 1.87 × 10^?3 and 5.70 × 10^?4, respectively. Using PIRI, offsite movement of pesticides by direct runoff was found to be greater than with the erosion of soil particles for the study area. Carbofuran and quinclorac are most mobile pesticides by direct runoff with runoff fractions of 0.01 and 0.08, respectively, at the studied area. Thiamethoxam and novaluron are the most mobile pesticides by erosion with erosion factions of 1.02 × 10^?4 and 1.05 × 10^?4, respectively. Expected pesticide residue levels in both surface and groundwater were predicted to remain below the USEPA health advisory levels, except for carbofuran, indicating that pesticide pollution is unlikely to exceed the available health guidelines in the Mahaweli river basin in Sri Lanka.     

北京地区稻田上空甲烷浓度的监测

通过对北京地区稻田种植上空甲烷浓度持续２ａ的观测发现,该地区大气中１９９２和１９９３年甲烷的年平均浓度１．１６,１．１７μｇ／Ｌ,且季节性变化规律以及年际变化规律有比较的趋势,一年中当地上空甲烷的浓度呈明显的冬春低夏秋高的趋势,且夏季甲烷浓度的变化幅度比较大。该地区甲烷浓度的日变化趋势不明显。在水稻期内的７、８月莘,稻上空甲烷浓度和水稻甲烷排放速率有密切的关系,动态分析表明,该地区大气中甲烷浓度年     

GIS支持下的广西早稻春季冷害区划研究

利用广西省90个气象台站1961-2006年气候资料和站点地理信息,建立了早稻冷害指标的空间分析模型;依托GIS软件平台,利用1:25万广西基础地理背景数据,按照1km×1km细网格推算出早稻冷害指标的空间分布;运用GIS技术划分出广西早稻低温冷害中无冷害、轻度冷害、中度冷害和严重冷害的4个区域的分区结果,并对区划结果进行了评述和建议.     

农杆菌介导的抗除草剂基因转入两系杂交稻恢复系的研究

利用农杆菌水稻高效转化系统,成功地将外源ＢＡＲ基因转入实用性两系要交稻恢复系Ｒ１８７和秀水０４,经过除草剂Ｂａｓｔａ田间涂布试验,其阳性率达到９０％以上。对转基因植株同步进行的ＰＣＲ特异扩增和总ＤＮＡ Ｓｏｕｔｈｅｒｎ检测结果也证实抗Ｂａｓｔａ的植株中含有ＢＡＲ基因。讨论了应用转ＢＡＲ基因的方法提高两系杂交水稻制种纯度的条件。图２表１参３