氟唑磺隆、甲基二磺隆、炔草酯和炔草酸在小麦中的残留分析

以QuEChERS前处理方法为基础,采用高效液相色谱-串联质谱(HPLC-MS/MS)检测技术,建立了除草剂氟唑磺隆、甲基二磺隆、炔草酯及其代谢物炔草酸4种化合物在小麦中残留的分析方法。麦粒样品中加入5 mL体积分数为0.1%的甲酸水溶液后,以10 mL乙腈提取,用50 mg C₁₈与100 mg 无水硫酸镁净化;麦秆样品中加入10 mL体积分数为2%的甲酸水溶液后,以10 mL乙腈提取,用100 mg C₁₈与200 mg无水硫酸镁净化。结果表明:氟唑磺隆在0.005、0.01和0.1 mg/kg,甲基二磺隆在0.01、0.02和0.1 mg/kg,炔草酯和炔草酸在0.05、0.1和0.5 mg/kg添加水平下,4种化合物在麦粒中的回收率在76%~97%之间,在麦秆中的回收率在83%~102%之间,相对标准偏差均小于10%,r > 0.99。4种化合物在麦粒和麦秆中的定量限分别为:氟唑磺隆0.005 mg/kg,甲基二磺隆0.01 mg/kg,炔草酯和炔草酸均为0.05 mg/kg。该方法可满足小麦样品中4种化合物的残留分析要求。     

高效液相色谱-串联质谱法测定小麦和土壤中氨氯吡啶酸的残留量

建立了小麦植株、麦粒、面粉、麦麸和土壤样品中氨氯吡啶酸的高效液相色谱-串联质谱(HPLC-MS/MS)检测方法。样品用丙酮提取,经N-丙基乙二胺(primary secondary amine,PSA)串联石墨化炭黑柱净化,以Agilent ZORBAX SB-C18 色谱柱分离,以电喷雾电离串联质谱正离子多反应监测(multiple reaction monitoring,MRM)模式进行测定。结果表明: 在0.01、0.1、0.5、1 mg/kg 4个添加水平下,氨氯吡啶酸在小麦植株、麦粒、面粉、麦麸和土壤中的平均回收率在78.9%~97.9%之间,相对标准偏差在3.6%~9.6%之间。该方法样品前处理简单、快速、分析时间短,灵敏度、准确度和精密度均符合农药残留检测要求,适用于小麦和土壤中氨氯吡啶酸残留的检测。     

氯溴异氰尿酸在烟叶及其土壤中的残留分析及消解动态

建立了烟叶及其土壤中氯溴异氰尿酸残留的检测方法,并测定了氯溴异氰尿酸在烟叶及其土壤中的消解动态和最终残留。样品经乙腈提取,三氯甲烷、石油醚萃取后,采用高效液相色谱(HPLC-UV)检测。结果表明:在0.01~0.5 mg/kg添加水平下,氯溴异氰尿酸在鲜烟叶、干烟叶和土壤中的平均回收率分别为82.7% ~91.6%、89.2% ~91.8%和89.2% ~94.4%,相对标准偏差(RSD)分别为1.1% ~3.9%、2.6% ~5.5%和1.5% ~4.6%,方法的检出限(LOD)均为0.003 mg/kg, 定量限(LOQ)均为0.01 mg/kg。田间消解动态结果表明,氯溴异氰尿酸在烟叶及其土壤中消解较快,半衰期分别为3.94~4.25 d和2.83~3.41d,施药后14d,其在烟叶和土壤中的消解率均达90%以上。氯溴异氰尿酸可湿性粉剂按有效成分600 g/hm2(推荐高剂量)和900 g/hm2(1.5倍推荐高剂量)于烟草现蕾期对水喷雾施药3~4次,距末次施药后间隔21d采样,烟叶中氯溴异氰尿酸的残留量为1.47~3.52 mg/kg,土壤中的残留量为未检出~0.43 mg/kg。     

高效液相色谱法测定糙米和土壤中6种杀虫剂的残留

建立了糙米和土壤中氟啶虫酰胺、氯虫苯甲酰胺、甲氧虫酰肼、氟虫双酰胺、虫螨腈和虱螨脲6种杀虫剂残留的高效液相色谱检测方法。样品用乙腈浸泡过夜后振荡提取,其中糙米过氨基小柱净化,土壤无需净化;采用高效液相色谱仪,以甲醇-乙腈-水为流动相,利用C18柱和二极管阵列检测器(检测波长:265、254、230 nm)对待测组分进行分离和测定。结果表明,在0.05~5 mg/L范围内,标准品质量浓度与峰面积之间呈良好的线性关系(R2=0.999 4~1)。在0.1、0.5和1 mg/kg 3个添加水平下,糙米和土壤中氟啶虫酰胺、氯虫苯甲酰胺、甲氧虫酰肼、氟虫双酰胺、虫螨腈和虱螨脲的平均回收率在84.5%~113.2%之间,相对标准偏差(RSD)≤9.3%;供试6种农药在样品中的检出限(LOD)为0.010~0.016 mg/kg,定量限(LOQ)为0.03~0.05 mg/kg。所建 立的方法具有准确、快速、简便、重复性好等特点,其准确度和精密度均能满足农药残留分析的要求。     

碱解法—液质联用测定小麦中2甲4氯异辛酯及其代谢物2甲4氯

本研究采用QuECHERS及碱解衍生技术，结合高效液相色谱-串联质谱法(HPLC-MS/MS)建立了测定小麦籽粒和秸秆中的2甲4氯异辛酯和其代谢产物2甲4氯及其共轭物的残留量的检测方法。籽粒和秸秆样品经0.1%甲酸乙腈提取，0.25 mol/L的氢氧化钠溶液碱解，1 mol/L盐酸酸化，上清液经固相萃取剂净化后，HPLC-MS/MS上机检测。结果显示2甲4氯异辛酯在籽粒和秸秆添加浓度0.02～5 mg/kg的范围内，回收率范围为86%～96%,相对标准偏差为2.1%～5.6%,2甲4氯在籽粒和秸秆添加浓度0.02～5 mg/kg的范围内，回收率范围为94%～106%,相对标准偏差范围为3.0%～6.3%,籽粒和秸秆的方法定量限均为0.02 mg/kg。该方法试剂和材料易得，操作过程简单快捷，回收率及精密度满足农药残留分析要求，可用于实际样品的2甲4氯异辛酯、2甲4氯及其共轭物的残留检测，便于2甲4氯异辛酯在小麦的膳食风险评估。     

QuEChERS-高效液相色谱-串联质谱法测定主要谷物和油料作物中氯虫苯甲酰胺的残留

采用QuEChERS样品前处理方法,建立了主要谷物和油料作物产品 (糙米、小麦、玉米和大豆) 中氯虫苯甲酰胺残留量的高效液相色谱-串联质谱 (HPLC-MS/MS) 检测方法。样品经乙腈-水提取及盐析处理后,用N-丙基乙二胺 (PSA) 和石墨化碳黑 (GCB) 固相萃取填料净化,高效液相色谱-串联质谱(HPLC-MS/MS)、多反应监测模式 (MRM) 下测定。基质标准曲线外标法定量。结果表明:在0.005~0.5 mg/L范围内,不同样品基质中氯虫苯甲酰胺的峰面积与其相应的质量浓度间均有良好的线性关系(R2>0.99),检出限 (LOD) 为0.001 mg/L。在0.02、0.05、0.1和0.5 mg/kg添加水平下,氯虫苯甲酰胺在4种基质中的平均回收率在89%~114%之间,相对标准偏差 (RSD) 在1.3%~11% (n = 5) 之间,4种基质中的最低检测浓度 (LOQ) 均为0.02 mg/kg。该方法适用于主要谷物和油料作物产品中氯虫苯甲酰胺残留量的检测。     

浓硫酸净化-气相色谱法检测茶叶中α-硫丹和拟除虫菊酯类农药残留

建立了一种茶叶中硫丹和5种拟除虫菊酯类农药(联苯菊酯、高效氯氟氰菊酯、氯氰菊酯、溴氰菊酯和氰戊菊酯)残留分析的新方法。样品以乙腈提取,浓硫酸-乙醇净化,毛细管柱气相色谱法(GC-ECD)测定。结果表明:在0.005～0.5 mg/kg添加水平内,4种茶叶样品中α-硫丹和5种拟除虫菊酯农药的添加回收率在81.6%～105.9%之间,相对标准偏差(RSD)为0.52%～13.0%(n=3)。α-硫丹和5种拟除虫菊酯农药在4种茶叶中的定量限(LOQ)均为0.005 mg/kg。本方法杂质干扰少,准确度及灵敏度满足农药残留检测要求,对检测硬件要求低,适用于茶叶中α-硫丹及拟除虫菊酯类农药残留的分析。     

超高效液相色谱-串联质谱法同时测定玉米及土壤中烟嘧磺隆和2甲4氯残留

采用分散固相萃取法进行样品前处理,建立了超高效液相色谱-电喷雾串联四极杆质谱(UPLC-MS/MS)同时快速检测玉米及其土壤中烟嘧磺隆和2甲4氯残留的方法。样品经乙腈-甲酸[V(乙腈):V(甲酸)=99.9:0.1]提取,C18基质固相分散(DSPE)净化后,采用UPLC-MS/MS、多反应监测模式(MRM)检测,外标法定量。结果显示,烟嘧磺隆和2甲4氯进样质量浓度与峰面积间线性关系良好,在0.005～0.1 mg/kg添加水平范围内,烟嘧磺隆和2甲4氯在不同基质中的平均回收率分别为74.6%～98.0%和81.3%～100.1%,相对标准偏差(RSD)分别为1.1%～3.4%和1.7%～10.5%,定量限(LOQ)均为0.005 mg/kg。     

气相色谱法同时测定水果中毒死蜱、苯醚甲环唑和哒螨灵的残留

建立了同时测定水果中毒死蜱、苯醚甲环唑和哒螨灵残留的气相色谱(GC/ECD)分析方法。样品经乙腈提取,氨基固相萃取小柱净化,GC/ECD检测,外标法定量。结果表明:在0.02~1 mg/L范围内,3种供试农药的线性相关系数均大于0.99,检出限(LOD)为0.006~0.007 mg/kg,定量限(LOQ)为0.02 mg/kg;在0.02、0.05和0.1 mg/kg 3个添加水平下,平均回收率在78%~108%之间,相对标准偏差(RSD)为2.9%~16%。该方法适用于水果中毒死蜱、苯醚甲环唑和哒螨灵的检测。     

超高效液相色谱-串联质谱法测定百合上的氯虫苯甲酰胺残留

建立超高效液相色谱-串联质谱(UHPLC-MS/MS)快速检测百合中氯虫苯甲酰胺残留的方法。样品经0.1%冰乙酸-乙腈(V/V)提取,乙二胺-N-丙基硅烷(PSA)净化,UHPLC-MS/MS检测,外标法定量。结果表明,在0.005～0.5 mg/L浓度范围内,氯虫苯甲酰胺的质量浓度与色谱峰面积间呈良好的线性关系(R²>0.99);在0.05、0.50、1.00 mg/kg 3个加标水平下,氯虫苯甲酰胺在鲜、干百合的平均回收率为82%～107%之间,相对标准偏差(RSD)在1.87%～7.09%之间,方法定量限(LOQ)为0.05 mg/kg。该方法简便、快捷、灵敏度高等优点,可用于氯虫苯甲酰胺在鲜、干百合中残留检测、定量分析及市场监督抽查等。     

固相萃取-超高效液相色谱-串联质谱法测定沉积物中二甲四氯残留

针对沉积物性质特殊以及二甲四氯 (MCPA) 在其中环境风险大等问题,建立了超高效液相色谱-串联三重四极杆质谱 (UPLC-MS/MS) 快速测定沉积物中MCPA残留的方法。样品先经酸化的乙腈溶液超声萃取后,以石墨化碳黑-氨基串联固相萃取柱净化,再以硅烷醇基部分裸露的HSS T3柱为分离柱,采用乙腈-水溶液为洗脱液进行梯度洗脱,将MCPA与杂质分离,后经电喷雾离子源负离子扫描 (ESI?)、多反应监测模式 (MRM),基质匹配标准溶液外标法定量。结果表明:在1~100 μg/L范围内,MCPA的质量浓度与对应的色谱峰面积间呈良好的线性关系,R2 = 0.9997,定量限为0.1 μg/kg。在0.1~5 μg/kg添加水平下,MCPA在沉积物中的回收率在80%~108%之间,相对标准偏差在3.6%~8.2%之间。该方法通过增强色谱柱对MCPA的吸附作用,均衡了UPLC-MS/MS法建立过程中MCPA的“色谱柱保留”同“质谱离子化”互相矛盾的问题,具有分析时间短、准确度好和灵敏度高等优点,适用于沉积物中MCPA残留的痕量分析。     

高效液相色谱法测定二甲四氯在铁铝土中的吸附特征

二甲四氯 (MCPA) 是铁铝土区域广泛使用的一种除草剂,生物毒性大。吸附是控制MCPA在土壤中迁移/转化的关键过程。本研究建立了以C₁₈为色谱柱、V(甲醇):V[水 (乙酸调pH值至2.5)] = 80 : 20为流动相、PDA为检测器 (检测波长280 nm) 的MCPA高效液相色谱检测方法,并结合批量平衡法评估MCPA在铁铝土中的吸附特征。结果表明:在0.5~40 mg/L内,MCPA的质量浓度与对应的峰面积间呈良好线性关系 (R2 = 0.999 9),检出限为0.2 mg/L,定量限为0.5 mg/L;回收率为98%~103%,相对标准偏差为3.5%~4.0%,适用于MCPA吸附试验的测定。铁铝土对MCPA的等温吸附过程符合Freundlich模型,吸附自由能△G<0,|△G|为9.34~14.73 kJ/mol,是一个自发的、非均质的、多层的物理吸附过程。吸附常数K_f值在0.85~4.24 L/kg之间,属于难吸附污染物,对地下水具有环境风险。不同铁铝土对MCPA的吸附作用受土壤pH值、有机质、矿物影响,表现为水稻土>暗红湿润铁铝土>简育湿润铁铝土。氢键结合、偶极间作用是吸附发生的关键作用力。     

固相萃取-高效液相色谱-串联质谱法检测稻田中硝磺草酮和2甲4氯钠残留

建立了一种同步检测稻田中硝磺草酮和2甲4氯残留的固相萃取-高效液相色谱-串联质谱（SPE-LC-MS/MS）分析方法。样品经乙酸乙酯提取后,用PSA吸附、C₁₈固相萃取小柱净化,C₁₈色谱柱分离,0.1%甲酸水-0.1%甲酸甲醇溶液为流动相,梯度洗脱分离,在电喷雾ESI离子源正、负离子模式下,采用质谱多反应监测（MRM）模式定性分析。结果表明:硝磺草酮和2甲4氯的检出限（LOD）分别为0.005和0.025 ng,定量限（LOQ）分别为0.01和0.05 mg/L。在0.001~2 mg/L和0.005~5 mg/L范围内,硝磺草酮和2甲4氯的质量浓度与对应的峰面积间呈良好的线性关系,其相关系数均大于0.999 7。在0.01~2 mg/L添加水平下,硝磺草酮在田水、土壤、植株、稻壳和糙米中的平均回收率为75%~103%,相对标准偏差（RSD）为0.1%~8.2%;在0.05~10 mg/L添加水平下,2甲4氯在田水、土壤、植株、稻壳和糙米中的平均回收率为90%~113%,RSD为0.5%~7.4%。说明该方法高效、快捷、精确度高,能够满足硝磺草酮和2甲4氯钠在稻田中的残留量检测分析要求。     

Untersuchungen über Sonchus arvensis L. III, Metabolismus von MCPA

Research on Sonchus arvensis L. III. Metabolism of MCPA Roots of Sonchus arvenis L. were injected with ¹⁴C-MCPA at the time of planting of the root sections and when the plants had leaves 3 cm, 5–7 cm and 12–15 cm long. After extraction with 70% ethanol and separation by thin layer chromatography, three components, termed 1, 2 and 3, were detected by scanning. Component 2 gave a chromatograph identical to MCPA and was probably the non-metabolized residue of the injected material. Component 3 appeared faster than component 1 but, when heated with 1 N HCl or 1 N NaOH, both of them yielded component 2 (MCPA). In this latter reaction the conversion of component 3 was again the fastest. The older the plants the more rapid was the metabolism of MCPA, the highest metabolic rate occurring in the main roots. In secondary roots and leaves this process occurred more slowly. Dormant roots were capable of metabolizing MCPA quite as well as non-dormant roots. Raising the temperature from 7^° to 23°C accelerated the metabolic process. The liberation of ¹⁴C0₂ proceeded very slowly. During a period of 4 days only 1.3% of the total radio-activity was released as ¹⁴CO₂. In biotests, with Raphanus sativus L. as test species, component 3 appeared to be as phytotoxic as component 2 (MCPA), whereas the more stable component 1 exhibited very low phytotoxicity.     

分散固相萃取-液相色谱-串联质谱法检测香蕉和葡萄中苯锈啶残留

采用液相色谱-串联质谱仪(LC-MS/MS)建立了香蕉和葡萄中苯锈啶残留的分析方法。样品采用乙腈振荡提取,N-丙基乙二胺(PSA)分散固相萃取净化,ESI(+)电离方式,在多反应监测模式(MRM)下选择m/z 274.3→147.1为定量离子对进行检测。结果表明,在香蕉和葡萄基质中苯锈啶的平均回收率在94.1%～118.2%之间,相对标准偏差在1.6%～8.8%之间,方法定量限(LOQ)为0.01 mg/kg。该方法操作简便,适用于苯锈啶主要登记作物中的残留检测。     

Asulam mixtures for weed control in flax

Five field experiments were conducted from 1972 to 1975 to evaluate weed control in flax (Linum usitatissimum L.) using post-emergence treatments of asulam [methyl (4-aminobenzenesulphonyl) carbamatel alone and in combination with other herbicides. The ¹⁴C-asulam absorption by leaf segments and roots of glasshouse grown wild oats (Avena fatua L.) was also investigated. Asulam at 1.12 kg/ha gave good wild oat control and acceptable control of green foxtail (Setaria viridis (L.) Beauv.). However, wild oat control was poorer when asulam was combined with other herbicides: on a 3-year average, as compared with asulam alone at equal rates, the asulam+MCPA mixture resulted in a greater antagonism and a significant 6% reduction in flax seed yield, whereas the asulam+bromoxynil/MCPA mixture gave the least antagonistic effect, improved broadleaf weed control and increased yield by 13%. In mixtures, the potassium salt of MCPA was more compatible with asulam for weed control than the amine form. Both leaf segments and roots of wild oats absorbed and distributed less ¹⁴C-asulam from solutions containing MCPA than from those containing bromoxynil or bromoxynil/MCPA.     

THE INFLUENCE OF IRRIGATION, FERTILIZING AND MCPA ON THE COMPETITION BETWEEN SPRING CEREALS AND WEEDS

Summary. The average air-dry yield of weeds on fallow plots was about four times as large (2660 kg/ha) as the yield of weeds which developed among spring cereal crops (740 kg/ha). Application of fertilizers increased the number of weeds and their average weight on both irrigated and non-irrigated plots. Treatment with MCPA reduced the weed yield to 36% on fallow plots and to 26% on weedy cereal plots. It was more effective on fertilized plots than on unfertilized plots, but irrigation made little difference to its effectiveness. The space left by the destroyed weeds was mainly occupied by Agropyron repens . Oats were better able to compete with weeds than were wheat and barley. On unfertilized and non-irrigated plots spraying with MCPA (1-26 kg/ha) at the beginning of shooting significantly reduced the yields of weed-free barley. The yields of sprayed oats and wheat were also below the yields from the unsprayed although the reductions were not significant at the 5% level. However, on a number of fertilized and irrigated plots, both weedy and hand-weeded , on which the plants had better growing conditions, MCPA resulted in a significant increase in the grain yield of barley and oats.
Influence de l'irrigation, de la fertilisation et du MCPA sur la compétition entre céréales de printemps et mauvaises herbes     

The effect of the annual use of pesticides on soil microorganisms,pesticide residues in the soil and barley yields

A study has been made of the influence of pesticides used annually on soil microorganisms and crop yields. The persistence of these pesticides in the soil was also investigated. The herbicides MCPA, glyphosate, maleic hydrazide and tri-allate, and the insecticide parathion, were applied on experimental plots on which barley was grown during the years 1973-1981. The fungicide 2-methoxyethylmercury chloride was used every year for dressing the seeds grown in pesticide-treated plots. The pesticide treatments did not affect significantly the numbers of several groups of soil microorganisms. A slight increase was, however, observed in the nitrification activity in the soil. The barley yields were on average higher on pesticide-treated plots than on controls because of successful weed control. Pesticide residues in the soil were generally very low; for example, for parathion they were below 0.02 mg kg^?1 within 11 days, and for MCPA 0.06 mg kg^?1 within 7 days. However, the glyphosate residue was 1.6 mg kg^?1 in the autumn 2 days after the treatment, and the residue settled to a level of 0.2 mg kg^?1 during the following summer. No clear dependence was observed between the residue level and the time between treatment and sampling.     

Response of winter wheat (Triticum aestivum L.) and weeds to tank mixtures of 2,4-D plus MCPA with clodinafop propargyl

Field and greenhouse experiments were conducted in 2004 and 2005 to study weed control and the response of winter wheat to tank mixtures of 2,4-D plus MCPA with clodinafop propargyl. The field experiments were conducted at Yazd and Oroumieh, Iran, with factorial combinations of 2,4-D plus MCPA at 0, 975, and 1300 g ai ha⁻¹ and with clodinafop propargyl at 0, 64, 80, 96, and 112 g ai ha⁻¹ in four replications. The greenhouse experiments further evaluated the effect of these tank mixtures on weed control, where each herbicide mixture was considered as one treatment and the experiment was established in a randomized complete block design with four replications. In the field experiments, the herbicides were applied at wheat tillering, while in the greenhouse experiments they were applied at the beginning of the tillering stage and at the four-leaf stage of the grass and broadleaf weeds, respectively. The results indicated antagonistic effects between 2,4-D plus MCPA and clodinafop propargyl. The best tank mixture with regard to weed control efficacy was 2,4-D plus MCPA at 975 g ai ha⁻¹ with clodinafop propargyl at 96 g ai ha⁻¹. The wheat grain yield was also increased by the tank mixture of clodinafop propargyl with 2,4-D plus MCPA. Generally, to inhibit clodinafop propargyl efficacy reduction due to tank-mixing with 2,4-D plus MCPA, it is recommended that the application dose of 64 g ai ha⁻¹ should be increased to 96 g ai ha⁻¹.