主题：【原创】熊猫求助－－丙森锌残留的分析方法（有效回答，积分酬谢）

分子式

性质：白色或微黄色粉末。160℃以上分解。蒸气压<1mPa(20℃)。相对密度d23 1.813g/ml。溶解性(20℃)：水0.01g/L，一般溶剂中<0.1g/L。在冷、干燥条件下贮存时稳定，在潮湿强酸、强碱介质中分解。雄大鼠急性经口LD508500mg/kg。1,2-亚丙基二胺与二硫化碳、氢氧化钠反应，生成物再与硝酸锌反应即制得本品。用于防治马铃薯、番茄白粉病、早疫病和晚疫病等。

丙森锌是一种速效、长残留 、 广谱的保护性杀菌剂 。 其杀菌机制不固定，作用部位多，主要抑制病原菌体内丙酮酸的氧化。

中文通用名称：缬霉威(建议用名)，丙森锌 英文通用名称：iprovalicarb，propineb 农药登记名称和商品名称：66.8%丙森·缬霉可湿性粉剂(霉多克) 理化性质：缬霉威原药(95%)外观为白色粉末，无特殊气味，熔点163℃-165℃，蒸气压7.7×10-8Pa(20℃)，水中溶解度(20℃)为0.011g/L(SR)，0.0068g/L(SS)，不易溶于水，与甲苯、二氯甲烷、2-丙醇等有机溶剂混溶。丙森锌母粉(80%)外观为白色粉末，有轻微的特殊气味，蒸气压1.6×10-8Pa(20℃)，水中溶解度(20℃)＜0.01g/L，在正已烷、甲苯、二氯甲烷、异丙醇等有机溶剂中溶解度＜0.1g/L。 毒性：缬霉威原药和丙森锌原药大鼠急性经口、经皮LD50均＞5000mg/kg，对皮肤、眼睛无刺激性，无致敏性。致突变试验：Ames试验、小鼠微核试验、生死细胞染色体畸变试验均为阴性。缬霉威原药和丙森锌原药大鼠(13周)亚慢性试验最大无作用剂量为5000mg/kg；两年慢性试验最大无作用剂量：大鼠雄性5000mg/kg，雌性500mg/kg。制剂大鼠急性经口LD50＞2500mg/kg，急性经皮LD50＞2000mg/kg，急性吸入LC50＞5003mg/m3，对皮肤、眼睛无刺激性，无致敏性。属低毒杀菌剂。 环境生物安全性评价：缬霉威原药对虹鳟鱼LC50(96h)＞22.7mg/L，翻车鱼LC50(96h)＞20.7mg/L，水蚤LC50(96h)＞19.8mg/L；对北美鹌鹑LD50＞5000mg/kg，蜜蜂107.49μg/蜂。丙森锌原药对虹鳟鱼LC50(96h)1.9mg/L，金鱼LC50(96h)133mg/L，水蚤LC50(96h)4.7mg/L；对日本鹌鹑LD50＞5000mg/kg。 应用：66.8%丙森·缬霉可湿性粉剂(霉多克)为广谱杀菌剂，针对霜霉科和疫霉属真菌引起的病害具有很好的保护、治疗和铲除作用。其中的缬霉威为氨基酸酯类衍生物，具有独特的全新仿生结构使其作用机理区别于其他防治卵菌纲的杀菌剂。其作用机理为作用于真菌细胞壁和蛋白质的合成，能抑制孢子的侵染和萌发，同时能抑制菌丝体的生长，导致其变形、死亡。且该药含有易于被作物吸收的锌元素，有利于促进作物生长和提高果实的品质。药效试验表明，对防治黄瓜霜霉病有较好的防效，每亩用有效成分67-89g(折用本制剂100-133g/mu，一般每亩用量加水75kg，稀释600-750倍液)，于发病前或发病初期喷药。视病害情况重复施药3次，间隔7-10d。该药持效期较长，对作物安全，未见药害发生。 产品登记情况：LS200175　66.8%丙森·缬霉可湿性粉剂(霉多克)：LS200177　缬霉威原药； 　LS200178　80%丙森锌母粉(安泰生)。

Determination of dithiocarbamate fungicide propineb and its main metabolite propylenethiourea in airborne samples
Elias A. Kazos, Constantine D. Stalikas, Christos G. Nanos and Constantina N. Konidari
Chemosphere
Volume 68, Issue 11, August 2007, Pages 2104-2110

Abstract
A simple, rapid and sensitive GC–MS method for the determination of dithiocarbamate fungicide propineb [polymeric zinc propylenebis (dithiocarbamate)] and an improved HPLC procedure for the simultaneous determination of its main metabolite, propylenethiourea, and ethylenethiourea, the main metabolite of all ethylenedithiocarbamates, in airborne samples are described. The method for the analysis of propineb involves the evolution of carbon disulfide (CS2), under acidic conditions in the presence of stannous chloride, extraction of the generated CS2 into a layer of isooctane which is then analyzed for CS2 content by GC–MS in SIM mode. Under the optimum conditions, the retention time of CS2 was 1.89 min and the total time of chromatographic analysis was 5 min. Recoveries from spiking glass microfibre filters (GF/A) and silica gel filters were 86 ± 7 (n = 9) and 89 ± 4 (n = 9), respectively. The limit of detection is 0.7 ng per filter, which is equivalent to about 0.8–1.0 ng m−3 in air. In parallel, an HPLC method with ultraviolet detection is presented for the simultaneous analysis of the metabolites. Separation of the two metabolites was attained in less than 5 min. Recoveries from spiking GF/A and silica gel filters for ethylenethiourea were 100 ± 1 (n = 3) and 98 ± 2 (n = 3), respectively, while for propylenethiourea were 102 ± 1 (n = 3) and 98 ± 1 (n = 3), respectively. The detection limits are about 36–43 and 40–49 ng m−3 in air for ethylenethiourea and propylenethiourea, respectively. All the analytes spiked in the filters are proven to be stable for more than one month, at −4 °C.

Keywords: Fungicides; Propineb; Propylenethiourea; Ethylenethiourea; Air sampling; Gas chromatography; HPLC

  http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6V74-4NC5V1F-2&_user=1915929&_rdoc=1&_fmt=&_orig=search&_sort=d&view=c&_acct=C000055340&_version=1&_urlVersion=0&_userid=1915929&md5=3227dd1f3d84a59c2cf860833a0c1397

Determination of Dithiocarbamate Fungicides by Reversed-Phase Ion-Pair Liquid Chromatography with Chemiluminescence Detection
Hiroyuki Nakazawa
Journal of Liquid Chromatography & Related Technologies, Volume 27, Issue 4 January 2005 , pages 705 - 713
Abstract
Dithiocarbamate fungicides react with luminol to produce an intense chemiluminescence in the presence of hexacyanoferrate(III) and hexacyanoferrate(II) in alkaline solution. Based on this fact, a simple and sensitive method for the determination of dithiocarbamate fungicides by reversed-phase ion-pair liquid chromatography with chemiluminescence was developed. The mancozeb and propineb of dithiocarbamate fungicides were able to be separated using 5 mM phosphate buffer (pH 7.5) contained 2.5 mM tetrabutylammonium hydrogen sulfate/methanol (75:25) in a short time. The proposed method could be applied to the analysis of vegetables spiked with dithiocarbamate fungicides. 
Keywords: Antioxidants; Chemiluminescence; Dithiocarbamate fungicides; Ion-pair chromatography; Luminol; Mancozeb; Propineb 

  http://www.informaworld.com/smpp/content~content=a713638715~db=all

Analytical method for residues of propineb and propylenethiourea in agricultural products.
Uno, M | Onji, Y | Nozawa, M | Nakahira, H | Tanigawa, K
J. FOOD HYG. SOC. JAP. Vol. 24, no. 2, pp. 201-206. 1983.

A method was developed for the determination of propineb and propylenethiourea in agricultural products. Propineb was measured as propylenediamine after hydrolysis with acidic stannous chloride. In the analysis of commercial products, propylenethioura was detected in 50% of beer samples in the range of 0.001 to 0.007 ppm.

  http://md1.csa.com/partners/viewrecord.php?requester=gs&collection=ENV&recid=603073&q=determination+propineb&uid=&setcookie=yes
楼主，你好，相关的只能提供链接，没有下载的权限。

前处理
    在冷冻状态下将番茄样切碎混匀，称取10.0g于50ml顶空瓶中，加0.05g抗坏血酸、20ml SnCl2/5MHCl、10ml正己烷，使用压盖器迅速将瓶口用聚四氟乙烯/硅橡胶密封垫（20mm）和密封铝盖（20mm）密封，放入85℃水浴中2个小时，每隔15分钟摇1次，时间到后拿出冷却至室温，吸取上层有机相，FPD(S)
测定。
分析测定条件 
    气相色谱仪，FPD检测器（S滤光片），玻璃填充柱10%SE-30(60-100目)Chromosorb W(AW-DMCS)1.5m×3mm；柱温：60℃，进样口温度：150℃；检测器温度：150℃；载气（高纯氮）：总压：140 Kp。填充柱压力：80 Kp  空气：80Kp；氢气：60Kp；进样量：2μl。
结果计算
    试验采取外标法定量，用标准曲线法进行校准。标准曲线的制备：标准工作液稀释成由低到高的6个浓度，0.05、0.1、0.2、0.5、1、2μg•ml-1。在浓度0.05-2μg•ml-1范围内，以峰面积（y）—CS2浓度(x)作标准工作曲线，浓度与峰面积呈线性相关。
  氨基甲酸酯在酸性条件下转化为二硫化碳，色谱测出浓度后再除以转化率就行了。

另外，氨基甲酸类的农药本身的毒性不大，主要的还是其降解产物ETU（乙撑硫脲）的致癌作用。

代森锰锌与其降解产物在谷物中的残留

原文由 187025577 发表:我晕，不让发附件啊

你好！附件是可以发的，只不过是需要版主等验证的。