Degradation of chloroacetanilide herbicides by anodic fenton treatment

Anodic Fenton treatment (AFT) is an electrochemical treatment employing the Fenton reaction for the generation of hydroxyl radicals, strong oxidants that can degrade organic compounds via hydrogen abstraction. AFT has potential use for the remediation of aqueous pesticide waste. The degradation rates of chloroacetanilides by AFT were investigated in this work, which demonstrates that AFT can be used to rapidly and completely remove chloroacetanilide herbicides from aqueous solutions. Acetochlor, alachlor, butachlor, metolachlor, and propachlor were treated by AFT, and parent compound concentrations were analyzed over the course of the treatment time. Degradation curves were plotted and fitted by the AFT kinetic model for each herbicide, and AFT model kinetic parameters were used to calculate degradation rate constants. The reactivity order of these five active ingredients toward hydroxyl radical was acetochlor approximately metolachlor > butachlor approximately alachlor > propachlor. Treatment of the chloroacetanilides by AFT removed the parent compounds but did not completely mineralize them. However, AFT did result in an increase in the biodegradability of chloroacetanilide aqueous solutions, as evidenced by an increase in the 5-day biochemical oxygen demand to chemical oxygen demand ratio (BOD5/COD) to >0.3, indicating completely biodegradable solutions. Several degradation products were formed and subsequently degraded, although not always completely. Some of these were identified by mass spectral analyses. Among the products, isomers of phenolic and carbonyl derivatives of parent compounds were common to each of the herbicides analyzed. More extensively oxidized products were not detected. Degradation pathways are proposed for each of the parent compounds and identified products.     

Structural influences in relative sorptivity of chloroacetanilide herbicides on soil

Adsorption of the chloroacetanilide herbicides acetochlor, alachlor, metolachlor, and propachlor was determined on soils and soil components, and their structural differences were used to explain their sorptivity orders. On all soils and soil humic acids, adsorption decreased in the order: metolachlor > acetochlor > propachlor > alachlor. On Ca(2+)-saturated montmorillonite, the order changed to metolachlor > acetochlor > alachlor > propachlor. FT-IR differential spectra of herbicide-clay or herbicide-humic acid-clay showed possible formation of hydrogen bonds and charge-transfer bonds between herbicides and adsorbents. The different substitutions and their spatial arrangement in the herbicide molecule were found to affect the relative sorptivity of these herbicides by influencing the reactivity of functional groups participating in these bond interactions. It was further suggested that structural characteristics of pesticides from the same class could be used to improve prediction of pesticide adsorption on soil.     

Pressurized fluid extraction for quantitative recovery of chloroacetanilide and nitrogen heterocyclic herbicides in soil

Pressurized fluid extraction (PFE) is a new sample extraction method operated at elevated temperatures and pressures with liquid solvents. The use of PFE was investigated for the extraction of four Hawaiian clayey soils fortified with the selected chloroacetanilide and nitrogen heterocyclic herbicides Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron. The effects of operation temperature, pressure, flush volume, and static cycles on PFE performance were studied. Water was the most effective modifier of PFE for quantitative recoveries of the five herbicides in soils. The simple extraction method required pretreatment of the soil with 37.6% water and subsequent two-static-cycle extraction with a total of 32 mL of acetone at 1500 psi and 100 degrees C. Average recoveries of Alachlor, Bromacil, Hexazinone, Metribuzin, and Tebuthiuron ranged from 93 to 103% by the water-assisted PFE, compared with only 68-83% recoveries of the corresponding chemicals when no water was used. The extraction time and total organic solvent consumption were reduced from 18 h and 300 mL by Soxhlet to 22 min or less and 80 mL or less of organic solvent by PFE.     

Kinetics and mechanism of the nucleophilic displacement reactions of chloroacetanilide herbicides: investigation of alpha-substituent effects

The ease with which alpha-chloroacetanilide herbicides undergo displacement reactions with strong nucleophiles, and their recalcitrance toward weak ones, is intimately related to their herbicidal properties and environmental chemistry. In this study, we investigate the kinetics and mechanisms of nucleophilic substitution reactions of propachlor and alachlor in aqueous solution. The role played by the alpha-amide group was examined by including several structurally related analogs of propachlor possessing modified alpha substituents. The overall second-order nature of the reaction, the negative DeltaS(double dagger) values, the weak influence of ionic strength on reactivity, and structure-reactivity trends together support an intermolecular S(N)2 mechanism rather than an intramolecular reaction for alpha-chloroacetanilides as well as the alpha-chlorothioacetanilide analog of propachlor. In contrast, the alpha-methylene analog exhibits kinetics and a salt effect consistent with anchimeric assistance by the aniline nitrogen. Electronic interactions with the alpha-anilide substituent, rather than neighboring group participation, can be inferred to govern the reactivity of alpha-chloroacetanilides toward nucleophiles.     

沼液沼渣对温室迷你黄瓜品质的影响

试验以化肥、农家肥为对照,研究了沼液、沼渣对迷你黄瓜品质的影响。结果表明,以沼渣为基肥,辅以植株叶面喷施沼液,对提高迷你黄瓜品质有明显的作用。其中施沼渣A2的处理对降低硝酸盐含量作用最明显,比CK1、CK2分别降低了14%和41%的硝酸盐。100%沼液(B2)叶面喷施可显著降低硝酸盐的含量,一次喷施可降低45%左右,其中A1B1、A1B2处理喷沼液后叶绿素含量平均提高了89%,A1B2处理的Vc上升了77%,综合评价后尤以A2B2处理效果最好,在保证高产的同时,Vc含量达48.63 mg/100 g鲜重,可溶性糖含量达22.16%,硝酸盐含量为90.74 mg/kg。     

沼渣营养价值及沼渣源饲料和其生产的猪肉重金属残留分析

对牛粪、玉米秸秆作为发酵原料生产沼气的发酵残留物--沼渣的营养价值及沼渣源配合饲料和沼渣源配合饲料生产的猪肉的重金属残留进行了分析.结果表明,风干沼渣中干物质、粗蛋白、粗脂肪、粗灰分、粗纤维含量分别为857.7mg·g-1、99.0mg·g-1、34.9mg·g-1、10.7mg·g-1、252.7mg·g-1;重金属元素镉、铅、铜含量分别为18.48P,g·kg-1、42.50μg·kg-1、20.80μg·kg-1,汞未检出.对照组、沼渣Ⅰ组、沼渣Ⅱ组饲料中镉、铅、铜、汞的含量均低于国家饲料卫生标准;猪肉中重金属镉、铅、铜含量对照组、沼渣Ⅰ组、沼渣Ⅱ组分别为0.033mg·kg-1、0.044mg·kg-1、0.058mg·kg-1,0.268mg·kg-1、0.364mg·kg-1、0.393mg·kg-1,5.555mg·kgM-1、7.180mg·kg-1、8.404mg·kg-1,汞均未检出.沼渣作为猪饲料源利用有一定的潜力,以2%～10%在饲料中添加不会引起猪肉重金属镉、铅、铜、汞含量超标.     

Nitrogen availability of various biogas residues applied to ryegrass

Biogas plants in Germany are producing an increasing amount of biogas residues to be recycled via agricultural crop production. To test whether the wide range of various substrates used in the anaerobic digestion can affect the chemical composition and nutrient availability, seven biogas residues derived from different substrates were investigated with respect to their N supply to ryegrass. Both the short‐term and the long‐term N availability were studied in a 309‐d pot experiment lasting for five successive growth cycles each starting with a fertilizer application. The organic fertilizers were applied based on an equal amount of ammonium‐N (300 mg N per pot) and compared to mineral N from ammonium nitrate of equal dosage. Biogas residues varied greatly in their chemical composition (ammonium‐N 0.20% to 0.51%, N_total 0.36% to 0.75%, and C_org 1.85% to 4.75% in fresh matter). After the first growth cycle, the N availability of the biogas residues applied based on ammonium‐N was at least equal to that from ammonium nitrate. Differences in N offtake after one fertilizer application were negatively correlated to the C_org : N_org ratio of the organic fertilizers. After five successive fertilizer applications, the N utilization of most of the organic fertilizers was increased compared to that of the mineral fertilizer. It is concluded that biogas residues provide plant‐available N at least corresponding to their ammonium content and that the accumulation of organic N in soil through repeated application of biogas residues contributes to N release.     

Fate of fatty acids derived from biogas residues in arable soil

Biogas residues are rich in microbial biomass and contribute to organic matter formation when applied to soils. Here we present a detailed analysis of the fatty acids derived from ¹³C-labelled biogas residues applied to arable soil and incubated for 378 days. We applied a differential approach using phospholipid fatty acids and total fatty acids to evaluate the carbon dynamics in living biomass and non-living soil organic matter. Biogas residue addition increased the microbial biomass in soil. The sum of ¹³C-labelled phospholipid fatty acids decreased to ∼60% during incubation whereas the decrease of t-FA was higher (to 33%). Compound-specific fatty acid analysis showed fatty acid specific incorporation or loss of ¹³C, indicating hints for the carbon flow within the microbial food web. Overall, microbial biomass in biogas residues may be a significant contributor to soil organic matter formation.     

沼气及其残留物综合利用途径、作用与效益

简述了沼气及其残留物综合利用途径、作用与效益，指出沼气发酵系统是生态农业的组成环节，在再生资源优化处理、农业生态经济系统及农村经济发展方面均起着重要作用，是农民脱贫致富的有效途径。     

改良剂与沼液配施对中度苏打盐碱土的改良效果研究

为了探究改良剂与沼液配施的合理方案,实现盐碱地改良,针对吉林省大安市盐碱地,通过大田试验,研究沼液与改良剂配施对苏打盐碱土的改良效果。试验结果表明,改良剂与沼液配施均能够有效提高土壤有机质、有效磷、速效钾、碱解氮的含量,增大总孔隙度,增加了土壤团聚体的数量,改善了土壤团聚体稳定性,水稻产量显著提升,并有效降低土壤pH值、土壤容重、碱化度、水溶性盐含量。综合分析,脱硫石膏与沼液配施对苏打盐碱土改良效果最好,对比未施用沼液的处理,有机质含量提升100%,有效磷含量提升34%,速效钾含量提升59%,碱解氮含量提升104%,总孔隙度提升14%,土壤团聚体数量显著增加,土壤团聚体稳定性得到明显改善,增产率为76.77%,土壤p H值降低12%,土壤容重降低9.9%,碱化度降低11%,水溶性盐含量降低48%。     

Microbial residues were increased by film mulching with manure amendment in a semiarid agroecosystem

Amino sugars, as a kind of microbial residue, are strongly associated with cycling of microbial-derived soil organic matter. However, responses of amino sugars to agricultural practices on the Loess Plateau in North-western China are poorly known. The objective was to evaluate effects of film mulching (no film mulching + NPK fertilizers, CK; film mulching + NPK fertilizers, PF; film mulching + NPK fertilizers + cow manure, FM) on accumulations of amino sugars in this region. FM significantly increased total amino sugar by 190.46 mg kg^?1 in 0–10 cm layer and 214.66 mg kg^?1 in 10–20 cm layer relative to CK, but PF significantly decreased it by 139.28 mg kg^?1 in 0–10 cm layer. Ratios of glucosamine to muramic acid were markedly decreased by 2.50 in 0–10 cm layer and 2.28 in 10–20 cm layer in FM than CK, suggesting a tendency of microbial residues pool shift towards bacterial residues in this agroecosystem. These results indicated film mulching alone was not benefitial to accumulation of amino sugar while organic manure contributed to the build-up of amino sugar partly due to manure contained microbial residues. The different patterns of amino sugars suggested significant changes in the quality of microbial-derived organic matter.     

Dynamics of dissolved and extractable organic nitrogen upon soil amendment with crop residues

Dissolved organic nitrogen (DON) is increasingly recognized as a pivotal pool in the soil nitrogen (N) cycle. Numerous devices and sampling procedures have been used to estimate its size, varying from in situ collection of soil solution to extraction of dried soil with salt solutions. Extractable organic N (EON) not only consists of DON but contains also compounds released from soil biomass and desorbed organic matter. There is no consensus whether DON or EON primarily regulates N mineralisation in soil, and their contribution to N mineralisation has not been quantified simultaneously. We evaluated three sampling procedures on their ability to determine the dynamic of dissolved organic N pools. The three procedures were the determination of DON in 1) soil solution collected by centrifugation, and the determination of EON in 2) a 0.01 M CaCl₂ extract of field moist or 3) dried soil. We added unlabeled leek and ¹⁵N-labeled ryegrass residues to a loamy sandy soil to create a temporarily increase in DON and EON, to stimulate microbial activity, and to test whether the source and dynamics of the three pools differ. We also tested whether the flow of N through DON or EON was associated with the production of inorganic N using ¹⁵N isotope tracing. Sampling procedures significantly affected the amount, but not the dynamics and origin of the three organic N pools. DON and EON (determined on field-moist and dried soils) showed all a significant increase upon crop amendment and returned to their background concentrations within 10 to 30 days. The fraction of DON and EON originating from the crop residue slightly decreased over 138 days and was not different for DON and EON. Field moist extraction of a loamy sandy soil with 0.01 M CaCl₂ gave a reliable estimate of the concentration of in situ dissolved organic N. In contrast, extraction of dried soil significantly increased EON compared to DON. The agreement in dynamics, ¹⁵N enrichment and C-to-N ratio’s indicate that dissolved and extracted organic N have a similar role in N mineralisation. Our results also suggest that they make a minor contribution to N mineralisation; changes in the turnover rate of EON were not associated with changes in the net N mineralisation rate.     

以沼渣为原料固态发酵生产Bt生物农药

沼渣是沼气工程中产生的副产物,由于其富含营养物质及微量元素,而广泛应用于农业,畜牧业,养殖业等方面。Bt生物农药是一类具有选择性和高效性的杀虫剂,但是由于其原料的成本较高从而限制了生物农药的发展,而沼渣中富含微生物所需要的各种养分并且价格低廉,因此该文以生产沼气后的沼渣为资源,运用固态发酵,探索了利用沼渣制备苏云金杆菌生物农药的可行性。首先对沼渣营养成分进行了分析,分析表明其营养物质丰富,适合苏云金芽孢杆菌的生长与增殖。其次对菌种的沼渣培养基进行了优化,优化后的培养基质量分数为：50%的沼渣添加35%啤酒糟,10%玉米粉,5%豆饼粉,并与常规培养基和单纯沼渣的发酵进程进行了对比。在优化培养基条件下,发酵48 h后,芽孢数达到5.23×1010 CFU/g,毒力效价为16 100 IU/mg。在传统培养基中芽孢数2.55×1010 CFU/g,毒力效价12 500 IU/mg,而在单纯沼渣中Bt产量及毒性为1.74×108 CFU/g,6000 IU/mg。采用沼渣发酵制备Bt生物农药与传统培养基比较,降低了36.3%的生产成本,且发酵性能优良,也为沼渣的利用寻找到崭新的途径。     

Determination of triazine and chloroacetanilide herbicides in soils by microwave-assisted extraction (MAE) coupled to gas chromatographic analysis with either GC-NPD or GC-MS

A simple and rapid method based on microwave-assisted extraction (MAE) coupled to gas chromatographic analysis was developed for the analysis of triazine (atrazine, cyanazine, metribuzine, simazine and deethylatrazine, and deisopropylatrazine) and chloroacetanilide (acetochlor, alachlor, and metolachlor) herbicide residues in soils. Soil samples are processed by MAE for 5 min at 80 degrees C in the presence of acetonitrile (20 mL/sample). Mean recovery values of most solutes are >80% in the 10 to 500 microg/kg fortification range with respective RSDs (relative standard deviations) < 20%. The limits of quantification (LOQ) and limits of detection (LOD) are 10 and 1 to 5 microg/kg, respectively. The method was validated with two types of soils containing 1.5 and 3.0% organic matter content, respectively; no statistically significant differences were found between solute recovery values from the two types of soils. The solute mean recovery values from freshly spiked (24 h aging) and spiked samples stored refrigerated for one week before processed were also not statistically different. Residue levels determined in field weathered soils were higher when soils were processed by MAE than with a comparison method based on flask-shaking of soil suspensions overnight. Extracts were analyzed by a gas chromatographic system equipped either with a thermionic (GC-NPD) or a mass spectrometric detector (GC-MS).     

利用牧草与沼渣栽培毛木耳及其残渣改良土壤效果

以不同比例牧草与沼渣替代木屑栽培毛木耳对其产量、品质及氨基酸含量影响各异。30%草粉 +30%沼渣替代木屑效果较好,生物效率为107.5%,产量比对照高82.2%,粗蛋白、氨基酸、粗脂肪、可溶性糖含量分别比对照高3.7%、1.75%、0.13%、0.37%;以50%草粉或沼渣替代木屑其毛木耳产量分别比对照高55.1%和61.0%。山地果园连续3年施用5t/hm²沼渣、5t/hm²菌渣和5t/hm²鲜草处理区与对照相比,其红壤中腐殖酸碳含量分 别提高22.9%、26.5%和16.5%;红壤中团粒结构依次提高78.5%、79.9%和69.3%,改良土壤效果较好。     

Use of rice straw biochar simultaneously as the sustained release carrier of herbicides and soil amendment for their reduced leaching

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.     

Nitrous oxide emissions as influenced by amendment of plant residues with different C:N ratios

To investigate the influence of plant residues decomposition on N₂O emission, laboratory incubations were carried out for a period of 21 days using urea and five plant residues with a wide range of C:N ratios from 8 to 118. Incorporation of plant residues enhanced N₂O and CO₂ emissions. The two gas fluxes were significantly correlated (R²=0.775, p<0.001). Cumulative emissions of N₂O and CO₂ were negatively correlated with the C:N ratio in plant residues (R²=0.783 and 0.986 for N₂O, and 0.854 for CO₂, respectively). A negative relationship between the N₂O-N/NO₃⁻-N ratio and the C:N ratio was observed (R²=0.867) when residue plus urea was added. We calculated the changes in dissolved organic C (DOC) and the relevant changes in N₂O emission. The incorporation of residues increased DOC when compared with the control, while the incorporation of residue plus urea decreased DOC. Cumulative emissions of N₂O and CO₂ were positively correlated with DOC concentration measured at the end of the incubation. In addition, the N₂O emission fraction, defined as N₂O-N emissions per unit N input, was not found to be a constant for either residue-N or urea-N amendment but dependent on C:N ratio when plant residue was incorporated.     

“四位一体”户用沼气工程建设对农民种植行为影响的计量经济学分析

运用统计学方法分别从描述统计量和计量经济模型两个方面分析了生态家园建设对农户种植行为的影响。结果发现，在实施了生态家园建设之后，农户的种植品种明显增加，种植热情和种植技术迅速提高，农业种植生产方式由原来的半自给自足的粗放式经营方式向以市场为导向的、以高投入高产出为特征的集约化经营方式转变。生态家园建设具有明显的增收作用。同时，农户参与生态家园项目建设具有明显的技术进步效应。它打破了过去农业生产常规模报酬的特征，改变了依赖要素投入提高产量和种植收入的传统种植思维和实践方式，有利于农业生产向依赖技术进步发挥规模报酬效应实现增收目标的生产方式转变。     

Bacterial community structure and microbial activity in different soils amended with biogas residues and cattle slurry

Anaerobic digestion of organic materials generates residues of differing chemical composition compared to undigested animal manures, which may affect the soil microbial ecosystem differently when used as fertilizers. This study investigated the effects of two biogas residues (BR-A and BR-B) and cattle slurry (CS) applied at rates corresponding to 70 kg NH₄⁺-N ha⁻¹ on bacterial community structure and microbial activity in three soils of different texture (a sandy, a clay and an organic clay soil). 16S rRNA genes were targeted in PCR reactions and bacterial community profiles visualized using terminal restriction fragment length polymorphism. General microbial activity was measured as basal respiration (B-resp), substrate-induced respiration (SIR), specific growth rate (μ_SIR), metabolic quotient (qCO₂) and nitrogen mineralization capacity (NMC). Non-metric multidimensional scaling analysis visualized shifts in bacterial community structure related to microbial functions. There were significant differences in bacterial community structure after 120 days of incubation (+20 °C at 70% of WHC) between non-amended (control) and amended soils, especially in the sandy soil, where CS caused a more pronounced shift than biogas residues. Terminal-restriction fragment (TRF) 307, the predominant peak in CS-amended sandy soil, was identified as possibly Bacillus or Streptococcus. TRF 226, the dominant peak in organic soil amended with BR-B, was classified as Rhodopseudomonas. B-resp significantly increased and SIR decreased in all amendments to organic soil compared with the control, potentially indicating decreased efficiency of heterotrophic microorganisms to convert organic carbon into microbial biomass. This was also reflected in an elevated qCO₂ in the organic soil. The μ_SIR level was higher in the sandy soil amended with BR-A than with BR-B or CS, indicating a shift toward species capable of rapidly utilizing glucose. NMC was significantly elevated in the clay and organic soils amended with BR-A and BR-B and in the sandy soil amended with BR-B and CS. Thus, biogas residues and cattle slurry had different effects on the bacterial community structure and microbial activity in the three soils. However, the effects of biogas residues on microbial activities were comparable in magnitude to those of cattle slurry and the bacterial community structure was less affected. Therefore, we do not see any reason not to recommend using biogas residues as fertilizers based on the results presented.     

Liquid chromatographic determination of multiple sulfonamide residues in bovine milk

A liquid chromatographic method has been developed for simultaneous determination of residues of 10 sulfonamide drugs at 10 ppb and above in raw bovine milk. The method is based on a chloroform-acetone extraction, evaporation of organic phase, dissolution of residues in an aqueous potassium phosphate solution, and extraction of fatty residue into hexane. The aqueous layer is collected, filtered, injected onto an LC system, and detected by ultraviolet absorption at 265 nm. To elute all 10 sulfonamides isocratically, 2 chromatographic conditions are required. Seven sulfonamides can be quantitated with 12% methanol in the mobile phase; 4 sulfonamides can be quantitated with 30% methanol. Sulfamethazine, the most widely used sulfonamide, is detected on both systems. Recoveries are 44-87% for individual sulfonamides, with only 2 below 60%. Coefficients of variation are 3-13% at 10 ppb.