多壁碳纳米管固相萃取气相色谱-串联质谱法测定乌龙茶及土壤中10种三嗪类除草剂残留

建立了乌龙茶及土壤中10种三嗪类除草剂(西玛津、莠去津、扑灭津、特丁津、敌草净、环丙津、西草净、莠灭净、扑草净和特丁净)残留的气相色谱-串联质谱(GC-MS/MS)分析方法。样品经乙腈提取后,以多壁碳纳米管(MWCNTs)、N-丙基乙二胺(PSA)、C18、MgSO4为净化剂分散净化后,在GC-MS/MS多反应监测(MRM)模式下进行测定,空白基质匹配标准曲线外标法定量。研究了不同提取溶剂、不同吸附剂种类及用量对提取净化效率的影响。结果表明:在各自质量浓度范围内(西草净和扑草净在10~500 μg/kg,其余8种除草剂在5~500 μg/kg)具有良好线性关系,相关系数(r)均大于0.99,10种三嗪类除草剂的定量限(LOQ)为5.0~10 μg/kg。在5~100 μg/kg添加水平下,10种三嗪类除草剂在乌龙茶和土壤中的平均回收率在75%~111%之间,相对标准偏差(RSD)在3.1%~8.7%(n=6)之间。该方法操作简单、净化效果好、灵敏度高,具有良好的适用性,能够满足乌龙茶及土壤中10种三嗪类除草剂残留分析测定的要求。     

漩涡辅助液液微萃取和气相色谱法分析水样中甲草胺、乙草胺和丁草胺残留

采用漩涡辅助液液微萃取技术作为前处理方法,气相色谱-微池电子捕获检测器作为色谱分析仪器,建立了水样中甲草胺、乙草胺和丁草胺3种酰胺类除草剂的残留分析方法。对影响微萃取效率的各种条件进行了优化,建立的微萃取条件为:在25 mL容量瓶中,依次加入20 mL水样和50 μL甲苯,在2 800 r/min下漩涡1 min。该方法线性范围在0.02 ~5 μg/L之间,相关系数(R2)大于0.997。方法的富集倍数大于500倍。按照信噪比为3时估算的检出限在3.0~4.5 ng/L之间(纯水),方法的报告限为0.05 μg/L(自来水)和0.5 μ/L(雪水)。使用该方法进行了自来水和雪水中的添加回收试验,在0.5,0.05 μg/L添加水平,方法的添加回收率在74.2% ~96.3%之间,相对标准偏差在4.9% ~ 12.1%之间。     

漂浮固化分散液-液微萃取-气相色谱法测定液态奶中5种拟除虫菊酯类农药残留

建立了漂浮固化分散液-液微萃取（DLLME-SFO）-气相色谱配电子捕获检测器（GCECD）,同时测定液态奶中甲氰菊酯、氟氯氰菊酯、氯氟氰菊酯、氰戊菊酯和溴氰菊酯5种拟除虫菊酯类农药的分析方法。样品经预处理后,加入25 μL十六烷（萃取剂）、600 μL丙酮（分散剂）及质量分数为6%的氯化钠,涡旋3 min,于–5℃、10 000 r/min下离心3 min后,去除水相,融化后经气相色谱测定。结果表明:在5.0～250.0 μg/kg范围内,5种拟除虫菊酯类农药的峰面积与相应的质量浓度间呈良好的线性关系,相关系数均大于0.999 0;在5～20 μg/kg添加水平下,平均回收率为90%～104%,日内相对标准偏差均低于5.9%（n=6）,日间相对标准偏差均低于7.8%（n=3）; 5种农药在液态奶中的检出限为0.75～2.17 μg/kg,定量限为2.52～7.22 μg/kg。该方法操作简便、溶剂用量少、定量准确、重现性好,适用于液态奶样品中拟除虫菊酯类农药残留分析。     

特丁津与扑草净、莠去津活性比较

温室盆栽条件下,以扑苹净、莠去津分别为对照药剂,研究了特丁津对马唐（Digitaria sanguinalis）、反枝苋（Amaranthus retroflexus）、马齿苋（Portulaca olercea）和稗草（Echinochloa crus-galli）的除草活性。结果表明：3种除草对阔叶杂草的防效都优于对禾本科杂草的防效．特丁津对马唐、稗草、反枝苋、马齿苋4种杂草的防治效果都高于莠去津和扑草净。     

丁香假单胞菌发酵液中的冠菌素含量测定方法及其应用

为了辅助提高工程菌种改良的效率,建立了一种简单、快速、高效的分散液-液微萃取-高效液相色谱检测丁香假单胞菌发酵液中冠菌素的分析方法。优化了蛋白沉淀法、萃取剂的种类和体积、分散剂的种类和体积、萃取时间和离心强度等对萃取率的影响。确定最优萃取条件为:以2.0 mL丙酮作为分散剂,以400 μL氯苯为萃取剂,萃取5 min,在5 000 r/min下离心5 min。高效液相色谱的检测条件为:流动相为V (甲醇) : V (0.5%乙酸水溶液) = 70 : 30,等梯度洗脱,流速1.0 mL/min,柱温30 ℃,检测波长220 nm。在3.2~100 mg/L范围内,冠菌素的峰面积与其质量浓度间呈良好的线性关系,相关系数 (r) 为0.999 8。方法的检出限为2.1 mg/L,定量限为6.5 mg/L。在6.5、25和100 mg/L添加水平下,冠菌素在丁香假单胞菌发酵液中的回收率在95%~98%之间,相对标准偏差 (n = 5) 在2.7%~5.1%之间。该方法可用于丁香假单胞菌发酵液中冠菌素含量的测定。     

液液萃取-气相色谱法测定水体中的45种有机氯和菊酯类农药残留

本文研究了液液萃取-气相色谱方法测定水体中有机氯和菊酯类农药残留的方法。用环己烷从水体中提取净化45种农药残留,运用GC-ECD进行分析。用外标法定量,加标浓度分别为0.005,0.05,0.1μg/mL时,回收率在70.36~114.96%之间,相对偏差≤10%。方法检出下限为0.001~0.005μg/mL,用该方法可实现对水体中农药残留的检测。     

气相色谱-串联质谱法测定葵花籽中28种农药残留

建立了气相色谱-串联质谱(GC-MS/MS)测定葵花籽中咯菌腈、氯氰菊酯、异丙甲草胺等28种农药残留的方法。样品经乙腈提取,凝胶渗透色谱(GPC)及固相萃取(SPE)净化,GCMS/MS测定,多反应监测模式(MRM)分析,外标法定量。结果表明:采用凝胶渗透色谱及固相萃取净化可有效排除大部分干扰成分;在0.01~0.5 mg/L范围内,28种农药的峰面积与对应的质量浓度间呈良好的线性关系,决定系数R2>0.994;在50、100和200 μg/kg 3个添加水平下,各农药的平均回收率在74%~120%之间,相对标准偏差在0.9%~9.5% (n=5)之间,定量限在0.2~7.6 μg/kg之间。该方法灵敏、准确、可靠,能满足农药残留检测的要求,可用于监测葵花籽生产过程中的农药残留。     

分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留

土壤中烟嘧磺隆和莠去津的高残留往往会导致后茬大豆药害问题。本研究建立了一种分散固相萃取-超高效液相色谱-串联质谱法同时检测大豆植株及土壤中烟嘧磺隆、莠去津及其代谢物残留方法。样品经含2%甲酸的乙腈提取, 经分散固相萃取净化, 以乙腈和0.2%甲酸水为流动相, 采用Poroshell 120 EC-C18色谱柱梯度洗脱, 基质匹配标准曲线外标法定量分析。结果表明:在0.01、0.10 mg/kg和1.00 mg/kg添加水平下, 烟嘧磺隆、莠去津及其代谢物的平均回收率为70%~113%, 相对标准偏差为0.3%~11.8%, 目标化合物质量浓度与对应的峰面积之间在0.001~1 mg/kg范围内线性关系良好, 决定系数R2≥0.984 1, 方法的定量限为0.01 mg/kg。该方法简便、快捷、准确, 适用于土壤和幼苗期至鼓粒期大豆植株中烟嘧磺隆、莠去津及其代谢物的检测。本研究为烟嘧磺隆和莠去津的科学使用及后茬作物的安全种植提供有效监测方法。     

超高效液相色谱-串联质谱法测定水体中烟嘧磺隆·乙草胺·莠去津

采用超高效液相色谱-串联质谱法建立了同时检测水体中烟嘧磺隆、乙草胺、莠去津的分析方法。以乙腈和0.2%甲酸水为流动相进行液相分离,ESI~+模式下进行多离子反应监测扫描。结果表明,在浓度为0.001~1mg/L范围线性关系良好,烟嘧磺隆、乙草胺、莠去津线性相关系数分别为0.9999、1.0000、1.0000,平均回收率分别为91.69%~94.61%、89.22%~90.95%、91.47%~91.62%,变异系数分别为1.56%、1.18%、1.22%。     

500g/L特丁噻草隆悬浮剂防治甘蔗地杂草田间试验

试验结果表明,用特丁噻草隆SC对甘蔗地进行封闭性除草,用量200g/667m2,整个生育期只喷药1次,药后70d防治效果仍达到90％,明显优于对照药乙草胺EC 200g/667m2和莠去津SC 200g/667m2,是乙草胺、莠去津等进行甘蔗地封闭性除草的理想替代药剂.     

Transport to ground‐water of six commonly used herbicides: a prediction for two Italian scenarios

In Italy suitable standard scenarios for pesticide risk assessment based on computer models are lacking. In this paper we examine the use of the VARLEACH model to assess the potential danger of ground‐water pollution by six herbicides (alachlor, atrazine, cyanazine, linuron, simazine and terbuthylazine) which are used to protect irrigated (maize) and non‐irrigated (sorghum) crops in the Po Plain, one of the most important agricultural lands in Italy. Two extreme scenarios are taken: real worst case (sandy soil) and real best case (clay loam soil). The simulation suggests that cyanazine, linuron and terbuthylazine can be safely used in clay loam soil in both non‐irrigated and irrigated crops, while alachlor, atrazine and simazine can be safely used only in non‐irrigated crops. On the other hand, the application of all the herbicides tested should be avoided in sandy soil, with the exception of linuron in non‐irrigated crops. © 2000 Society of Chemical Industry     

Reduced rates of residual and post-emergence herbicides for weed control in vineyards

In 1997 and 1998, five field studies were conducted at four Portuguese wine‐growing regions in order to evaluate the effectiveness of the chemical control of vineyard weeds under Mediterranean conditions using either reduced doses of residual herbicides or only foliar herbicides. Amitrole (3440 g a.i. ha^?1), amitrole + glyphosate mono‐ammonium salt (1720 + 900 g a.i. ha^?1), amitrole (3400 g a.i. ha^?1), amitrole + diuron (2580 + 1500 g a.i. ha^?1), amitrole + simazine (2580 + 1500 g a.i. ha^?1), amitrole + terbuthylazine (2580 + 1500 g a.i. ha^?1) and amitrole + diuron + simazine (2580 + 1300 + 1400 g a.i. ha^?1) were assayed and compared with the following reference herbicides: glyphosate isopropylamine salt (1800 g a.i. ha^?1), amitrole + diuron (2520 + 1680 g a.i. ha^?1), diuron + glyphosate + terbuthylazine (1275 + 900 + 1425 g a.i. ha^?1), amitrole + simazine (1900 + 3900 g a.i. ha^?1) and glyphosate + simazine (800 + 2200 g a.i. ha^?1). The herbicides were applied during late winter. The results indicated that good control was achieved by the application of foliar herbicides alone or of reduced rates of a mixture of residual herbicides with foliar herbicides for at least 2 months. Three months after application, the efficacy of post‐emergence herbicides and lower rates of residual herbicides decreased significantly in clay soils and under heavy rainfall conditions. Convolvulus arvensis– a weed that is becoming increasingly significant in Portuguese vineyards – was poorly controlled, even when glyphosate was used. Despite this, it can be assumed that in those regions in which the trials were conducted, it is possible to employ weed control strategies that entail the elimination or a reduction in the rate of residual herbicides.     

气相色谱-串联质谱法测定西瓜和黄瓜中吡唑萘菌胺及其代谢物残留

基于分散固相萃取与气相色谱-串联质谱建立了快速检测西瓜和黄瓜中吡唑萘菌胺及其代谢物残留的分析方法。样品经乙腈提取,N-丙基乙二胺 (PSA) 和C₁₈净化,气相色谱-串联质谱 (GC-MS/MS) 测定,多反应检测模式 (MRM) 分析,内标法定量。考察了提取溶剂及吸附剂种类对分析结果的影响,优化了气相色谱-质谱条件。结果表明:在1~500 μg/L范围内,吡唑萘菌胺及其代谢物的质量浓度与对应的峰面积间均呈良好的线性关系,相关系数 (r) 为0.994 3~0.999 9。在0.01、0.1和1 mg/kg 3个添加水平下,吡唑萘菌胺及其代谢物在西瓜中的平均回收率为70%~105%,相对标准偏差 (RSD,n = 5) 为3.4%~13%;在黄瓜中的添加回收率为82%~104%,相对标准偏差 (RSD,n = 5) 为1.3%~9.3%。吡唑萘菌胺及其代谢物的定量限 (LOQ,S/N = 10) 为0.3~0.6 μg/kg,检出限 (LOD,S/N = 3) 为0.1~0.2 ng。该方法简单、高效、快速,满足残留分析的要求,适用于西瓜、黄瓜中吡唑萘菌胺及其代谢物残留的快速检测。     

Triazine herbicide residues in central European streams

Triazine herbicide residues were monitored in the rivers Adour, Danube, Garonne, Herault, Loire, Marne, Oise, Rhine, and Rh?ne from spring 1976 to fall 1977 to determine whether the continued use of the compounds resulted in accumulations of undesirable residues in the streams. Samples were generally collected monthly or bimonthly and analyzed for the parent compounds atrazine, simazine, terbumeton, terbuthylazine, and dealkylated metabolites GS 26571 (2-amino-4-etert-butylamino-6-methoxy-1,3,5-triazine) and G 30033 (2-amino-4-chloro-6-ethylamino-1,3,5-triazine). The compounds were extracted into dichloromethane and quantitated by gas chromatography (GC) with nitrogen-specific detection. Selected results were verified by GC with mass fragmentographic detection. Limit of detection was usually 0.4 mg/m3; 80 percent of all results were below 0.4 mg/m3, 14 percent were 0.4-1 mg/m3, 6 percent were 1-10 mg/m3, and 0.3 percent were higher than 10 mg/m3. Detectable residues were mainly atrazine from the downstream sampling sites. Residues usually peaked during June.     

Survey of herbicide residues in soil and wells in three citrus orchards in Valencia, Spain

Soil samples taken in summer 1989 and winter 1990 at different depths from three citrus orchards of the Valencia region (Spain) with a long history of residual herbicide treatments were analysed with bioassays and chromatographic procedures. The herbicides involved were atrazine, bromacil, diuron, simazine, terbuthylazine, terbumetone, terbutryn and trifluralin. Water samples from wells in the orchards were also analysed. The concentrations of the herbicides were very low, often below the limit of determination, and were always highest in the upper layers of soil. After a very unusual period of heavy rain, small quantities of some chemicals were found in the well water. The conclusion was that in these orchards the herbicides applied at currently used rates are unlikely to accumulate in any layers of the soil.     

Increased herbicidal activity of triazine herbicides by piperonyl butoxide

Piperonyl butoxide (PB) is a known Synergist which enhances the activity of insecticides by inhibiting their biotransformation to less active products. We have evaluated the possible use of PB as a herbicide synergist using triazine herbicides in sensitive, tolerant, and resistant plants. The effects of PB, triazine herbicides, and their combinations were examined in whole plants as well as in chloroplasts isolated from triazine-sensitive (S) and -resistant (R) weed biotypes. PB itself, applied postemergence (0.1–0.5%, v/v), was slightly toxic to the plants tested. However, foliar application of PB combined with atrazine, terbutryn or prometryn to maize seedlings significantly increased the phytotoxicity of the herbicides. Low rates of atrazine, prometryn, and terbutryn in a tank-mixture with PB, effectively controlled Solatium nigrum L. and Abutilon theophrasli Medik. PB enhanced atrazine efficacy in both S and R biotypes of Lolium rigidum Gaud. The synergistic effect of PB was evident also in vitro when atrazine and methabenzthiazuron were used to inhibit photosystem II electron transport in chloroplasts isolated from resistant weeds. These data demonstrate the potential of PB as a herbicide synergist and its possible utilization as an aid for improving the activity of triazine herbicides in sensitive, tolerant and resistant plants.