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.     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

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.     

Natural soil colloids To retard simazine and 2,4-D leaching in soil

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.     

Layered double hydroxides as supports for the slow release of acid herbicides

A Mg/Al layered double hydroxide (LDH) was intercalated with the anionic herbicides 2,4-D, MCPA, and picloram by using three different methodologies: (i) direct synthesis (DS), (ii) regeneration (RE), and (iii) ion exchange (IE). The resulting complexes were characterized and assayed by batch release and column leaching tests, aiming at the controlled release of these herbicides. All the tested LDH-herbicide complexes displayed similar slow herbicide release properties in water, although the IE method seemed to result in complexes with a greater fraction of herbicide in a readily available form. Apparently, the LDH-herbicide complexes released most of the active ingredient present in the complexes at the end of the batch release experiment. This was attributed to the replacement of the intercalated herbicide by carbonate and hydroxyl anions from the aqueous solution. Compared to the free herbicides, the application of the three LDH-herbicide complexes (RE) to soil columns resulted in reduction in the maximum herbicide concentration in leachates and led to the retardation of herbicide leaching through the soil. All LDH-herbicide complexes presented an herbicidal efficacy similar to that of the free (technical) herbicides. Our results indicated the potential applicability of LDHs as supports for the preparation of slow release formulations of acid herbicides such as 2,4-D, MCPA, or picloram.     

Ethylcellulose formulations for controlled release of the herbicide alachlor in a sandy soil

The development of controlled-release formulations of alachlor to diminish its leaching in sandy soils, avoiding groundwater contamination and maintaining its efficacy, was studied. For this purpose, ethylcellulose (EC) microencapsulated formulations (MEFs) of alachlor were prepared under different conditions and applied to soil columns to study their mobility. The results show that in all cases the release into water of alachlor from MEFs was retarded when compared with commercial formulation. Total leaching losses in soil columns were reduced to 59% from 98%. The mobility of alachlor from EC microspheres into soil columns has been greatly diminished in comparison with its current commercial formulation (CF), above all with increasing EC/herbicide ratios. Distribution of alachlor applied as MEFs at different depths in the soil was higher in the soil surface (66.3-81.3% of herbicide applied at the first 12 cm). In contrast, the residues from CF along the complete soil column were only 20.4%. From the results of bioassays, MEFs showed a higher efficacy than CF at 30 days after the treatment. The use of ME formulations could provide an advantage in minimizing the risk of groundwater contamination by alachlor and reducing the application rates, as a result of maintaining the desired concentration of the herbicide in the top soil layer, obtaining longer periods of weed control.     

Sulfosulfuron incorporated in micelles adsorbed on montmorillonite for slow release formulations

Slow release formulations of the anionic herbicide sulfosulfuron (SFS) were prepared by incorporating it in micelles of an organic cation octadecyltrimethylammonium, which adsorb on the clay-mineral montmorillonite. The fraction of SFS adsorbed on the micelle-clay complex reached 98%, whereas for monomer-clay complexes, its adsorption was insignificant. Fluorescence studies showed surface contact between the micelles and the clay surface. The rate of SFS release from the micelle-clay formulations in aqueous suspensions was slow (<1%, 72 h). Spraying SFS formulations on a thin soil layer in a funnel, followed by irrigations (50 mm), resulted in complete elution of SFS from the commercial formulation (dispersible granular) versus 4% from the micelle-clay formulation. A plant bioassay in Rehovot soil showed that these respective formulations yielded 23 and 65% of shoot growth inhibition of foxtail. Consequently, the slow release micelle-clay formulations of SFS yield significantly reduced leaching and enhanced biological activity, thus providing environmental and agricultural advantages.     

Organo-clay formulations of the hydrophobic herbicide norflurazon yield reduced leaching

The study aimed to reduce leaching of the hydrophobic herbicide norflurazon (4-chloro-5-methylamino-2-(alpha,alpha, alpha)-trifluoro-m-tolylpyridazin-3-(2H)-one) by adsorbing it on clays or organo-clays. The surface of the clay mineral montmorillonite was modified from hydrophilic to hydrophobic by preadsorbing it with organic cations, of which thioflavin-T (TFT) at a loading corresponding to (5)/(8) of the cation-exchange capacity of the clay mineral yielded the highest affinity of adsorption of norflurazon. Pillared clay (PC) used without organic cations exhibited enhanced affinity for norflurazon adsorption, much higher than that of montmorillonite or sepiolite. Fourier transform infrared (FTIR) results showed interactions between aromatic moieties of preadsorbed TFT and the herbicide. Stronger interaction of the herbicide with a clay mineral or organo-clay corresponded to its slower release. Formulations prepared on the basis of montmorillonite-TFT and PC were more effective in reducing herbicide leaching in soil columns in comparison to the commercial formulation, whereas the herbicidal efficiencies were comparable.     

Selective modification of clay minerals for the adsorption of herbicides widely used in olive groves

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.     

Effect of liming on hexazinone sorption and desorption behavior in various soils

Liming is a practice commonly used to modify soil acidity, neutralize aluminum, and increase calcium and magnesium in the soil. Liming can change herbicide retention processes and consequently weed control and potential environmental contamination. The effects of liming on the sorption and desorption of hexazinone in different soils were evaluated. Samples from seven Brazilian soils were collected and separated into two subsamples, with and without limestone incubation. Hexazinone was quantified using ultra high-performance liquid chromatography. The sorption and desorption coefficients were determined in soils using Freundlich isotherms. Increasing the pH did not alter the sorption kinetics of hexazinone in the same soil class. The shortest sorption time of hexazinone occurred in soils with higher organic matter (OM) and clay content. Liming reduced the sorption and increased the desorption of hexazinone in the soils, which was caused by the increase in pH and reduction of OM content. Although the application of limestone increased desorption, the rate at which this process occurred was less than the sorption rate of hexazinone in most cases. In alkaline soils, the recommended dose of hexazinone for pre-emergence application should be low to avoid leaching and reduce the contamination of groundwater resources.     

Adsorption and leaching behaviour of the herbicide alachlor (2-chloro-2', 6'diethyl-N-(methoxymethyl) acetanilide) in a soil specific management

Abstract. Uniform application rates of fertilizers and herbicides may result in over-treating some soils and under-treating others; costs may be unnecessarily large and soil, ground water and surface waters may be contaminated. An alternative is site specific treatment, tailored to individual soil types present in agricultural fields of any size. To study the pollution hazards of the herbicide alachlor, leaching and adsorption experiments used disturbed samples and undisturbed soil columns. Adjoining Ves, Normania and Webster soil series (Udic Haplustoll; Aquic Haplustoll; Typic Haplaquoll) were sampled and analysed for various properties. Ring uniformly ¹⁴C-labelled alachlor was used to study adsorption and leaching characteristics in these soils. Results show different alachlor behaviour in topsoil and subsoil layers.     

Sulfentrazone adsorbed on micelle-montmorillonite complexes for slow release in soil

Interactions of the herbicide sulfentrazone with the cationic surfactants octadecyltrimethylammonium (ODTMA), hexadecyltrimethylammonium (HDTMA), and benzyldimethylhexadecylammonium (BDMHDA) have been studied for the design of slow-release formulations based on sulfentrazone adsorbed on a micelle-montmorillonite complex. Adsorbed amounts of sulfentrazone on ODTMA- and BDMHDA-montmorillonite complexes were 99.2-99.8% of that added, and desorption of herbicide in water during 24 h was low. After 10 washings in funnels with soil, only 2.6% of herbicide was released from ODTMA-montmorillonite formulations versus 100% release from the commercial formulation. The strong binding of sulfentrazone to micelles was confirmed by pH and spectroscopic measurements and was explained by the formation of ionic pairs between cationic surfactant and anionic herbicide. The ODTMA-clay and commercial formulations of sulfentrazone yield almost complete and 40% growth inhibition of green foxtail, respectively, at 700 g of active ingredient/ha. Hence, the slow release from micelle-clay formulations of sulfentrazone promotes its biological activity and reduces environmental contamination.     

Slow-release formulations of sulfometuron incorporated in micelles adsorbed on montmorillonite

The design and tests of slow-release formulations of sulfometuron (SFM), an anionic sulfonylurea herbicide, are described. The formulations are based on incorporation of the herbicide in octadecyltrimethylammonium (ODTMA) micelles, which adsorb on a clay mineral, montmorillonite. An optimization of herbicide/micelle clay ratios yielded high adsorption of SFM (95%), and at a 1% (w/w) water suspension only 0.5% of the adsorbed SFM was released at times varying from hours to 9 days. An analytical test in Seville soil showed that under excessive irrigation (400 mm) 100% of the commercial formulation leached, whereas the micelle-clay formulations showed only 50-65% elution. A plant bioassay in Rehovot soil showed that the commercial dispersible granule formulation (Oust, 75% ai sulfometuron methyl) yielded only 23% root elongation inhibition at the top 5 cm of the soil, whereas complete inhibition was achieved with the micelle-clay formulation. The detected concentration of SFM for the micelle-clay formulation at a depth of 15-20 cm was half of that detected for the commercial one, indicating a reduction in leaching when applying the micelle-clay formulation. A 10-fold reduction in the applied dose of SFM in the micelle-clay formulations resulted in good herbicidal activity of 60-87% inhibition. These characteristics make the new formulation promising from the environmental and economic points of view.     

Sulfometuron incorporation in cationic micelles adsorbed on montmorillonite

The aim of this study was to understand the interactions between alkylammonium cations present as monomers and micelles and a clay mineral, montmorillonite, to develop slow release formulations of anionic herbicides, such as sulfometuron (SFM) whose leaching in soils is an environmental and economic problem. In the proposed formulation the herbicide is incorporated in positively charged micelles of quaternary amine cations, which in turn adsorb on the negatively charged clay. The adsorption of hexadecyltrimethylammonium (HDTMA) and octadecyltrimethylammonium (ODTMA) on montmorillonite was studied above and below their critical micelle concentrations (CMC). At concentrations above the CMC, the loading exceeded the clay's cation exchange capacity (CEC) and indicated higher affinity of the cation with the longer alkyl chain. An adsorption model could adequately simulate adsorption at concentrations below the CMC, and yield fair predictions for the effect of ionic strength. The model indicated that above the CMC adsorbed micelles contributed significantly to the amount of ODTMA adsorbed. Evidence for adsorption of ODTMA micelles on montmorillonite was provided by X-ray diffraction, freeze-fracture electron microscopy, and dialysis bag measurements. SFM was not adsorbed directly on the clay mineral, and adsorbed at low levels, when the organic cation was adsorbed as monomers. In contrast, a large fraction of SFM adsorbed on the clay mineral when incorporated in micelles that adsorbed on the clay.     

Organo-clay formulation of acetochlor for reduced movement in soil.

This study aimed to design ecologically acceptable formulations of acetochlor by adsorbing it on montmorillonite exchanged by a small organic cation, phenyltrimethylammonium (PTMA). Adsorption of acetochlor on the clay mineral exchanged with different organic cations and its release from these complexes were determined by GC and modeled by Langmuir equation. Interactions between acetochlor molecules and the exchanged organic cation on the clay surface were studied by Fourier transform infrared spectroscopy. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA at a loading of 0.5 mmol/g of clay were higher than at a loading up to the cation-exchange capacity, i.e., 0.8 mmol/g, and were higher than obtained by using a clay mineral exchanged by other organic cations. Preloading montmorillonite by PTMA at 0.5 mmol/g yielded maximal shifts of the infrared peaks of the herbicide. The above formulation of acetochlor yielded slow release in water and showed improved weed control in field and greenhouse experiments in comparison with the commercial formulation. The PTMA-clay formulation of acetochlor maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching and persistence under field conditions. The application of this formulation can minimize the risk to groundwater and can reduce the applied rates.     

不同类型耕地紫色土中3,5,6-三氯-2-吡啶醇迁移试验与模拟

3,5,6-三氯-2-吡啶醇(TCP)的化学结构稳定、水溶性高、运移能力强,对水体具有潜在的污染风险。在有机质含量低、大孔隙度高、导水性好的紫色土地区,风险更加显著。为研究TCP在紫色中的迁移规律,该研究依据紫色土的典型耕作类型,在中国科学院盐亭国家紫色土农业生态试验站采集3组土样(小麦-玉米轮作的坡地、水稻-油菜轮作的水旱农田和萝卜-白菜套种的菜地),通过批量平衡法研究紫色土对TCP的吸附特征,并采用稳定流场饱和均质土柱的易混合置换试验研究TCP的动态迁移过程,最后对其迁移动态进行模拟。结果表明:紫色土对TCP的吸附特征呈线性,在坡地、水旱农田和菜地中的吸附系数分别为1.94、1.22和1.02 L/kg,且黏土含量和矿物组成是主要影响因子;TCP的出流平衡浓度分别为初始浓度的77%(坡地)、84%(水旱农田)和92%(菜地),相应的平衡时刻分别为2.88PV、4PV和6.5PV,表明TCP对环境的污染风险较高;用非平衡两点对流弥散模型模拟TCP在3种耕作条件下迁移,表明TCP以瞬时吸附为主,其水动力弥散系数和分形系数在坡地、水旱农田和菜地中依次减小,但一阶动力学常数依次增大。研究结果为探索TCP在紫色土壤中的迁移机制和预测防止TCP对环境的污染提供了参考依据。     

Leaching of nitrogen forms from controlled‐release nitrogen fertilizers

Abstract

Application of soluble forms of nitrogen (N) fertilizers to sandy soils may cause leaching of nitrate N (NO₃‐N) resulting in contamination of groundwater. The leaching loss of N may be reduced to a certain extent by the use of controlled‐release N formulations. A leaching column study was conducted to evaluate the leaching of urea, ammonium N (NH₄‐N), and NO₃‐N forms from selected urea‐based controlled‐release formulations (Meister, Osmocote, and Poly‐S) and uncoated urea under eight cycles of intermittent leaching and dry conditions. Following leaching of 1,760 mL of water (equivalent to 40 cm rainfall) through the soil columns, the recovery of total N (sum of all forms) in the leachate accounted for 28, 12, 6, or 5% of the total N applied as urea, Poly‐S, Meister, and Osmocote, respectively. Loss of urea‐N from all fertilizer sources was pronounced during the initial leaching events (with the exception of Meister). Cumulative leaching of urea‐N was 10% for uncoated urea while <1.7% for the controlled‐release formulations. Cumulative leaching of NH₄‐N was 6.2% for uncoated urea while <0.5% for the controlled‐release formulations. Cumulative leaching loss of NO₃‐N was 3.78% for Osmocote, 4.6% for Meister, 10.4% for urea, and 10.5% for Poly‐S. This study demonstrates a significant reduction in leaching of N forms from controlled‐release formulations as compared to that from the soluble form.     

Influence of soil moisture on sorption and degradation of hexazinone and simazine in soil.

Sorption and degradation rates of hexazinone and simazine on soil were determined in a sandy loam soil incubated, during 44 days, at 25 degrees C with moisture contents ranging from 4% to 18%. Herbicide levels in soil solution were also measured, after extraction of this solution by a centrifugation method. All experiments were conducted with treated soil in plastic columns, and the results showed that this method is suitable for the simultaneous study of pesticide sorption and degradation in soil at different environmental conditions. In general, sorption of both herbicides was higher for aged herbicide residues compared to recently applied herbicides, and soil subjected to drying and rewetting cycles had the highest sorption values. K(f) values ranged from 0.5 to 1.2 for simazine and from 0.2 to 0.4 for hexazinone. Degradation rates increased with soil moisture content for both herbicides, and drying-rewetting of soil yielded degradation rates slower than that obtained at 10% soil moisture content. Hexazinone concentration in soil solution decreased with incubation time faster than simazine.     

Organoclay formulations of acetochlor: effect of high salt concentration

This study aimed to evaluate new methodology for designing ecologically acceptable formulations of acetochlor. Modification of montmorillonite with phenyltrimethylammonium chloride (PTMA) or benzyltrimethylammonium chloride (BTMA) and organoclay formulations of acetochlor were prepared in the presence of high concentrations of sodium chloride (150 g/L). Acetochlor concentration in the equilibrium solutions was determined by HPLC. Release of acetochlor in a water system was performed by a funnel experiment. Leaching of acetochlor in soil was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of acetochlor on montmorillonite exchanged by PTMA or BTMA were increased as NaCl concentration increased in the equilibrium solution. Leaching of acetochlor from organoclay formulations was significantly inhibited to the top soil layer (0-5 cm) when the formulations were prepared at extreme NaCl concentration (100-150 g/L). These results are in accord with a funnel experiment that showed a reduction in acetochlor release from the montmorillonite-based formulations. The application of this method for herbicide formulation would produce ecologically acceptable herbicide formulations that can significantly minimize the risk to groundwater pollution.     

Montmorillonite-phenyltrimethylammonium yields environmentally improved formulations of hydrophobic herbicides

This study aimed to design formulations of hydrophobic herbicides, alachlor and metolachlor, by adsorbing them on the clay mineral montmorillonite preadsorbed by the small organic cation phenyltrimethylammonium (PTMA). An adsorption model that considers electrostatics and specific binding and the possibility of cation adsorption above the cation exchange capacity (CEC) could explain and yield predictions for PTMA adsorption in the presence of NaCl concentrations from 0 to 500 mM. Adsorption of alachlor and metolachlor from aqueous solution on a clay mineral preadsorbed by PTMA was determined by GC and modeled by Langmuir equation. Herbicide interactions with the organoclay were studied by Fourier transform infrared spectroscopy. Leaching of herbicides was determined by a bioassay using a column technique and Setaria viridis as a test plant. The adsorbed amounts of alachlor and metolachlor on montmorillonite preadsorbed by PTMA at a loading of 0. 5 mol/kg (Mont-PTMA0.5) were higher than at a loading up to the CEC, that is, 0.8 mol/kg, and were higher than those obtained by using several other organic cations. Herbicide formulations based on Mont-PTMA0.5 yielded the largest shifts of the infrared peaks of the herbicides. These formulations based on Mont-PTMA0.5 gave slower release and showed improved weed control in comparison with formulations based on other organoclays. These formulations maintained herbicidal activity in the topsoil and yielded the most significant reduction in herbicide leaching.     

炭基肥和竹炭对土壤氮素淋失和微生物的影响

为了研究竹炭和炭基缓释肥添加对毛竹林土壤氮素流失和细菌群落结构的影响,采用室内土柱淋溶试验,测定了淋溶水中NH_4⁺—N和NO_3^-—N浓度,分析了细菌群落多样性和组成。结果表明,与对照相比,炭基缓释肥的添加可以使土柱NH_4⁺—N和NO_3^-—N累积淋溶量分别降低12.5%和13.6%。此外,竹炭的添加可以显著降低NH_4⁺—N累积淋溶量(P<0.05),但是对NO_3^-—N的影响不显著。炭基缓释肥的添加可以增加土壤Nitrospira(硝化螺菌属)、Nitrosospria(亚硝化螺菌属)和Nitrobacter(硝化杆菌属)细菌的相对丰度,提高下层淋溶土壤反硝化优势菌群(丰度>0.1%)Burkholderia(伯克霍尔德菌属)、Cupriavidus(贪铜菌属)和Bradyrhizobium(慢生根瘤菌属)的相对丰度。炭基缓释肥添加对土壤NH_4⁺—N和NO_3^-—N的淋溶影响可能与土壤氮素循环微生物密切相关。