Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Impact of Sublethal Doses of 2,4-D,Simulating Drift,on Tomato Yield

Abstract

Tomato is considered one of the most sensitive crops regarding 2,4-D drift. In many cases, such susceptibility has led to important restrictions in the use of 2,4-D based products. Field experiments were carried out for two consecutive years in tomato, by applying sublethal doses of 2,4-D (ranging from 0.42 to 13.44 g a.i. ha^?1) directly to plants, at different stages of growth, as a simulation of eventual drifts to the crop. The range of rates was based on the assumption of a 0.0625–2.0% drift level of a 1 L ha^?1 of the most common formulated herbicides. For this crop, the range of rates between 0.42 and 13.44 g a.i ha^?1 applied at the beginning of flowering caused a linear crop reduction. On the other hand, rates ≤13.44 g a.i. ha^?1 applied after full development of fourth truss stage or latter had no effect on crop yield or development. For tomato, tolerance to 2,4-D strongly increases with plant age.     

Spiking solvent, humidity and their impact on 2,4-D and 2,4-DCP extractability from high humic matter content soils

The 2,4-dichlorophenoxyacetic acid (2,4-D) is a hormone-like herbicide widely used in agriculture. Although its half life in soil is approximately two weeks, the thousands of tons introduced in the environment every year represent a risk for human health and the environment. Considering the toxic properties of this compound and its degradation products, it is important to assess and monitor the 2,4-D residues in agricultural soils. Furthermore, experiments of phyto/bioremediation are carried out to find economic and environmental friendly tools to restore the polluted soils. Accordingly, it is essential to accurately measure the amount of 2,4-D and its metabolites in soils. There is evidence that 2,4-D extraction from soil samples seriously depends on the physical and chemical properties of the soil, especially in those soils with high content of humic acids. The aim of this work was to assess the variables that influence the recovery and subsequent analysis of 2,4-D and its main metabolite (2,4-dichlorophenol) from those soils samples. The results showed that the recovery efficiency depends on the solvent and method used for the extraction, the amount and kind of solvent used for dissolving the herbicide and the soil water content at the moment of spiking. An optimized protocol for the extraction and quantification of 2,4-D and its main metabolite from soil samples is presented.     

紫茎泽兰的化学防除及生态修复效果

紫茎泽兰是我国重要的外来入侵生物,一旦入侵,就排挤当地物种,很快成为优势种群,在西南地区已对当地的农业、畜牧业,以及生态环境造成严重的破坏.2年的试验和示范结果表明,磺酰脲类除草剂嘧磺隆187.5～375g/hm2(有效成分,下同)、噻吩磺隆375g/hm2、氯嘧磺隆375g/hm2和吡啶类除草剂氨氯吡啶酸1 080g/hm2对紫茎泽兰均有优异的防除效果.而2,4-滴1 500g/hm2、乙羧氟草醚150g/hm2、氟磺胺草醚500g/hm2、咪唑乙烟酸1 500g/hm2、嗪草酸甲酯50g/hm2、环嗪酮2 500g/hm2、氯草定750～1 500g/hm2不能完全杀死紫茎泽兰.针对山区水源短缺,运水不便的的问题,通过在除草剂中加入2 L/hm2机油乳油,采用很低容量喷雾法,用水量可由常量喷雾的900～1 200L/hm2减少到30～40L/hm2,施药效率较常量喷雾提高8～10倍.此外,还可将除草剂制成颗粒剂或采用毒土法撒施,不需施药器械,且可以节省大量水运输费用.紫茎泽兰用上述除草剂防除后,能选择性地促进非靶标植物的生长.大面积防除2年后,生态恢复率为40%～90%.     

氯代酰胺类除草剂降解菌的分离及降解性能

从生产乙草胺的农药厂废水生物处理池活性污泥中分离到一株氯代酰胺类除草剂降解细菌,命名为Y3B-1.根据表型特征、生理生化特性和16S rDNA序列系统发育分析,将其鉴定为副球菌属(Paracoccus sp.).研究了菌株Y3B-1在不同条件下对多种氯代酰胺类除草剂的降解性能.结果表明:菌株Y3B-1能以乙草胺为碳源生长,并能降解乙草胺、丁草胺和丙草胺,3 d对这3种氯代酰胺类除草剂的降解率分别达到86.7%、65.5%和69.1%,不能降解异丙甲草胺.该菌降解乙草胺的最适温度为30℃,最适pH为7.0,对乙草胺的降解效果与接种量成正相关,对较低浓度的乙草胺有很好的降解效果,过高的起始浓度抑制其对乙草胺的降解,外加营养如酵母膏和土壤悬液则显著促进其对乙草胺的降解.图7参23     

固相萃取-高效液相色谱法同时测定水中12种磺酰脲类除草剂

采用固相萃取-高效液相色谱法同时测定水中12种磺酰脲类除草剂,样品经磷酸调节pH值为2后,经Watens Oasis HLB SPE柱净化浓缩,乙腈洗脱,选择检测波长为230 nm,以乙腈-水溶液(0.02%磷酸)为流动相梯度洗脱,保留时间在14 min～32 min范围内.12种磺酰脲类除草剂在0.050 mg/L～...     

Ability of Poplar (Populus spp.) to Detoxify Chloroacetanilide Herbicides

The ability of poplar trees to resist chemical stress caused by chloroacetanilide herbicides was studied. Detached leaves of Lombardy poplar (Populus nigra L.) were exposed to seven chloroacetanilide herbicides via uptake through the cut petiole. The leaves showed high tolerance against the phytotoxicity of these compounds. Their tolerance was further enhanced by treatment with 2-oxothiazolidine-4-carboxylic acid (OTC, a precursor of the amino acid cysteine). High levels of glutathione (GSH) and GSH S-transferase (GST) activity were detected in poplar leaves. Treatments with chloroacetanilide herbicides left the GSH content in the leaves unchanged but strongly induced the GST activity. In contrast, in OTC-treated leaves increased GSH contents were measured, but GST activities remained unchanged. It therefore appears that a highly active and inducible GSH-conjugation Phase II detoxification system in their leaves may make poplar trees useful for phytoremediation of soils contaminated with chloroacetanilide herbicides. Based on these findings a phytoremediation project using different poplar hybrids at a site heavily polluted with such compounds in Hungary has been launched.     

Absorption and translocation of sulfometuron-methyl in sugarcane (Saccharum officinarum L.) at different growth stages

ABSTRACT

In Brazil, weed management in sugarcane fields is mainly done with the use of selective herbicide formulations. For many years, diuron+hexazinone was one of the main herbicide mixture formulations used in sugarcane. Later, sulfometuron-methyl was included in the same mixture, which was marketed as a new herbicide formulation for residual in-season weed control in sugarcane. The mixture diuron+hexazinone+sulfometuron-methyl has been widely used in commercial sugarcane fields in Brazil. However, recent field observations have shown that sugarcane plants at different growth stages varied in their phytotoxicity levels after treatment with diuron+hexazinone+sulfometuron-methyl. Greenhouse and laboratory studies were conducted to determine ¹⁴Csulfometuron-methyl absorption and translocation, as well as ¹⁴C distribution in sugarcane at two growth stages, 2 to 3 leaves and 5 to 6 leaves. ¹⁴Csulfometuron-methyl absorption by sugarcane did not differ between the two growth stages. Different patterns of ¹⁴C accumulation were observed, which may explain variations in sulfometuron-methyl phytotoxic responses observed in the field.     

Responses of different fungal and plant species to acetolactate synthase inhibitors and their derivatives

Abstract

The effect of sulfonylurea (SU) acetolactate synthases (ALS) inhibitors (chlorsulfuron and triasulfuron) and their 13 guanidine and 7 azole derivatives was studied on 17 fungal and 21 plant species. The efficacy of chlorsulfuron and triasulfuron against Fusarium oxysporum and Thielaviopsis basicola was higher than carbendazim. Two azole derivatives were highly selective for maize. The antifungal activity spectrum of both guanidine and azole derivatives differed from that of chlorsulfuron and triasulfuron, and did not exert notable antifungal activity in vitro. However, they had significant anti‐Fusarium efficacy on rye that surpassed that of carbendazim.     

Simultaneous voltammetric determination of four triazine herbicides in water samples with the aid of chemometrics

A novel differential pulse voltammetry (DPV) method was developed for the simultaneous analysis of herbicides in water. A mixture of four herbicides, atrazine, simazine, propazine and terbuthylazine was analyzed simultaneously and the complex, overlapping DPV voltammograms were resolved by several chemometrics methods such as partial least squares (PLS), principal component regression (PCR) and principal component–artificial networks (PC–ANN). The complex profiles of the voltammograms collected from a synthetic set of samples were best resolved with the use of the PC–ANN method, and the best predictions of the concentrations of the analytes were obtained with the PC-ANN model (%RPE_T = 6.1 and average %Recovery = 99.0). The new method was also used for analysis of real samples, and the obtained results were compared well with those from the GC-MS technique. Such conclusions suggest that the novel method is a viable alternative to the other commonly used methods such as GC, HPLC and GC-MS.