表面铜螯合磁性二氧化硅固定化漆酶及其催化降解水中2，4-二氯酚

利用磁性二氧化硅表面接枝的聚丙烯酰胺络合Cu2＋离子，制备了表面铜螯合磁性SiO：材料，采用傅立叶红外光谱（FT．IR），X射线衍射（XRD）对该磁性材料进行了表征，并通过配位作用固定化漆酶，考察了其对水中2，4-二氯酚（2，4-DCP）的催化降解效能及主要影响因素。结果表明，表面铜螯合磁性SiO：固定化漆酶对2，4-DCP具有较好的催化降解效能，利用8g／L固定化漆酶催化降解50mL初始浓度为24．25mg／L的2，4-DCP，反应12h2，4-DCP去除率达91％；当pH值在3．0～6．0范围内时，2，4-DCP的去除率随反应pH值的增加而升高；2，4-DCP初始浓度在14．39～257．6mg／L范围内时，反应12h，2，4-DCP的去除率均达85％以上；给酶量增加促进2，4-DCP的去除，但过多的给酶量导致单位质量固定化漆酶催化降解2，4-DCP的速率下降；水中硫酸根离子对固定化漆酶催化降解2，4-DCP具有明显的促进作用，而碳酸氢根离子明显抑制反应的进行。     

EDTA优化纳米Pd/Fe对2,4-D的催化脱氯研究

采用EDTA优化纳米Pd/Fe催化脱氯水中2,4-二氯苯氧乙酸(2,4-D),并考察了EDTA投加浓度、pH、钯化率、温度等因素对2,4-D还原的影响.结果表明,EDTA的加入络合了纳米Pd/Fe在催化脱氯过程中生成的铁离子,抑制纳米Pd/Fe颗粒表面钝化层的形成,提高了体系的反应活性.适宜的EDTA浓度、低pH、高钯化率、低温等有利于2,4-D的还原脱氯.当EDTA浓度为25.0 mmol·L-1,纳米铁含量为1.0 g·L-1,初始pH=4.3、钯化率为0.5%,温度为25.0℃,搅拌速率为200 r·min~(-1)时,反应50 min,10.0 mg·L-1的2,4-D去除率及苯氧乙酸(PA)生成率均达到100%.     

还原脱氯-生物联合降解2,4-二氯苯氧乙酸

采用Pd/Fe双金属对2,4-二氯苯氧乙酸(2,4-D)进行催化还原脱氯,以活性污泥对2,4-D脱氯产物进行生物氧化,考察初始pH、活性污泥量、污染物初始浓度、温度等因素对生物氧化的影响情况.通过PCR-变性梯度凝胶电泳分析污泥体系菌群变化情况,高效液相色谱测定来推测目标污染物的降解过程.结果表明:1 Pd/Fe双金属可有效还原2,4-D,其主要先还原为2-氯苯氧乙酸(2-CPA),最终顺序脱氯为苯氧乙酸(PA).2 2,4-D具有较大生物毒性,其脱氯产物毒性下降,更易被生物降解.3 pH=7、污泥量50 mL/200 mL、适量的初始PA浓度(14.6 mg·L-1)和30℃均有利于PA的去除.在该条件下反应96 h,PA去除率可达84.3%.     

棉秆基活性炭的制备及其对2,4-二硝基苯酚的吸附

以棉秆为原料，以KOH为活化剂，制备了高比表面棉秆基生物质活性炭。分析了制得的活性炭的元素组成、表面官能团、吸附能力等物化性能，探讨了浸渍比，活化温度，活化时间等工艺参数对制备活性炭得率、表面官能团、碘值、亚甲基蓝值等性能的影响，并通过静态吸附实验比较了不同条件下制备活性炭对2，4-二硝基苯酚的吸附性能，探讨了典型炭样品对2，4-二硝基苯酚的等温吸附特性。结果表明，KOH活化棉秆基生物质活性炭的表面物化性质随浸渍比、活化温度等工艺参数变化而变化，活化适宜条件为浸渍比1：3、活化温度800℃、活化时间90 min，在此条件下制得的炭样的碘值为1 251 mg/g，亚甲基蓝吸附值为478 mg/g，分别是国家一级品标准的1.25倍与3.54倍；对2，4-二硝基苯酚的Langmuir最大吸附量为747 mg/g，与Freundlich模型相比，Langmuir模型能较好地描述2，4-二硝基苯酚在炭样上的吸附行为，表明制备活性炭样品表面吸附位的能量分布较为均一。     

2,4-D mineralization in unsaturated and near-saturated surface soils of an undulating,cultivated Canadian prairie landscape

The herbicide 2,4-D [2,4-(dichlorophenoxy) acetic acid] is one of the most widely used pesticides in the Canadian prairies and is frequently detected as a ground and surface water contaminant. The objective of this paper was to determine the magnitude and extent of variation of 2,4-D mineralization in a cultivated undulating prairie landscape. Microcosm incubation experiments, using a 4 × 3 × 2 factorial experimental design (soil moisture, 4 levels: 60, 85, 110, 135% of field capacity; slope position, 3 levels: upper-, mid- and lower-slopes; soil depth, 2 levels: 0–5 and 5–15 cm), were used to assess 2,4-D mineralization. The first-order mineralization rate constant (k₁) varied from 0.03 to 0.22 day^{? 1}, while total 2,4-D mineralization varied from 31 to 52%. At near-saturated conditions (110 and 135% of field capacity), the onset of 2,4-D degradation was delayed in soil obtained from the upper- and mid-slopes but not in soils obtained from the lower-slope position. The k₁ and total 2,4-D mineralizationwas significantly influenced by all three factors and their interactions. The Freundlich sorption coefficient of 2,4-D ranged from 0.83 to 2.46 ug ^1–1/ng^{? 1} mL^1/n and was significantly influenced by variations in soil organic carbon content across slope positions. The infield variability of 2,4-D sorption and mineralization observed across slope positions in this undulating field was comparable in magnitude and extent to the regional variability of 2,4-D sorption and mineralization observed in surface soils across Manitoba. The large variability of 2,4-D mineralization and sorption at different slope positions in this cultivated undulating field suggests that landform segmentation models, which are used to delineate slope positions, are important considerations in pesticide fate studies.     

Dissipation and effect of chlorophenoxy herbicide on plant pigments and carbohydrates of sunflower (Helianthus annuus L.)

The dissipation pattern of the chlorophenoxy herbicides (2,4‐D and 2,4,5‐T) residues in sunflower plants (Helianthus annuus L.) has been studied along with its effect on the changes of plant pigments (chlorophyll‐a,b, total chlorophyll, carotene and anthocyanin), sugar and starch in different parts of the plant. The residues of 2,4‐D and 2,4,5‐T remained for larger period of time (10 days) at higher concentrations than the lower concentration. The concentrations of chlorophylls and carotene were found to be reduced with the application of both 2,4‐D and 2,4,5‐T. But the chlorophyll concentrations were slowly normalized accompanied with the reduction of the herbicide residues. For anthocyanin, there was no significant effect. In case of carbohydrate, the sugar concentration was found to be raised by all doses in leaf and stem. The change in starch content in different plant parts did not follow an uniform pattern at different doses of herbicides.     

The effects of triclopyr on 2,4‐D mineralization in two soils

Abstract

The effects of the herbicide triclopyr (3,5,6‐trichloro‐2‐pyridinyloxyacetic acid) on the mineralization of 2,4‐D (2,4‐dichlorophenoyxacetic acid) in two soils which differed in their histories of prior exposure to the two herbicides were investigated. The relative effects of triclopyr on 2,4‐D mineralization and most probable numbers of 2,4‐D degraders were dependent upon the soil. Triclopyr was shown to increase 2,4‐D mineralization rates in a soil which had been exposed to both 2,4‐D and triclopyr, but decreased the mineralization rate of 2,4‐D and inhibited the increase of most probable numbers of 2,4‐D degraders in a soil that had not been directly exposed to either herbicide.     

Effects of 2,4-dichlorophenoxyacetic acid formulation on medulla spinalis of Poecilia reticulata: A histopathological study

This study investigated the possible effects of a commonly used foliar herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) formulation on medulla spinalis of lebistes. Fish were exposed to 2,4-D (15, 30, 45 mg L⁻¹), behavioral changes were monitored. Fish were fixed, histopathological examination was carried out on sections taken from the upper parts of the fish body. Histopathology showed increase in neuronal loss, swelling indicating formation of intracellular edema, vacuolization noticed as the formation of vacuoles within or adjacent to cells, deformation in the Nissl granules, pyknosis and gliosis in medulla spinalis. Behavioral changes were decreased general activity, grouping, shortness in breath, sudden rotations and jumping, loss of equilibrium and colour. In conclusion, this commercial formulation of 2,4-D is considerably neurotoxic to lebistes. Fish constitute the last link in the chain of the feeding cycle in aquatic eco-system, number of studies investigating acute and chronic neurotoxicity of various herbicides in fish should be increased.     

Sorption of 2,4-D on Natural and Organic Amended Soils of Different Characteristics

The effect of one organic amendment consisting of an urban waste compost (UWC) was assessed on the sorption properties of the herbicide 2,4-D on four soils of different physicochemical characteristics. The soils chosen were a Typic Haphorthod (ST), a Typic Endoaquept (SR), an Entic Pelloxerert (TO), and a Typic Eutrochrept (AL). Adsorption experiments were performed on the original soils, and on mixtures of these soils with UWC at a rate of 6.25% (w/w). These mixtures were used just after preparation, and after aging for 8 and 25 weeks. 2,4-D adsorption was the highest on ST soil, whereas the lowest adsorption was for SR soil. This behavior is related to the high amount of organic matter (OM) and amorphous iron and aluminum oxides content on soil ST, whereas soil SR had the lowest OM content and specific surface area of the soils of this study. Addition of exogenous OM to soils caused an increase in the 2,4-D adsorption by three of the soils treated with UWC, with the only exception being ST soil, due to an observed decrease in its specific surface area. The adsorbed amounts of the herbicide on aged organic fertilized soils diminished in three of the amended soils, but was still greater than on unamended soils. In contrast, the ST soil showed the largest adsorption for unamended soil.     

2,4-D Mineralization in soil profiles of a cultivated hummocky landscape in Manitoba,Canada

The objective of this study was to quantify 2,4-D (2,4-dichlorophenoxyacetic acid) mineralization in soil profiles characteristic of hummocky, calcareous-soil landscapes in western Canada. Twenty-five soil cores (8 cm inner diameter, 50 to 125 cm length) were collected along a 360 m transect running west to east in an agricultural field and then segmented by soil-landscape position (upper slopes, mid slopes, lower slopes and depressions) and soil horizon (A, B, and C horizons). In the A horizon, 2,4-D mineralization commenced instantaneously and the mineralization rate followed first-order kinetics. In both the B and C horizons, 2,4-D mineralization only commenced after a lag period of typically 5 to 7 days and the mineralization rate was biphasic. In the A horizon, 2,4-D mineralization parameters including the first-order mineralization rate constant (k ₁), the growth-linked mineralization rate constant (k ₂) and total 2,4-D mineralization at the end of the experiment at 56 days, were most strongly correlated to parameters describing 2,4-D sorption by soil, but were also adequately correlated to soil organic carbon content, soil pH, and carbonate content. In both B and C horizons, there was no significant correlation between 2,4-D mineralization and 2,4-D sorption parameters, and the correlation between soil properties and 2,4-D mineralization parameters was very poor. The k ₁ significantly decreased in sequence of A horizon (0.113% day^?1) > B horizon (0.024% day^?1) = C horizon (0.026% day^?1) and in each soil horizon was greater than k ₂. Total 2,4-D mineralization at 56 days also significantly decreased in sequence of A horizon (42%) > B horizon (31%) = C horizon (27%). In the A horizon, slope position had little influence on k ₁ or k ₂, except that k ₁ was significantly greater in upper slopes (0.170% day^?1) than in lower slopes (0.080% day^?1). Neither k ₁ nor k ₂ was significantly influenced by slope position in the B or C horizons. Total 2,4-D mineralization at 56 days was not influenced by slope positions in any horizon. Our results suggest that, when predicting 2,4-D transport at the field scale, pesticide fate models should consider the strong differences in 2,4-D mineralization between surface and subsurface horizons. This suggests that 2,4-D mineralization is best predicted using a model that has the ability to describe a range of non-linear mineralization curves. We also conclude that the horizontal variations in 2,4-D mineralization at the field scale will be difficult to consider in predictions of 2,4-D transport at the field scale because, within each horizon, 2,4-D mineralization was highly variable across the twenty-five soil cores, and this variability was poorly correlated to soil properties or soil-landscape position.