Procedure for the determination of 2,4‐D and dicamba in inhalation,dermal, hand‐wash,and urine samples from spray applicators

Abstract

Analytical procedures for the simultaneous determination of residues of 2,4‐D and dicamba from polyurethane foam plug air samplers, ethylene glycol impregnated glass‐fiber filter paper dermal samplers, 1% sodium bicarbonate hand wash solution, and urine are presented. Residues were derivatized with diazomethane and quantitated using electron capture gas chromatography. Recoveries were greater than 80% at the limit of detection in all substrates. The limits of detection for both herbicides were 0.1 μg/foam plug and 0.5 μg/filter paper, and in the urine, 1.7 μg/100 mL and 5.0 μg/100 mL for dicamba and 2,4‐D, respectively.     

The use of naturally generated volatile fatty acids for herbicide removal via denitrification

This research focuses on the removal of 2, 4-D via denitrification, with a particular emphasis on the effect of adding naturally generated volatile fatty acids (VFAs) as a carbon source. These VFAs had been produced from an acid-phase anaerobic digester (mean VFA concentration of 3153 ± 801 mg/L [as acetic acid]). The first step involved developing 2, 4-D degrading bacteria in a sequencing batch reactor (SBR) fed with both sewage and 2, 4-D (30–100 mg/L). Subsequent denitrification batch tests demonstrated that the specific denitrification rate increased from 0.0119 ± 0.0039 to 0.0192 ± 0.0079 g NO₃-N/g volatile suspended solids (VSS) per day, when using 2, 4-D alone versus 2, 4-D plus natural VFAs from the digester as a carbon source. Similarly, the specific 2, 4-D consumption rate increased from 0.0016 ± 0.0009 to 0.0055 ± 0.0021 g 2,4-D/g VSS per day, when using 2, 4-D alone as compared to using 2, 4-D plus natural VFAs. Finally, a parallel increase in the percent 2, 4-D removal was observed, rising from 28.33 ± 11.88 using 2, 4-D alone to 54.17 ± 21.89 using 2, 4-D plus natural VFAs.     

Pesticide risk assessment: A study on inhalation and dermal exposure to 2,4-D and paraquat among Malaysian paddy farmers

A cross-section analytical study was conducted to evaluate the risk of pesticide exposure to those applying the Class II pesticides 2,4-D and paraquat in the paddy-growing areas of Kerian, Perak, Malaysia. It investigated the influence of weather on exposure as well as documented health problems commonly related to pesticide exposure. Potential inhalation and dermal exposure for 140 paddy farmers (handlers of pesticides) were assessed. Results showed that while temperature and humidity affected exposure, windspeed had the strongest impact on pesticide exposure via inhalation. However, the degree of exposure to both herbicides via inhalation was below the permissible exposure limits set by United States National Institute of Occupational Safety and Health (NIOSH). Dermal Exposure Assessment Method (DREAM) readings showed that dermal exposure with manual spraying ranged from moderate to high. With motorized sprayers, however, the level of dermal exposure ranged from low to moderate. Dermal exposure was significantly negatively correlated with the usage of protective clothing. Various types of deleterious health effects were detected among users of manual knapsack sprayers. Long-term spraying activities were positively correlated with increasing levels of the gamma-glutamyl transpeptidase (GGT) liver enzyme. The type of spraying equipment, usage of proper protective clothing and adherence to correct spraying practices were found to be the most important factors influencing the degree of pesticide exposure among those applying pesticides.     

Polynomial response of 2,4-D mineralization to temperature in soils at varying soil moisture contents,slope positions and depths

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is a widely used broadleaf control agent in cereal production systems. Although 2,4-D soil-residual activity (half-lives) are typicaly less than 10 days, this herbicide also has as a short-term leaching potential due to its relatively weak retention by soil constituents. Herbicide residual effects and leaching are influenced by environmental variables such as soil moisture and temperature. The objective of this study was to determine impacts of these environmental variables on the magnitude and extent of 2,4-D mineralization in a cultivated undulating Manitoba prairie landscape. Microcosm incubation experiments were utilized to assess 2,4-D half-lives and total mineralization using a 4 × 4 × 3 × 2 factorial design (with soil temperature at 4 levels: 5, 10, 20 and 40°C; soil moisture at 4 levels: 60, 85, 110, 135 % of field capacity; slope position at 3 levels: upper-, mid- and lower-slopes; and soil depth at 2 levels: 0–5 cm and 5–15 cm). Half-lives (t_1/2) varied from 3 days to 51 days with the total 2,4-D mineralization (M _T ) ranging from 5.8 to 50.9 %. The four-way interaction (temperature × moisture × slope × depth) significantly (p< 0.001) influenced both t_1/2 and M _T. Second-order polynomial equations best described the relations of temperature with t_1/2 and M_T as was expected from a biological system. However, the interaction and variability of t_1/2 and M_T among different temperatures, soil moistures, slope positions, and soil depth combinations indicates that the complex nature of these interacting factors should be considered when applying 2,4-D in agricultural fields and in utilizing these parameters in pesticide fate models.     

Residues of 2,4‐D in air samples from Saskatchewan: 1966–1975

Abstract

Residues of 2,4‐D (2,4‐dichlorophenoxyacetic acid) in air samples from several sampling sites in central and southern Saskatchewan during the spraying seasons in the 1966–68 and 1970–75 periods were determined by gas‐liquid Chromatographic techniques. Initially, individual esters of 2,4‐D were characterized by retention times and confirmed further by co‐injection and dual column procedures. Since 1973, however, only total 2,4‐D acid levels in air samples have been determined after esterification to the methyl ester and confirmed by gc/ms techniques whenever possible.

Up to 50% of the daily samples collected during the spraying season at any of the locations and during any given year contained 2,4‐D, with butyl esters being found most frequently. The daily 24‐hr mean atmospheric concentrations of 2,4‐D ranged from 0.01 to 1.22 μg/m³, 0.01 to 13.50 μg/m³, and 0.05 to 0.59 μg/m for the iso‐propyl, mixed butyl and iso‐octyl esters, respectively. Even when the samples were analysed for the total 2,4‐D content, i.e. from 1973 onwards, the maximum level of the total acid reached only 23.14 μg/m. In any given year and at any of the sampling sites, about 30% of the samples contained less than 0.01 μg/m³ of 2,4‐D. In another 40% of the samples, the levels of 2,4‐D ranged from 0.01 to 0.099 yg/m. Only about 30% of the samples contained 2,4‐D concentrations higher than 0.1 μg/m³, with only 10% or less exceeding 1 μg/m³.

None of the samples, obtained with the high volume particu‐late sampler, showed any detectable levels of 2,4‐D, indicating little or no transport of 2,4‐D adsorbed on dust particles or as crystals of amine salts.     

Effect of exogenous 2,4-epibrassinolide on grain filling and yield formation of Tartary buckwheat北大核心CSCD

为明确外源2,4-表油菜素内酯影响苦荞生长、粒重与产量形成的生理机制,以苦荞品种晋荞2号为试验材料,研究不同浓度的外源2,4-表油菜素内酯处理(0、0.1、0.5、1.0和2.0 mg/L)对苦荞籽粒的灌浆特性、淀粉合成酶、根系形态及活力、叶片抗氧化酶活性及光合特性、农艺性状及产量的影响.结果表明:0.5 mg/L处理时苦荞籽粒的灌浆起始势(R0)、最大灌浆速率(Gmax)和平均灌浆速率(Gmean)最大,而达最大灌浆速率的时间(Tmax.G)最小;随2,4-表油菜素内酯施用量的增加,苦荞籽粒的腺苷二磷酸葡萄糖焦磷酸化酶(AGPase)和可溶性淀粉合成酶(SSS)活性、根系总长度等根系形态指标和根系活力、叶片抗氧化酶活性及光合特性指标、株高、主茎直径、单株粒重和千粒重均呈先增加后降低的趋势,且都在0.5 mg/L处理时达最大.外源2,4-表油菜素内酯的施用能在一定程度上促进苦荞产量的增加,其中0.1、0.5和1.0 mg/L处理与对照相比分别提高产量1.10、1.31和1.06倍,2.0 mg/L处理则降低0.96倍.本研究表明适宜的外源2,4-表油菜素内酯处理(0.5 mg/L)能促进苦荞籽粒灌浆,提高粒重和最终的产量.(图1表8参32)     

Effect of feeding time on the performance of a sequencing batch reactor treating a mixture of 4-CP and 2,4-DCP

This paper investigated the biodegradation kinetics of 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) separately in batch reactors and mixed in sequencing batch reactors (SBRs). Batch reactor experiments showed that both 4-CP and 2,4-DCP began to inhibit their own degradation at 53 and 25 mg l(-1), respectively, and that the Haldane equation gave a good fit to the experimental data because r(2) values were higher than 0.98. The maximum specific degradation rates (q(m)) were 130.3 and 112.4 mg g(-1) h for 4-CP and 2,4-DCP, respectively. The values of the half saturation (K(s)) and self-inhibition constants (K(i)) were 34.98 and 79.74 mg l(-1) for 4-CP, and 13.77 and 44.46 mg l(-1) for 2,4-DCP, respectively. The SBR was fed with a mixture of 220 mg l(-1) of 4-CP, 110 mg l(-1) of 2,4-DCP, and 300 mg l(-1) of peptone as biogenic substrate at varying feeding periods (0-8h) to evaluate the effect of feeding time on the performance of the SBR. During SBR operation, in addition to self-inhibition, 4-CP degradation was strongly and competitively inhibited by 2,4-DCP. The inhibitory effects were particularly pronounced during short feeding periods because of higher chlorophenol peak concentrations in the reactor. The competitive inhibition constant (K(ii)) of 2,4-DCP on 4-CP degradation was 0.17 mg l(-1) when the reactor was fed instantaneously (0 h feeding). During longer feedings, increased removal/loading rates led to lower chlorophenol peak concentrations at the end of feeding. Therefore, in multi-substrate systems feeding time plus reaction time should be determined based on both degradation kinetics and substrate interaction. During degradation, the meta cleavage of 4-chlorocatechol resulted in accumulation of a yellowish color because of the formation of 5-chloro-2-hydroxymuconic semialdehyde (CHMS), which was further metabolized. Isolation and enrichment of the chlorophenols-degrading culture suggested Pseudomonas sp. and Pseudomonas stutzeri to be the dominant species.     

剧毒化学品甲苯-2，4-二异氰酸酯运输危险性评估

为探讨低挥发性剧毒化学品甲苯-2，4-二异氰酸酯在运输过程中大量泄漏引起群体中毒事故的可能性以及对环境的影响，对本品的急性毒性、扩散模型、环境转归、生态毒性，以及运输泄漏事故资料进行综合分析和评估。评估结果本品吸人中毒的潜在危险性指数为低度危险物质；扩散模型运输泄漏模拟危险区域下风向距离小于某些非剧毒品；环境转归研究显示本品在环境介质中没有持久性，没有明显的生物蓄积性，生态毒性较低；历年来运输泄漏事故分析未见发生大规模严重群体中毒和环境污染事故。认为本品在运输过程中大量泄漏，不会大范围扩散引起严重群体中毒事故，也不会对环境造成严重和长期的危害，建议在运输环节中运输条件适当放宽，按照一般有毒品进行管理。     

Photodegradation of 2,4-D induced by NO2- in aqueous solutions：The role of NO2

To elucidate the effect of nitrite ion （NO2^-） on the photodegradation of organic pollutants, a 300 W mercury lamp and Pyrex tubes restricting the transmission of wavelengths below 290nm were used to simulate sunlight, and the photodegradation processes of 2,4-dichlorophenoxyacetic acid （2,4-D） with different concentrations of NO2^- in freshwater and seawater were studied. The effect of reactive oxygen species （ROS） on the photolysis of 2,4-D was also demonstrated using electron paramagnetic resonance （EPR）. The results indicated that the 2,4-D photolysis reaction followed the first-order kinetics in freshwater and seawater under different concentrations of NO2^-. Meanwhile, the photochemical reaction rate of 2,4-D increased with increasing concentration of NO2^-. When the concentration of NO2^- was lower than 23 mg/L, the photodegradation rate of 2,4-D in seawater was higher than that in freshwater. However, when the concentration of NO2^- was reached 230 mg/L, 2,4-D degradation slowed down in seawater. It was important to note that EPR spectra showed NO2 radical was generated in the NO5 solution under simulated sunlight irradiation, indicating that 2,4-D photodegradation could be induced by NO2. These results show the key role of NO2^- in photochemistry and are helpful for better understanding of the phototransformation of environmental contaminants in natural aquatic systems.     

微生物燃料电池强化去除农药2,4-二氯苯氧乙酸及同步产电性能

研究了广泛应用的农药2,4-二氯苯氧乙酸(2,4-D)存在对微生物燃料电池(microbial fuel cell,MFCs)产电性能、污染物去除及微生物群落结构的影响,并探讨了阳极预曝气对2,4-D的强化去除及产电影响.结果表明,向以乙酸钠为燃料的双室型微生物燃料电池阳极室内加入2,4-D,会降低系统输出电压,降低功率密度,增加内阻.当300 mg·L~(-1)的2,4-D与乙酸钠(850 mg·L~(-1))共存时,与乙酸钠单基质相比,最大功率密度从0.151 W·m~(-2)迅速下降到0.057 W·m~(-2),内阻相应从524Ω增加到1 230Ω.为了加快系统中2,4-D的去除,减少其对产电菌的抑制效应,采用阳极预曝气6 h的运行方式,显著提高了2,4-D去除效率,同时获得了0.42~0.47 V的最高输出电压.2,4-D加入后MFC阳极微生物群落结构发生了变化,选择出了多种2,4-D降解菌及具有2,4-D耐受能力的产电菌.研究表明,可以通过阳极预曝气方式强化2,4-D去除的同时从MFCs系统回收电能.