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1.
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.  相似文献   

2.
Biochar, the solid residual remaining after the thermochemical transformation of biomass for carbon sequestration, has been proposed to be used as a soil amendment, because of its agronomic benefits. The effect of amending soil with six biochars made from different feedstocks on the sorption and leaching of fluometuron and 4-chloro-2-methylphenoxyacetic acid (MCPA) was compared to the effect of other sorbents: an activated carbon, a Ca-rich Arizona montmorillonite modified with hexadecyltrimethylammonium organic cation (SA-HDTMA), and an agricultural organic residue from olive oil production (OOW). Soil was amended at 2% (w/w), and studies were performed following a batch equilibration procedure. Sorption of both herbicides increased in all amended soils, but decreased in soil amended with a biochar produced from macadamia nut shells made with fast pyrolysis. Lower leaching of the herbicides was observed in the soils amended with the biochars with higher surface areas BC5 and BC6 and the organoclay (OCl). Despite the increase in herbicide sorption in soils amended with two hardwood biochars (BC1 and BC3) and OOW, leaching of fluometuron and MCPA was enhanced with the addition of these amendments as compared to the unamended soil. The increased leaching is due to some amendments' soluble organic compounds, which compete or associate with herbicide molecules, enhancing their soil mobility. Thus, the results indicate that not all biochar amendments will increase sorption and decrease leaching of fluometuron and MCPA. Furthermore, the amount and composition of the organic carbon (OC) content of the amendment, especially the soluble part (DOC), can play an important role in the sorption and leaching of these herbicides.  相似文献   

3.
The herbicides 2,4-diclorophenoxiacetic and 4-chloro-2-methylphenoxyacetic acids (2,4-D and MCPA) are widely used in agricultural practices worldwide. Not only are these practices responsible of surface waters contamination, but also agrochemical industries through the discharge of their liquid effluents. In this investigation, the ability of a 2,4-D degrading Delftia sp. strain to degrade the related compound MCPA and a mixture of both herbicides was assessed in batch reactors. The strain was also employed to remove and detoxify both herbicides from a synthetic effluent in a continuous reactor. Batch experiments were conducted in a 2-L aerobic microfermentor, at 28 °C. Continuous experiments were carried out in an aerobic downflow fixed-bed reactor. Bacterial growth was evaluated by the plate count method. Degradation of the compounds was evaluated by UV spectrophotometry, gas chromatography (GC), and chemical oxygen demand (COD). Toxicity was assessed before and after the continuous process by using Lactuca sativa seeds as test organisms. Delftia sp. was able to degrade 100 mg L?1 of MCPA in 52 h. When the biodegradation assay was carried out with a mixture of 100 mg L?1 of each herbicide, the process was accomplished in 56 h. In the continuous reactor, the strain showed high efficiency in the simultaneous removal of 100 mg L?1 of each herbicide. Removals of 99.7, 99.5, and 95.0% were achieved for 2,4-D, MCPA, and COD, respectively. Samples from the influent of the continuous reactor showed high toxicity levels for Lactuca sativa seeds, while toxicity was not detected after the continuous process.  相似文献   

4.
The sustained release and reduced leaching of herbicides is expected for enhancing their efficacy and minimizing their pollution. For this purpose, the rice straw biochar made at a relatively low temperature (350 °C) (RS350) was used simultaneously as the carrier for incorporating herbicides besides as the soil amendment. In this way, the sustained release of herbicides acetochlor and 2,4-D was obtained in the release experiments, due to the high and reversible sorption by RS350 biochar. Besides, the RS350 biochar significantly reduced the leached amount of herbicides by 25.4%-40.7% for acetochlor, and by 30.2%-45.5% for 2,4-D, depending on the depth (50 or 100 mm) of biochar-amended soil horizon. The high retention of both herbicides in the biochar-amended topsoil makes it possible to extend their efficacy. The results suggest a potential way of using low temperature biochars to reduce the leaching of herbicides without impacting their efficacy.  相似文献   

5.
农药在土壤中的吸附和淋溶特性是评价其环境行为的重要指标,特别是决定了其在土壤中的迁移性。本文分别利用振荡平衡法和柱淋溶法研究了2,4-二氯苯氧基乙酸（2,4-D）在不同土壤中的吸附和淋溶特性及其影响因素。结果表明,2,4-D在3种供试土壤上的吸附特性能较好地用线性吸附等温线拟合,吸附常数心在0．95-1．54L·kg^-1之间,很难被土壤吸附。影响2,4-D在土壤中吸附的因素主要是土壤pH值,其次是有机质含量。土壤pH值增高,离子态的2,4-D量增加,吸附减弱;2,4-D在土壤中具有较强的淋溶性,影响其淋溶性能的主要因素是土壤pH值,pH值越高,淋溶性能越强。  相似文献   

6.
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 Kdand Kfr, 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.  相似文献   

7.
Two solid-phase enzyme immunoassays were developed to measure 2,4-dichlorophenoxyacetic acid (2,4-D), using 2 sets of structurally distinct immunogens and enzyme ligands. The 2,4-D analog, 2-methyl-4-chlorophenoxyacetic acid (MCPA), gave a similar response with both methods, whereas other phenoxy herbicides cross-reacted differently. In method A, the aromatic moiety of 2,4-D was distal from the carrier protein and labeled enzyme, whereas in method B, the acetic acid portion of the herbicide was distal. The use of both methods to screen for this herbicide in ground water and municipal and river water reduced the number of false-positive responses. Water sources having a low background response could be monitored with either method alone. When a concentration step, with disposable C18 extraction columns, was used, the limit of sensitivity was 5 micrograms/L. Method A was the more sensitive of the 2 methods with a limit of detection of 10 micrograms/L without the concentration step.  相似文献   

8.
Microbial populations able to degrade 2,4-D (2,4-dichlorophenoxyacetate) and MCPA (4-chloro-2-methylphenoxyacetate) were enumerated by means of a most probable number (MPN) procedure in eight Natal soils not previously treated with these herbicides. Estimated 2,4-D-degrading populations ranged from 1.26 to 245.2 and MCPA-degrading populations from 0.34 to 1377 g?1 dry soil; in seven of the soils the populations of these organisms were less than 40 and 30 g?1, respectively. Such counts indicate that for the successful isolation of 2,4-D- or MCPA-degrading microorganisms from soil, at least 1 g dry weight of soil should be used for enrichment cultures. The 2,4-D-degrading organisms occurred among the aerobic soil bacteria detectable by plate count, at frequencies of only 1 in 30 × 103 to 1 in 36 × 106 and the MCPA-degrading organisms at frequencies of 1 in 5 × 103 to 1 in 133 × 106; the ease with which the herbicide-degrading organisms can be isolated from enriched soil cultures treated with 2,4-D or MCPA is evidence of their massive preferential proliferation in response to the herbicides.Log 2,4-D- and MCPA-degrading populations did not differ significantly in four soil samples, but in the others either the 2,4-D- or the MCPA-degrading population was dominant. The longer persistence of MCPA compared with that of 2,4-D could therefore not be ascribed to quantitative differences in the populations of MCPA- and 2,4-D-degrading soil microorganisms.No relationship was evident between the soil populations of 2,4-D- or MCPA-degrading microorganisms and aerobic soil bacteria, and variations of the three populations among the soil samples were not associated in any obvious way with the soil physical and chemical characteristics, except perhaps an association of the highest counts of herbicide-degrading organisms with a sugar cane soil of sandy texture and high C: N ratio.  相似文献   

9.
Natural or synthetic sorbents for pesticides can be used to reduce contamination of soils and natural waters. The sorption of simazine and 2,4-D on montmorillonite minerals has been studied and their potential use to retard pesticide leaching in soil evaluated. Simazine and 2,4-D did not sorb on high-layer charge montmorillonite, whereas sorption on the lower layer charge montmorillonite SWy varied depending on the saturating cation. Simazine sorption increased in the order Ca(2+)SWy < K(+)SWy < Fe(3+)SWy. Simazine molecules sorb on hydrophobic microsites of the montmorillonite. Once protonated, further sorption through cation exchange takes place in the interlamellar space of the montmorillonite, as corroborated by X-ray diffraction and FT-IR studies. 2,4-D does not sorb on K(+)SWy or Ca(2+)SWy, but does sorb on Fe(3+)SWy, because the acidic character of this sorbent allows the molecular form of 2, 4-D to sorb by hydrogen bonding and/or by hydrophobic interactions. Leaching experiments in hand-packed soil columns indicate that simazine and 2,4-D application as a complex with FeSWy renders later breakthrough and lower maximum concentration peaks, and the total herbicide leached is lower than when applied as the pure analytical grade compound. These results suggest the possible use of natural soil colloids as sorbents for herbicides such as simazine and 2,4-D to retard pesticide leaching in soil, thus reducing their ground water contamination potential.  相似文献   

10.
The sorption and leaching of atrazine and MCPA (0.02 M CaCl(2) aqueous solution at 25 degrees C) by a calcareous soil from Southeastern Spain, after organic carbon (OC) amendment with a commercial peat (from 0.18% to 4.61% OC), were studied in batch and soil column experiments. Adsorption capacity (K(f)) values, obtained by fitting the experimental data to the Freundlich equation, ranged from 0.24 mg kg(-)(1) for MCPA sorption on the original soil to 5.47 mg kg(-)(1) for atrazine sorption on the peat-amended soil containing 4.61% OC. The breakthrough curves obtained from the step-function soil column experiments indicated that the amount of herbicide adsorbed ranged from 17.5 mg kg(-)(1) for MCPA in the original soil to 331 mg kg(-)(1) for atrazine in the peat-amended soil containing 1.67% OC. The results obtained from the pulse experiments indicate that the mobility of MCPA is much greater than that corresponding to atrazine.  相似文献   

11.
Aromatic acids can reach the soil from direct anthropogenic activities or, indirectly, from the degradation of many aromatic compounds, such as pesticides or polycyclic aromatic hydrocarbons. Because of the anionic character of aromatic acids at the pH of most soil and sediment environments, they are expected to move rapidly through the soil profile and to pose a great risk of ground water contamination. We designed batch and column leaching tests to characterize the behaviour of three aromatic acids differing in their chemical structures, picloram (4‐amino‐3,5,6‐trichloropicolinic acid), phthalic acid (2,2‐benzenedicarboxylic acid), and salicylic acid (2‐hydroxybenzoic acid), in four European soils with different physicochemical characteristics. Batch experiments revealed that the persistence of the three acids in soil:water suspensions decreased in the order: picloram ? phthalic acid > salicylic acid, and their dissipation curves were relatively independent of soil type. Sorption by the soils, their clay‐size fractions and model sorbents indicated much greater affinity of soil constituents for salicylic acid than for picloram or phthalic acid, most likely due to the ability of salicylic acid to form bidentate complexes with positively charged soil components. The extent of leaching of the aromatic acids in hand‐packed soil columns decreased in the order: picloram (90–96%) > phthalic acid (25–90%) > salicylic acid (0–37%), which was consistent with the sorption and persistence results of the batch tests. The organic C content, the amount of small‐size pores, and the initial concentration of aromatic acid in soil appeared to be important factors influencing the leaching patterns of phthalic acid and salicylic acid in the soils studied, but did not greatly influence the leaching pattern of picloram. Sorption and leaching of polar aromatic acids in soil can therefore vary considerably depending on the structural characteristics of the aromatic acid or soil type.  相似文献   

12.
Method 8150, published in the second edition of Test Methods for Evaluating Solid Waste, Manual SW-846, required optimization, ruggedness testing, linearity determinations, precision tests, bias testing, gas chromatographic/mass spectrometric confirmation, and quality control guidelines for validation of the protocol. This single-laboratory validation, which is applicable to the determination of the herbicides dicamba, silvex, 2,4-D, 2,4-DB, 2,4,5-T, dinoseb, MCPP, MCPA, and dichlorprop in hazardous waste extracts, was completed and is described in this report. Final ruggedness testing of the optimized procedure gave a mean recovery of 89.3% with a standard deviation of 4.3%. Percent relative standard deviations are less than 10 (n = 20, each analyte) over a 10(2) linear range of concentration for MCPP and MCPA and over a 10(3) linear range of concentration for the other target herbicide esters. Instrumental detection limits for electron capture detection and mass spectrometric identity confirmation were determined and found to be matrix-dependent.  相似文献   

13.
The physiological and biochemical basis for quinclorac resistance in a false cleavers (Galium spurium L.) biotype was investigated. There was no difference between herbicide resistant (R) and susceptible (S) false cleavers biotypes in response to 2,4-D, clopyralid, glyphosate, glufosinate-ammonium, or bentazon. On the basis of GR(50) (growth reduction of 50%) or LD(50) (lethal dose to 50% of tested plants) values, the R biotype was highly resistant to the acetolactate synthase (ALS) inhibitor, thifensulfuron-methyl (GR(50) resistance ratio R/S = 57), and quinolinecarboxylic acids (quinclorac R/S = 46), resistant to MCPA (R/S = 12), and moderately resistant to the auxinic herbicides picloram (R/S = 3), dicamba (R/S = 3), fluroxypyr (R/S = 3), and triclopyr (R/S = 2). The mechanism of quinclorac resistance was not due to differences in [(14)C]quinclorac absorption, translocation, root exudation, or metabolism. Seventy-two hours after root application of quinclorac, ethylene increased ca. 3-fold in S but not R plants when compared to controls, while ABA increased ca. 14-fold in S as opposed to ca. 3-fold in R plants suggesting an alteration in the auxin signal transduction pathway, or altered target site causes resistance in false cleavers. The R false cleavers biotype may be an excellent model system to further examine the auxin signal transduction pathway and the mechanism of quinclorac and auxinic herbicide action.  相似文献   

14.
Ground and surface water contamination by herbicides applied to olive groves in Spain and other Mediterranean countries is demanding strategies to prevent and remediate the environmental problems repeatedly caused by such herbicides. In this study, six different organic cations (L-carnitine, spermine, hexadimethrine, tyramine, phenyltrimethylammonium, and hexadecyltrimethylammonium) were incorporated into Na-rich Wyoming montmorillonite (SWy-2) and Ca-rich Arizona montmorillonite (SAz-1) at two different loadings (50% and 100% of the cation exchange capacity of the clays) as a strategy to enhance the affinity of the clay minerals for three herbicides widely used in olive groves: terbuthylazine, diuron, and MCPA. The modified montmorillonites were characterized and tested as adsorbents of the herbicides through batch adsorption tests. At the experimental conditions used, some of the modified montmorillonites removed more than 95% of the herbicide initially present in aqueous solution, whereas the unmodified clays removed less than 15%. All three herbicides displayed very strong affinities for SAz-1 exchanged with hexadecyltrimethylammonium cations, particularly when these were incorporated at 100% of the cation exchange capacity of the clay mineral. Terbuthylazine and diuron also displayed very strong affinities for SWy-2 exchanged with L-carnitine and spermine, respectively. The chemical characteristics of the organic cation greatly influenced the adsorptive properties of the resultant organoclay. The herbicides were in general reversibly adsorbed by the modified clays. The results indicate that some of the tested modified clays could be suitable for the removal of the assayed herbicides from contaminated water and also as possible supports for the design of slow release formulations of such herbicides to attenuate their environmental impact when used in high-risk scenarios such as olive groves.  相似文献   

15.
Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.  相似文献   

16.
通过盆栽小麦试验,研究了除草剂苯磺隆和2,4-D对小麦生长过程中土壤微生物量碳、氮以及碳/氮比(Cmic/Nmic)的影响。结果表明,苯磺隆、2,4-D对土壤微生物量碳、氮的影响主要表现为先抑制后激活,抑制作用随着时间的延长和浓度的增大而增强,与对照相比达极显著差异水平。苯磺隆、2,4-D对微生物量碳的抑制作用第14天和第7天分别达到最大,为54.9%和45.2%;对微生物量氮的抑制作用均为第7天最大,分别为51.0%和 65.4%。2种除草剂处理均在第28天微生物量碳、氮达到最大,为对照的1.09和1.33倍,呈极显著的激活作用,且激活作用随着浓度的增大而增强;对土壤微生物量碳/氮的影响主要呈增加-降低-增加的变化趋势。研究表明苯磺隆、2,4-D对土壤微生物量碳、氮的影响主要与处理的浓度和时间有关,与除草剂的种类无关。  相似文献   

17.
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.  相似文献   

18.
Abstract

A field study was conducted to assess the fate and mobility of two commonly used herbicides, dicamba (3,6‐dichloro‐2‐methoxybenzoic acid), and picloram (4‐amino‐3,5,6, trichloro‐2 pyridinecarboxylic acid), in an irrigated pasture. The herbicides were applied at two application rates to four plots (two replicates) that contained soil‐water collectors. Herbicide concentrations as a function of depth and application rate were evaluated statistically to determine if replicate data could be combined. Results indicated dicamba concentration variations were low, suggesting the mean value of the replicate plots could be compared; however, picloram concentration variations were high, and the replicate plot data could not be combined. Half‐time values for herbicide disappearance (time required for herbicide concentration to diminish from its maximum to half maximum levels), calculated from the arithmetic mean of the logistic equations, were found to be useful in describing herbicide transport. Half‐time values were dependent upon application rate, collector depth, pesticide type, and plot location. Dicamba applied at the low application rate was detected at 15 and 30 cm depths only, and was not detected throughout the entire study period (467 days) at deeper depths. Significant differences occurred between plots receiving the high dicamba application rate, which was attributed to permeability differences that affected herbicide migration in the soil profile. Picloram half‐time values were also affected by soil organic carbon, which increased picloram adsorption. In general, differences in herbicide concentrations were observed within plots receiving the high picloram application rates, which was primarily attributed to spatial differences in hydraulic conductivity. Herbicide disappearance was most rapid at the shallow depth (e.g., 15 cm) within plots receiving lower herbicide application rates.  相似文献   

19.
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.  相似文献   

20.
The degradation of 2, 4-D, 2, 4, 5-T, and picloram in two Philippine soils was investigated under upland and flooded (submerged) conditions. These herbicides degraded in both upland and flooded Maahas clay and Luisiana clay soils. The rate of degradation of the herbicides was more rapid in the Maahas clay soil than in the Luisiana clay soil. Among the three herbicides, 2, 4-D was the least persistent and picloram was the most persistent in both soils under both submerged and upland conditions. 2, 4, 5-T degraded more actively in the two Philippine soils in this study than studies previously reported in the available literature. The fact that both the 2, 4-D and 2, 4, 5-T did not degrade in sterilized soils during the incubation period suggests that the degradation is due to the microbial activity in the soils.  相似文献   

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