溴苯腈在土壤及水中残留分析方法的研究

本文研究建立了溴苯腈在土壤及水中的残留测定方法。研究了溴苯腈在土壤及水中残留分析的不同检测法、提取净化法,比较了不同提取溶剂和提取次数对水中溴苯腈残留的提取效果及索氏提取法、振荡提取法和超声-微波协同萃取法对土壤中溴苯腈残留的提取效果。结果表明,溴苯腈在土壤及水中的残留测定适合采用高效液相色谱法;确立了溴苯腈在水中的残留测定方法为正己烷作萃取溶剂,液-液分配萃取2次,用高效液相色谱测定。当溴苯腈在水中的添加浓度为0.10～1.00mg·L-1时,标准添加回收率为98.7%～111.1%、变异系数为0.80%～7.85%;溴苯腈在土壤中残留分析的3种提取方法均能达到农药残留分析的要求,通过比较不同提取时间和溶剂用量的提取效果,最终确定了溴苯腈在土壤中的残留分析方法为用丙酮∶水∶冰乙酸=80∶18∶2(V∶V∶V)经振荡提取或超声-微波协同萃取,再经液-液分配净化,最后用高效液相色谱测定。当溴苯腈在土壤中的添加浓度为0.05～5.00mg·kg-1时,振荡提取法相应的标准添加回收率为90.9%～102.0%、变异系数为0.08%～18.44%,超声-微波协同萃取法相应的标准添加回收率为95.6%～109.4%、变异系数为0.18%～16.01%,均符合农药残留分析的要求。     

Use of a potentiometric vital dye to determine the effect of the herbicide bromoxynil octanoate on mitochondrial bioenenergetics in Chlamydomonas reinhardtii

BACKGROUND: The aims of the present study were to validate a vital mitochondrial potentiometric staining method in Chlamydomonas reinhardtii and to utilise this method to examine the effect of the herbicide bromoxynil octanoate on mitochondrial potential in this species. A range of stains was investigated, including Rhodamine 123, DASPMI, Mitotracker Green, Mitotracker Orange and JC‐1. RESULTS: Rhodamine 123 (R123) had the highest utility of several candidate stains. Incubation with both 5 and 10 µM carbonyl cyanide 3‐chlorophenylhydrazone caused significant fluorescence collapse [Dunn's post test (40.00, P < 0.01) and (45.49, P < 0.01) respectively], demonstrating that the R123 fluorescence reported mitochondrial potential. The effect of the herbicide bromoxynil octanoate was examined. Exposure to 0.1 mM of bromoxynil resulted in a significant increased mitochondrial fluorescence compared with the baseline (Mann–Whitney U = 222, P < 0.002), while concentrations of 1 mM and greater resulted in significant, almost complete loss of mitochondrial potential [mean fluorescence ratio = 1.193–1.289 (where a ratio of 1 represents total potential loss), Mann–Whitney U = 0.0, P < 0.001 (1 mM ), 0.0, P < 0.0001 (2 mM ), 0.0, P < 0.0001 (5 mM )]. EC₅₀ of the collapse in mitochondrial potential owing to bromoxynil incubation occurred at 0.72 mM , and the mean t₅₀ of bromoxynil octanoate action was 93 s. CONCLUSIONS: R123 is a sensitive potentiometric dye in C. reinhardtii that may find further use in investigations of both mitochondrial bioenergetics in plants and environmental toxicology. Copyright © 2011 Society of Chemical Industry     

Communication to the Editor Degradation of Bromoxynil,Ioxynil, Dichlobenil and their Mixtures by Agrobacterium radiobacter 8/4

Degradation of three benzonitrile herbicides, bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), ioxynil (3,5-diiodo-4-hydroxybenzonitrile), dichlobenil (2,6-dichlorobenzonitrile), and their mixtures by the soil micro-organism Agrobacterium radiobacter 8/4 was studied in batch cultures. Bromoxynil was found to be most rapidly degraded, while dichlobenil had the lowest toxicity to our strain. All transformations of studied benzonitriles were performed by the nitrile hydratase which has been shown to act on a broad range of substituted aromatic nitriles. © 1997 SCI.     

Demonstrating formation of potentially persistent transformation products from the herbicides bromoxynil and ioxynil using liquid chromatography-tandem mass spectrometry (LC-MS/MS)

It is shown that potentially persistent transformation products can be formed from the herbicides bromoxynil (3,5-dibromo-4-hydroxybenzonitrile) and ioxynil (3,5-diiodo-4-hydroxybenzonitrile), and possible leaching to groundwater is discussed. A similar process to the formation of BAM (2,6-dichlorobenzamide) from the herbicide dichlobenil (2,6-dichlorobenzonitrile) can be anticipated as bromoxynil and ioxynil are analogues of dichlobenil and they are degraded by the enzymes nitrilase, nitrile hydratase and amidase. A biodegradation study using cultured Variovorax sp. DSM 11402, a species commonly found in soil, demonstrated that ioxynil and bromoxynil were fully transformed into their corresponding amides in 2-5 days. These amides were not further degraded within 18 days, and formation of other degradation products was not observed. These results are in agreement with biodegradation experiments with dichlobenil. In soil, dichlobenil is transformed into its only observed degradation product BAM, which is persistent and mobile, and has been found in 19% of 5000 samples of Danish groundwater. Variovorax sp. is known to degrade the non-halogenated analogue benzamide, suggesting that degradation of the three amides may be hindered by the halogenated substituents (meta-Br; meta-I; ortho-Cl). This hypothesis is supported by QSAR modelling of fundamental properties. Using a new optimised liquid chromatography-tandem mass spectrometry (LC-MS/MS) method, the sorption and desorption properties of bromoxynil and ioxynil were characterised in sandy topsoil at four concentration levels. The estimated sorption coefficient K(d) was 1.4 L kg(-1) for bromoxynil and 5.4 L kg(-1) for ioxynil, indicating weak to moderate sorption to topsoil. Desorption of the herbicides showed that they were strongly and irreversible bound to the soil (K(des) > K(d)). The amount of herbicide desorbed depended on the initial concentration level. At low levels, K(des) values were higher, indicating stronger binding than at higher levels. The isocratic LC-MS/MS method developed for simultaneous detection of bromoxynil, ioxynil and their main degradation products is described. Using negative electrospray ionisation (ESI-), the detection limits were 0.4-1.0 microg L(-1), with relative standard deviations of 4-10% (n = 10) using direct injection without clean-up steps. The standard curves showed linearity in the range 5-100 microg L(-1) with r(2) > 0.992.     

辛酸蔗糖酯的合成与杀虫活性研究

该文以无水碳酸钾为催化剂,低毒的二甲基亚砜为溶剂,采用酯交换法在减压条件下高效合成了一类新型绿色杀虫剂——辛酸蔗糖酯,并针对其合成条件进行了初步的优化.通过单因子实验得到合成辛酸蔗糖酯最佳条件为:蔗糖与辛酸乙酯的投料摩尔比2∶1,反应温度95～100℃,反应时间5 h,催化剂用量（占辛酸乙酯质量分数）16%,反应绝对压力11 kPa,产率为79.11%.所得产物经柱色谱分离、质谱表征,以及傅立叶红外光谱分析,确定分离得到的为辛酸蔗糖单酯、二酯和三酯.合成的辛酸蔗糖酯、分离得到的单酯、二酯和三酯分别对舞毒蛾1龄幼虫进行杀虫实验,单酯的杀虫活性为最高;对农业害虫大豆蚜虫的室内防治实验,在施药5 d后,高浓度处理的校正虫口减退率在80%左右,证明了产物具有一定的杀虫活性.      

茉莉酸甲酯对‘小白玫瑰’和‘玫瑰香’葡萄酒香气的影响

为提高麝香葡萄酒中萜烯类物质的含量,从而提高葡萄酒的香气质量,本研究以‘小白玫瑰’‘玫瑰香’2种麝香葡萄为材料,于转色期在葡萄果实表面喷施10 mmol/L茉莉酸甲酯（Methyl jasmonate,MeJA）,成熟后采收、酿酒,测定葡萄酒的基本理化指标,并用气相色谱-质谱联用仪分析MeJA对葡萄酒香气物质的影响。结果表明：MeJA处理后‘小白玫瑰’‘玫瑰香’葡萄酒中总酸含量、酒精度和总酚含量均显著增加;在处理组和对照组酒样中共检测出39种挥发性物质,处理组酒样中醇类、酯类、萜烯类物质的含量以及香气物质总量均显著增加;酒样中共有的且气味活性值（Odor activity value,OAV）值大于1的香气物质包括丁酸乙酯、乙酸异戊酯、辛酸乙酯和芳樟醇,这些物质是麝香型葡萄酒的主要特征香气物质,其中辛酸乙酯的OAV值最大,对葡萄酒香气贡献最大。在MeJA处理后,‘小白玫瑰’葡萄酒的花香明显提升,贡献突出的是丁酸乙酯、己酸丁酯、己酸乙酯、芳樟醇、反式-β-罗勒烯和香叶醇,‘玫瑰香’葡萄酒的果香明显提升,贡献突出的是癸酸乙酯、乙酸异戊酯、β-月桂烯、D-柠檬烯和香茅醇。综上,MeJA处理麝香葡萄果实可提高葡萄酒中香气物质含量,使葡萄酒的花香和果香更明显,本研究可为提高麝香葡萄酒的品质提供理论依据。     

喹草酮与辛酰溴苯腈复配应用于小麦田的除草效果及对小麦的安全性

为明确新型除草剂喹草酮应用于小麦田的除草效果及对小麦的安全性,在温室内采用共毒系数法对喹草酮与辛酰溴苯腈联合作用进行测定,并验证喹草酮与辛酰溴苯腈两者混用以及与双氟磺草胺三者混用时对小麦田杂草的防效,以及对小麦的安全性。温室试验结果表明,喹草酮对阿拉伯婆婆纳Veronica persica防效优,试验剂量下全部死亡,对播娘蒿Descurainia sophia和麦家公Lithospermum arvense的GR₅₀分别为12.67 g (a.i.)/hm²和152.99 g (a.i.)/hm²;辛酰溴苯腈对播娘蒿和麦家公防效优,其GR₅₀分别为26.22 g (a.i.)/hm²和13.36 g (a.i.)/hm²,对阿拉伯婆婆纳防效略差,GR₅₀为85.12 g (a.i.)/hm²。喹草酮与辛酰溴苯腈按有效成分用量1∶1～1∶2.5配比时,阿拉伯婆婆纳全部死亡,对播娘蒿的共毒系数在140.34～202....     

Impacts of long-term application of buctril super (bromoxynil) herbicide on microbial population,enzymes activity,nitrate nitrogen,Olsen-P and total organic carbon in soil

Long-term impact of buctril super (bromoxynil) herbicide in the wheat fields on soil microbial population, nitrate-N, Olsen-P, total organic carbon (TOC) and enzyme activities was evaluated in 18 sites in Pakistan. Nine sites were randomly selected from those places where bromoxynil herbicide had been used for the last 10 years designated as soil ‘X’ and other nine where no herbicide was used in that period designated as soil ‘Y’. Very importantly, it was found that long-term application of this herbicide in wheat fields reduced the actinomycetes and fungi population up to 19.7 and 14.3%, respectively, urease and dehydrogenase activity by 17.5 and 28.2%, respectively, and reduced nitrate-N, Olsen-P and TOC up to 55, 17 and 28.57%, respectively. Presence of high clay and organic matter contents enhanced the detrimental effect of herbicide by prolonging its persistence as compared to light-textured soils with low organic matter. As in Pakistan this herbicide is being used most frequently in wheat fields, data are scarce on the long-term effect of this herbicide on soil microbial activities and soil health. These findings could give new insights about the use of alternate herbicide in wheat fields, particularly in clay-textured and high organic matter contained soils for maintaining soil health.     

A psbA mutation in Kochia scoparia (L) Schrad from railroad rights-of-way with resistance to diuron, tebuthiuron and metribuzin

Kochia [Kochia scoparia (L) Schrad] has become resistant to many herbicides used in cropland and railroad rights-of-way in North Dakota and Minnesota. Kochia scoparia plants that had survived annual treatments with diuron and tebuthiuron were sampled along railroad rights-of-way in North Dakota and Minnesota. The samples were screened in the greenhouse for resistance to diuron, tebuthiuron, metribuzin and bromoxynil from 0.5x to 32x the recommended use rates. A resistant K scoparia accession (MN-3R) was confirmed with resistance up to 16-fold higher than recommended use rates for tebuthiuron and diuron and up to 4-fold higher for metribuzin. However, the resistant K scoparia accession was susceptible to bromoxynil even at 50% of the recommended use rate. The herbicide binding region of the psbA gene fragment of eight resistant (R) and seven susceptible (S) K scoparia accessions was PCR-amplified and sequenced for detection of mutations. The psbA gene of four R K scoparia accessions was mutated at residue 219 with substitution of isoleucine for valine (GenBank accession number AY251265). The seven S K scoparia accession sequences were wild-type at this residue (GenBank accession number AY251266). The other four R accessions sequences showed a previously known triazine R mutation with substitution of glycine for serine at residue 264. All 15 K scoparia accessions were wild-type at all other psbA residues within the region analyzed. Resistance to diuron, tebuthiuron and metribuzin among the railroad rights-of-way K scoparia is probably due to the mutation at residue 219 of the psbA gene in some plants, but due to the previously reported Ser(264)Gly substitution in other plants. Target-site resistance associated with a change of valine to isoleucine at residue 219 of the psbA target-site in weeds has previously been reported for Poa annua L selected in diuron-treated grass seed fields, and for Amaranthus powelli S Wats selected in linuron-treated carrot fields. This is the first report of the mutation in herbicide-resistant K scoparia.