Dissipation of 2,4-D glyphosate and paraquat in river water

Dissipation of herbicides in river water was determined by adding different concentrations of 2,4-D, glyphosate and paraquat to samples of river water. A small variation of dissipation of radioactivity for¹⁴C-2,4-D in higher and lower concentrations and in different samples of river water was found. But about half the radioactivity disappeared from water samples of original glyphosate concentration at 100 mg L^?1 and, in the case of 100 μg L^?1, only 11 to 22% remained in the samples of river water after 56 d incubation except the sample from Hsin-Tien River. More than 80% of paraquat remained in water samples. Determination of octanol-water partition coefficient (Kow) showed a large difference in amounts of 2,4-D partitioned in water phase at different pH values, 97.4% at the higher pH of ionic state and 5.2% at the lower pH of molecular state, implying that pH value of water might affect the bioaccumulation process of 2,4-D. The result showed that 95.0% of glyphosate present in water phase in ionic form (higher pH) and 82.3% in molecular form (lower pH), indicating that glyphosate might have no affect on the biomagnification, since most of glyphosate could be excreted with water by organisms.     

2,4-D丁酯的水解与光解特性研究

通过室内模拟试验,研究2,4-D丁酯在不同pH值和温度下的水解动态和在有机溶剂中的光解特性。结果表明,2,4-D丁酯的水解与光解均符合一级动力学方程。在pH7以下的缓冲溶液中,2,4-D丁酯的水解反应十分缓慢,但在碱性溶液中其水解速率加快。25℃下2,4-D丁酯在pH5、7和9的缓冲溶液中的水解半衰期分别为23.5、5.8d和10.7min。2,4-D丁酯的水解速率随温度升高而增加,在温度为15、25℃和35℃的pH7缓冲溶液中的水解半衰期分别为21.5、5.8、3.9d,平均温度效应系数为2.57。2,4-D丁酯水解反应的活化能与温度之间无明显相关性,而活化熵与温度呈显著相关性。2,4-D丁酯的水解主要由活化熵所驱动。采用GC-MS技术对2,4-D丁酯水解产物进行鉴定,确定水解产物主要是2,4-二氯苯氧乙酸和2,4-二氯苯酚。2,4-D丁酯在正己烷中光解速率比在甲醇中快,在丙酮中几乎不发生光解,其光解速率随浓度的升高而减慢。     

不同地区凤眼莲的光合生态功能型及其生态因子分析

以江苏省农业科学院太湖雪堰、南京和滇池白山湾的试验点内种养的凤眼莲为研究材料, 在相同种养时间内, 统一测定不同地区植株的株高和干重的变化及不同叶位光合参数和光合功能叶片的光合-光响应曲线等, 以期阐明不同生态区凤眼莲株型特征形成的生态生理机制, 并为不同地区人工放养凤眼莲的高产栽培提供理论参考和技术支持。结果表明: (1)不同地区种养的凤眼莲株型有较大差异, 滇池的为短地上部分和长根的株型, 其茎叶长/根长为0.4±0.1; 南京的为中等长度的地上部分和短根的株型, 其茎叶长/根长为7.1±0.3;太湖的为长地上部分和中等根长的株型, 其茎叶长/根长为2.0±0.2。(2)形态有差异的不同地区凤眼莲植株的光合表现存在差异, 与南京和滇池地区的相比, 太湖凤眼莲不同叶位的净光合速率(Pn) 最高(25.9~35.3μmol·m^-2·s^-1); 相关性分析表明, 南京凤眼莲的Pn 与其相对湿度呈极显著负相关(r=-0.831^**, n=6), 滇池凤眼莲的Pn 与气孔导度呈显著正相关(r=0.769^*, n=6), 太湖凤眼莲的相对湿度与叶片蒸腾速率呈显著负相关(r=-0.818^*, n=6)。可见影响不同地区Pn 的外界因子有差异, 但除外界光强外, 相对湿度也是影响其Pn 高低的重要生态因子。(3)不同生态地区形态有差异的植株已形成了相应的光合潜力, 生长能力最强的太湖地区植株,光合能力也最强, P_max 最大(36.29±1.21 μmol·m^-2·s^-1)且光饱和点最高(LSP, 2 350.0±69.0 μmol·m^-2·s^-1); 相关性分析进一步表明, 株高和光补偿点(LCP)以及茎叶长度与光饱和点均呈显著正相关, 相关系数分别为r=0.998^*、r=0.997^*(n=10)。本研究可为不同地区利用凤眼莲净化富营养水域的高产栽培提供参考。     

Potential applications of water hyacinth for water,air recycling in closed systems

Russian space scientists have done much work on closed ecological life support systems (CELSS) using higher plants and algae both for recycling water and air and regeneration of food. Research in this country has been directed mostly towards physiochemical methods for recycling water and air. Development of CELSS using biological components such as aquatic vascular plants (water hyacinth) has recently been recommended. Use of water hyacinth in open systems for municipal wastewater treatment has been studied extensively along with its many other terrestrial uses (animal feed, source of fresh water through evapotranspiration, methane source, fertilizer and compost). After reviewing the research work in CELSS, controlled environment agriculture, and water hyacinth and its uses, potential applications of water hyacinth in closed ecological systems for water, air recycling are outlined.     

The millimetre-scale distribution of 2,4-D and its degraders drives the fate of 2,4-D at the soil core scale

The biodegradation of organic compounds in soil is a key process that has major implications for different ecosystem services such as soil fertility, air and water quality, and climate regulation. Due to the complexity of soil, the distributions of organic compounds and microorganisms are heterogeneous on sub-cm scales, and biodegradation is therefore partly controlled by the respective localizations of organic substrates and degraders. If they are not co-localized, transfer processes become crucial for the accessibility and availability of the substrate to degraders. This spatial interaction is still poorly understood, leading to poor predictions of organic compound dynamics in soils. The objectives of this work were to better understand how the mm-scale distribution of a model pesticide, 2,4-dichlorophenoxyacetic acid (2,4-D), and its degraders drives the fate of 2,4-D at the cm soil core scale. We constructed cm-scale soil cores combining sterilized and “natural” soil aggregates in which we controlled the initial distributions of 2,4-D and soil microorganisms with the following spatial distributions: i) a homogeneous distribution of microorganisms and 2,4-D at the core-scale, ii) a co-localized distribution of microorganisms and 2,4-D in a single spot (360 mm³) and iii) a disjoint localization of microorganisms and 2,4-D in 2 soil spots (360 mm³) separated by 2 cm. Two sets of experiments were performed: one used radiolabeled ¹⁴C-2,4-D to study the fate of 2,4-D, and the other used ¹²C-2,4-D to follow the dynamics of degraders. Microcosms were incubated at 20 °C and at field capacity (−31.6 kPa). At the core scale, we followed 2,4-D mineralization over time. On three dates, soil cores with microorganisms and 2,4-D localized in soil spots, were cut out in slices and then in 360 mm³ soil cubes. The individual soil cubes were then independently analysed for extractable and non-extractable ¹⁴C and for degraders (quantitative PCR of tfdA genes). Knowing the initial position of each soil cube allowed us to establish 3D maps of 2,4-D residues and degraders in soil. The results indicated that microorganisms and pesticide localizations in soil are major driving factors of i) pesticide biodegradation, by regulating the accessibility of 2,4-D to degrading microorganisms (by diffusion); and ii) the formation of non-extractable residues (NER). These results also emphasized the dominant role of microorganisms in the formation and localization of biogenic NER at a mm-scale. To conclude, these results demonstrate the importance of considering micro-scale processes to better understand the fate of pesticides and more generally of soil organic substrates at upper scales in soil and suggest that such spatial heterogeneity should not be neglected when predicting the fate of organic compounds in soils.     

水葫芦颗粒燃料成型工艺优化

为了提高水葫芦颗粒燃料的成型品质,该文对水葫芦颗粒燃料的致密成型工艺进行了试验研究,分析了加工压力、温度、原料含水率和粉碎粒度与水葫芦颗粒燃料的颗粒密度和径向抗压力的关系。单因素和多因素正交试验研究结果表明:影响水葫芦颗粒燃料的颗粒密度的主次工艺参数排序为:压力粒度温度含水率;工艺参数温度、压力和粒度的对水葫芦颗粒燃料的径向抗压力的影响差别不大,而原料含水率的影响最小。水葫芦颗粒燃料的最佳工艺参数条件为:压力6 k N、温度100℃、含水率12%、粒度0.58 mm,在此最佳工艺参数条件下,水葫芦颗粒燃料的颗粒密度和径向抗压力可分别达到1 362.21 kg/m3和1.44 k N。研究结果为工业化生产高质量的水葫芦颗粒燃料提供理论依据。     

Leaching of 2,4-D and dicamba from home lawns

Leaching of the broadleaf herbicides 2,4-D and dicamba from home lawns was monitored with ceramic extraction plates placed at a 0.2 m depth beneath undisturbed sod. The site was located on a Merrimac sandy loam. Four treatments, consisting of two rates of herbicide applications coupled with two irrigation regimes. were evaluated on 12 plots. The low herbicide rate consisted of 1.1 and 0.1 kg ha^?1 yr^?1 of 2,4-D and dicamba, respectively. The high rate used was 3.3 and 0.33 kg ha^?1 yr^?1 of 2,4-D and dicamba applied in three equal applications. Irrigation treatments were (1) minimal irrigation to avoid drought stress and percolation from the root zone and (2) overwatering at 37.5 mm week^?1. Geometric mean concentra tions of 2,4-D ranged from 0.55 to 0.87 μg L^?1 compared to 0.26 to 0.55 μg L^?1 for dicamba. The low application-minimum irrigation treatment generated significantly higher concentrations than the other treatments for both herbicides. The low concentrations observed for both herbicides suggest that excellent degradation conditions exist in the root zone of turfgrass during the summer months when application occurs.     

Development of an analytical scheme for simazine and 2,4-D in soil and water runoff from ornamental plant nursery plots

The transport and fate of pesticides applied to ornamental plant nursery crops are not well documented. Methodology for analysis of soil and water runoff samples concomitantly containing the herbicides simazine (1-chloro-4,6-bis(ethylamino)-s-triazine) and 2,4-D ((2,4-dichlorophenoxy)acetic acid) was developed in this research to investigate the potential for runoff and leaching from ornamental nursery plots. Solid-phase extraction was used prior to analysis by gas chromatography and liquid chromatography. Chromatographic results were compared with determination by enzyme-linked immunoassay analysis. The significant analytical contributions of this research include (1) the development of a scheme using chromatographic mode sequencing for the fractionation of simazine and 2,4-D, (2) optimization of the homogeneous derivatization of 2,4-D using the methylating agent boron trifluoride in methanol as an alternative to in situ generation of diazomethane, and (3) the practical application of these techniques to field samples.     

Sorption Studies of 2,4-D on Selected Soils

Adsorption/desorption characteristics of the herbicide 2,4-D on various types of soils were investigated. Batch equilibrium techniques were used in the laboratory experiments. Data were fitted to the linear and Freundlich sorption equations. K and Kf values ranged between 0.32–1.89 L- 1 mg and 2.6 × 10-3 – 7.4 mg kg- 1, respectively. Results showed that both for linear and Freundlich adsorption equations, for all soils, K and Kf were correlated to the organic matter content (r = 0.87 and r = 0.66, respectively). Adsorption was also positively correlated with silt and clay content of soils (r = 0.53) and negatively correlated with sand content.     

Fate of 14C-ring-labeled 2,4-D, 2,4-dichlorophenol and 4-chlorophenol during straw composting

Experiments were carried out to study the transformation of ¹⁴C-ring-labeled 2,4-D and the two related chlorophenols 4-chlorophenol (4-CP) and 2,4-dichlorophenol (4-DCP) during straw composting under controlled laboratory conditions. Incubation under sterile and nonsterile conditions was done to evaluate the relative importance of the biotic and abiotic processes. Pre-composted straw was treated with the three chemicals. The availability of the different chemicals was monitored during incubations as well as their degradation. Under nonsterile conditions, the mineralization of both chlorophenols reached 20% of the applied compounds, whereas it was 52% for 2,4-D. Transitory water-soluble metabolites of 2,4-D and chlorophenols were formed but they disappeared rapidly. After 21 days, 21% of the 2,4-D and 38% of the 2,4-DCP was stabilized as nonextractable (bound) residues under nonsterile conditions. Bound residues of both chemicals were negligible under sterile conditions. Availability of chemicals as estimated by water extraction decreased during incubation proportionally to mineralization and to the formation of bound residues. The increase in immobilization of the chemical residues was stronger under nonsterile conditions than under sterile conditions. Under nonsterile conditions 71% of the 4-CP was recovered as bound residues, whereas under sterile conditions 30% of the applied 4-CP formed bound residues after formaldehyde addition and only 8% with autoclaved straw. Global microbial activity decreased in the presence of the chlorophenols probably due to their toxic effect. These data indicate that the biological activity associated with straw transformation during composting stimulates the depletion of 2,4-D and chlorophenols by mineralization and by formation of bound residues. Received: 6 September 1996     

Extractability of 2,4-D,Dicamba and MCPP from Soil

The adsorption of herbicides on soil colloids is a major factor determining their mobility, persistence, and activity in soils. Solvent extraction could be a viable option for removing sorbed contaminants in soils. This study evaluated the extractability of three herbicides: 2,4 dichlorophenoxy-acetic acid (2,4-D), 4-chloro-2-methylphenoxypropanoic acid (mecoprop acid or MCPP), and 3,6-dichloro-2-methoxybenzoic acid (dicamba). Three solvents (water, methanol, and iso-propanol) and three methods of extraction (column, batch, and soxhlet) were compared for their efficiencies in removing the herbicides from three soils (loamy sand, silt loam, and silty clay). Both linear and non-linear Freundlich isotherms were used to predict sorption intensity of herbicides on soils subjected to various extraction methods and conditions. High K_dand K_fr, and low N values were obtained for all herbicides in silty clay soil by batch extraction. Methanol was the best solvent removing approximately 97% of all added herbicides from the loamy sand either by column or soxhlet extraction method. Isopropanol ranked second by removing over 90% of all herbicides by soxhelet extraction from all three soils. However, water was ineffective in removing herbicides from any of the soils using any of the three extracting procedures used in this study. In general, the extent of herbicide removal depended on soil type, herbicide concentration, extraction procedure, solvent type and amount, and extraction time.     

水葫芦固液分离机脱水参数优化及中试运行效果

为了获得低成本、高效率的水葫芦规模化处理处置技术参数,该研究基于50t/d处理能力的工况,以自主研发的SHJ-400型水葫芦固液分离机和卧式甩刀粉碎机为基础,通过单因素试验研究了粉碎粗细、进料量和挤压脱水停留时间对水葫芦规模化脱水效果的影响,同时获得了脱水残渣与挤压汁液中的干物质、氮磷钾养分分布规律,为水葫芦脱水作业后残渣及汁液的资源化利用提供参考。结果表明,适宜的水葫芦固液分离技术参数,即水葫芦适宜粉碎粗细为20～30mm、进料量为8t/h和挤压脱水停留时间为3min;水葫芦脱水残渣和挤压汁液中的干物质分布比例分别为61.67%～65.48%和34.52%～38.33%,而大部分氮磷钾养分保留于挤压汁液中,水葫芦粉碎和固液分离环节的减容率分别为50.25%和93.70%。此外,以处理能力50 t/d示范工程为试验平台,获得了实际运行工况的脱水作业运行效果参数,即在水葫芦初始含水率95.08%条件下,经固液分离后水葫芦脱水残渣含水率为83.21%,脱水率为78.59%,水葫芦固液分离机处理能力为6.25 t/h,并通过成本测算得到水葫芦固液分离成本为4.40元/t。该研究所获得低成本、高效率的水葫芦规模化处理脱水作业技术方案,为形成水葫芦规模化处理处置工程整体解决方案提供技术支撑。     

Isolation of Cd-binding protein of water hyacinth (Eichhornia crassipes) grown in Nile river water

Many investigators have reported that water hyacinth plants can accumulate toxic heavy metal ions and may be useful for elutriation of polluted water. The purpose of our study was to search for the mechanism by which these plants tolerate and accumulate toxic metal ions. Cadmium was accumulated in the plants against the concentration gradient, mostly as a soluble form in the cytoplasm. Isolation and Purification of Cd-binding protein with sephadex A-25 and fractionation on sephadex G-100 showed that the accumulated Cd was associated with two major protein fractions.The first with molecular weight 25 - 20 kD contained about 35% of bound Cd. The second fraction with molecular weight 12 - 8 kD contained about 40% of bound Cd. The two forms were found also in water hyacinth cultivated in Nile water as a control, although the amount of Cd accumulated was less than those exposed to excess Cd.     

Relationships between microbial biomass and dissipation of 2,4-D and dicamba in soil

A study was conducted to evaluate relationships between microbial biomass and the dissipation of 2,4-D (2,4-dichlorophenoxy acetic acid) and dicamba (2-methoxy-3,6-dichlorobenzoic acid) in soil. We hypothesized that the size of the microbial biomass should be a strong predictor of the pesticide degradation capacity of a particular soil. Soils with a high microbial biomass should have relatively high levels of general microbial activity and should support a diversity of degradation pathways. In this study, we quantified the degradation of 2,4-D and dicamba in a range of soils with different concentrations of microbial biomass. The herbicides 2,4-D and dicamba were added to similar soils collected from five different land use types (home lawn, cornfield, upland hardwood forest, wetland forest, and aquifer material) and incubated for 80 days under laboratory conditions. Herbicide residue and microbial biomass (C and N) analyses were performed 5, 10, 20, 40, and 80 days following herbicide application. Microbial biomass-C and -N and soil organic matter content were positively correlated with dissipation of 2,4-D and dicamba. The results suggest that there are relationships between the size of the soil microbial biomass and the herbicide degradation capacity of an ecosystem. These relationships may be useful for developing approaches for evaluating and predicting the fate of pesticides in different ecosystems.     

Bioavailability of the herbicide 2,4-D formulated with organoclays

Research on organoclays as sorbents of pesticides has shown the usefulness of these materials as pesticide supports to prolong the efficacy of soil-applied pesticides and to reduce the large transport losses that usually affect pesticides applied in an immediately available form. Nevertheless, little information exists on the availability of organoclay-formulated pesticides for bacterial degradation. In this work, laboratory experiments were conducted to determine the adsorption-desorption behavior of two hexadecyltrimethylammonium-treated Arizona montmorillonites (SA-HDTMA₅₀ and SA-HDTMA₁₀₀) for the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), and to evaluate the ability of these organoclays to slow the release of the herbicide and to reduce herbicide leaching losses as compared to the free (technical) compound. The kinetics of mineralization of free and formulated 2,4-D by adapted bacteria was also determined. Organoclay-based formulations of 2,4-D displayed slow release properties in water and reduced herbicide leaching through soil columns, while maintained a herbicidal efficacy similar to that of the free (technical) 2,4-D. The total amount of ¹⁴C-2,4-D mineralized at the end of the biodegradation experiment (t=130 h) ranged between 30% and 46% of the formulated herbicide, which represented 53-81% of the amount of free 2,4-D mineralized in the same conditions. The release, leaching, and mineralization patterns of the formulated herbicide were found to depend both on the affinity of the organoclay for the herbicide and on the degree of interaction promoted during the preparation of the herbicide-organoclay complex. This suggests the possibility to select diverse preparations to achieve the desired release, leaching and biodegradation behavior.