Surfactants in glyphosate products in Japan
Surfactants in glyphosate products in Japan
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日本草甘膦产品中的表面活性剂
DOI：
10.1080/15563650.2019.1648818
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发表时间：
2020
影响因子：
3.3
通讯作者：
M. Katagi
中科院分区：
文献类型：
--
作者：
H. Kamata;Shihoko Nakano;N. Shima;Y. Fujita;Kiyotaka Usui;Y. Kamijo;Tomoki Hanazawa;M. Katagi
据编辑说，草甘膦在世界各地作为一种非选择性除草剂使用。然而，草甘膦产品引起中毒的报道很多，大量摄入草甘膦产品会导致多器官损伤[1]。RoundupVR是一种典型的草甘膦产品，自20世纪70年代末草甘膦首次上市以来，已被广泛分发。草甘膦产品中含有表面活性剂作为添加剂，最近发现，在包括农达在内的许多产品中，表面活性剂是非离子聚氧乙烯烷基胺(POEA)。因此，草甘膦产品造成的器官毒性可能不是由主要成分草甘膦引起的，而是由表面活性物质POEA[2]引起的。此外，POEA毒性研究表明，POEA可能仍是一种环境残留物，它具有很强的细胞毒性，对包括海洋生物和两栖动物在内的许多生物都有毒性。它被认为比草甘膦本身毒性更大。在传统的草甘膦产品中，草甘膦被列为异丙胺或铵盐，但在2003年，草甘膦的钾盐在日本被注册为杀虫剂。在此之后，一种含有钾盐的草甘膦产品被发布销售(Roundup MaxloadR)，该产品现在被广泛分销。农达MaxloadR含有高浓度的钾(2.6mEq/ml)，因此摄入它会导致高钾血症，导致心功能异常，如室性心律失常，这可能是致命的[3]。然而，它不会导致多器官损伤，就像摄入传统的草甘膦产品一样[4]，这表明该产品可能不含POEA。因此，我们使用我们最近建立的LC-HRMS方法分析了五种草甘膦产品中存在的表面活性物质，包括目前可用的Roundup MaxloadR。分析表明，Roundup MaxloadR不含POEA，但它确实含有阳离子季铵盐基表面活性剂烷基双(2-羟乙基)甲基铵和非离子表面活性剂烷基葡萄糖苷(表1)。虽然被检测的阳离子表面活性剂烷基双(2羟乙基)甲基铵可能具有类似POEA的刺激性，但根据其基于铵的结构，其在消化系统中的吸光度预计较低(图1)。另一种被检测的表面活性剂烷基葡萄糖苷被认为是一种低刺激性的非离子表面活性剂。因此，据估计，将POEA改为氨基表面活性物质和低刺激性表面活性物质的混合物将减少作为Roundup MaxloadR中毒症状的多器官损伤。这种明显的毒性降低可能意味着生物利用度的降低，细胞毒性的降低，或者两者的某种组合。因此，Roundup MaxloadR产品引起的中毒症状将以高钾血症为主。然而，如表1所示，含有草甘膦异丙胺盐和POEA的产品目前仍然可用，因此必须认识到，多器官损伤可能是草甘膦中毒的症状
To the editor Glyphosate is used throughout the world as a non-selective herbicide. However, there are many reports of poisoning caused by glyphosate products, and ingestion of massive quantities of the products is known to cause multiple organ injuries [1]. RoundupVR is a typical glyphosate product that has been widely distributed since glyphosate was first marketed in the late 1970s. Glyphosate products contain surfactants as additives, and it has recently come to light that in many products, including RoundupR , the surfactant is the non-ionic polyoxyethylenealkylamine (POEA). Hence, the organ toxicity caused by glyphosate products may not be caused by glyphosate, the main ingredient, but rather by the surfactant, POEA [2]. Furthermore, POEA toxicity studies have indicated that POEA is likely to remain as an environmental residue, that it is potently cytotoxic, and that it is toxic to many organisms, including marine life and amphibians. It is thought to be more toxic than glyphosate itself. In conventional glyphosate products, glyphosate is included as the isopropylamine or ammonium salt, but in 2003 the potassium salt of glyphosate was registered as a pesticide in Japan. After that, a glyphosate product containing the pottasium salt is released for sales (Roundup MaxloadR ) and this product is now widely distributed. Roundup MaxloadR contains a high concentration (2.6 mEq/ mL) of potassium, so its ingestion can cause hyperkalemia, resulting in abnormal cardiac function, such as ventricular arrhythmia, and this can be fatal [3]. However, it does not tend to cause multiple organ injuries, as seen with ingestion of conventional glyphosate products [4] which suggests that this product may not contain POEA. Therefore, we analyzed the surfactants present in five glyphosate products, including the currently available Roundup MaxloadR , using a liquid chromatography/high resolution mass spectrometry (LC-HRMS) method which we have recently established [5]. The analysis revealed that Roundup MaxloadR does not contain POEA, but that it does contain the cationic quaternary ammonium-based surfactant, alkylbis(2-hydroxyethyl)methylammonium, and non-ionic surfactant, alkyl glucoside (Table 1). While the detected cationic surfactant, alkylbis(2hydroxyethyl)methylammonium might have a irritancy similar to POEA, its absorbance from the digestive system is expected to be low, according to its ammonium-based structure (Figure 1). The other detected surfactant, alkyl glucoside is known as a low irritant non-ionic surfactant. Therefore, it is estimated that alteration from POEA to mixture of the ammonium-based surfactant and the low irritant surfactant would have led to reduction of multiple organ injuries as a symptom of Roundup MaxloadR poisoning. This reduced apparent toxicity may represent reduced bioavailability, reduced cytotoxicity, or some combination of both. Thus the poisoning symptoms caused by the product, Roundup MaxloadR , would be dominated by the effect of hyperkalemia. However, as shown in Table 1, products containing the glyphosate isopropylamine salt and POEA are still currently available, so it is essential to be aware that multiple organ injuries can be a symptom of poisoning by glyphosate