Adsorption,desorption and dissipation of metolachlor in surface and subsurface soils

BACKGROUND: Variations in soil properties with depth influence retention and degradation of pesticides. Understanding how soil properties within a profile affect pesticide retention and degradation will result in more accurate prediction by simulation models of pesticide fate and potential groundwater contamination. Metolachlor is more persistent than other acetanilide herbicides in the soil environment and has the potential to leach into groundwater. Reasonably, information is needed about the dissipation and eventual fate of metolachlor in subsoils. The objectives were to evaluate the adsorption and desorption characteristics and to determine the dissipation rates of metolachlor in both surface and subsurface soil samples. RESULTS: Adsorption of metolachlor was greater in the high‐organic‐matter surface soil than in subsoils. Lower adsorption distribution coefficient (K_ads) values with increasing depth indicated less adsorption at lower depths and greater leaching potential of metolachlor after passage through the surface horizon. Desorption of metolachlor showed hysteresis, indicated by the higher adsorption slope (1/n_ads) compared with the desorption slope (1/n_des). Soils that adsorbed more metolachlor also desorbed less metolachlor. Metolachlor dissipation rates generally decreased with increasing soil depth. The first‐order dissipation rate was highest at the 0–50 cm depth (0.140 week^?1) and lowest at the 350–425 cm depth (0.005 week^?1). Degradation of the herbicide was significantly correlated with microbial activity in soils. CONCLUSION: Metolachlor that has escaped degradation or binding to organic matter at the soil surface might leach into the subsurface soil where it will dissipate slowly and be subject to transport to groundwater. Copyright © 2009 Society of Chemical Industry     

Adsorption-desorption behaviour of flufenacet in five different soils of India

Adsorption-desorption of the herbicide flufenacet (FOE 5043) has been studied in five soils from different locations in India (Delhi, Ranchi, Nagpur, Kerala and Assam) varying in their physicochemical properties. The organic matter (OM) content varied from 0.072 to 0.864%, clay content from 2.5 to 43.7% and pH from 4.45 to 8.35. The adsorption studies were carried out using a batch equilibration technique. Ten grams of soil were equilibrated with 20 ml of aqueous 0.01 M CaCl2 solution containing different concentrations (0-30 mg litre-1) of flufenacet. After equilibration, an aliquot of supernatant was taken out for analysis. During desorption, the amount withdrawn for analysis was replenished with fresh 0.01 M CaCl2 solution and further equilibrated. Desorption studies were carried out with the 30 mg litre-1 concentration of flufenacet only. The adsorption studies revealed that there was moderate to high adsorption of flufenacet considering the comparatively low organic carbon content in the five test soils. Average Kd values ranged from 0.77 to 4.52 and Freundlich KF values from 0.76 to 4.39. The highest adsorption was observed in Kerala soil (OM 0.786%; clay 25%; pH 4.45) followed by Ranchi, Nagpur and Delhi soils, and the lowest in Assam soil (OM 0.553%; clay 2.5%; pH 6.87). The trend in adsorption could be attributed to the chemical nature of flufenacet and the physicochemical properties of the soil such as pH, OM and clay contents. OM and clay contents were positively correlated whereas pH was negatively correlated. Soils having low pH, high OM and high clay contents showed higher adsorption. Desorption studies revealed that there was a hysteresis effect in all the soils. Hysteresis coefficient values (ratio of n(ad) and n(des)) varied from 0.09 to 0.45. The study implies that, because of its moderate to high adsorption, flufenacet is likely to persist in soil for some time. However, the possibility of its movement by leaching or surface run off is less.     

Desorption of diuron and isoproturon from undispersed clay loam soil

Studies were conducted to investigate the desorption of diuron and isoproturon adsorbed on undispersed clay loam soil, and the influence of residence time in soil on desorption. The soil was treated at 0·6 or 3 mg kg^-1, at 70% moisture content and in the presence of sodium azide to prevent degradation. Measurement of herbicide concentrations in soil solution sampled by means of glass microfibre filters showed that adsorption mainly occurred for one day but long-term sorption proceeded for >two weeks. After a one-day or three-week residence time, soil solution was partly replaced (28%). Measurement of concentrations in solution showed rapid desorption, with equilibria being achieved within 1 h (diuron) or a few hours (isoproturon). After 16 successive desorptions done at 30-min or 12-h intervals, equilibration times tended to be longer. For the short residence time, desorption and long-term sorption could occur simultaneously and equilibration might be faster. Residence time had no significant effect on desorption kinetics nor on the small hysteresis observed for diuron. The aging effect, involving long-term sorption only, decreased the proportion of diuron removed from the soil by successive desorptions but, for isoproturon, desorption frequency and desorption kinetics were more important. © 1997 SCI     

Characterization of triadimefon sorption in soils using supercritical fluid (SFE) and accelerated solvent (ASE) extraction techniques

Sorption–desorption of the fungicide triadimefon in field‐moist silt loam and sandy loam soils were determined using low‐density supercritical fluid extraction (SFE). The selectivity of SFE enables extraction of triadimefon from the soil water phase only, thus allowing calculation of sorption coefficients (K_d) at field‐moist or unsaturated conditions. Triadimefon sorption was influenced by factors such as soil moisture content and temperature; sorption increased with increased moisture content up to saturation, and decreased with increased temperature. For instance, K_d values for triadimefon on the silt loam and the sandy loam soils at 40 °C and 10% water content were 1.9 and 2.5 ml g⁻¹, respectively, and at 18% water content, 3.3 and 6.4 ml g⁻¹, respectively. Isosteric heats of sorption (ΔH_i) were −42 and −7 kJ mol⁻¹ for the silt loam and sandy loam soils, respectively. Sorption–desorption was also determined using an automated accelerated solvent extraction system (ASE), in which triadimefon was extracted from silt loam soil by 0.01 M CaCl₂. Using the ASE system, which is basically a fast alternative to the batch equilibration system, gave a similar ΔH_i value (−29 kJ mol⁻¹) for the silt loam soil (K_f = 27 µg^{1 − 1/n} ml^1/n g⁻¹). In order to predict transport of pesticides through the soil profile more accurately on the basis of these data, information is needed on sorption as a function of soil water content. © 2000 Society of Chemical Industry     

不同肥力土的土壤颗粒分布及其磷素吸附—解析规律

采用干筛法和培养实验,研究了不同肥力土的颗粒分布以及不同颗粒对磷素的吸附、解析规律。结果表明,在所筛分的5个粒径中,土以>5 mm、2～5 mm和0.25～1 mm 3个颗粒为主,随着土壤肥力提高,0.25～1 mm和1～2 mm两个粒径的土壤颗粒有明显增加。土壤颗粒由小到大变化,颗粒中磷素含量呈现由高到低的变化趋势。高肥力土壤和低肥力土壤相比,0.25～1 mm和1～2 mm两个粒径中的磷素含量分别增加40%和43%,差异达显著水平。土壤颗粒愈小对磷的吸附量越高。与土壤原样相比,<0.25 mm和0.25～1 mm两个粒径的颗粒对磷的吸附量高于土壤原样的,而1～2 mm、2～5 mm和>5 mm土壤颗粒对磷的吸附则小于土壤原样的。随着土壤颗粒径变大,磷的解析率增加。总体看来,高肥力土使中等大小土壤颗粒增多,对磷的吸附量有所减少,但对磷的解析量增大,这有助于提高磷肥的有效性,但也增加了磷素径流损失的风险。     

不同种类化肥对塿土吸附解吸铅、镉行为的影响

通过塿土对重金属Pb和Cd的吸附解吸试验,研究了5种不同类型氮、磷化肥对重金属Pb、Cd的吸附解吸特性的影响。结果表明:在吸附过程中,添加不同种类肥料能够改变塿土对Cd的吸附量,对Pb影响不大;土壤对Pb~(2+)的等温吸附曲线用Langmuir方程拟合效果好,对Cd的吸附曲线用Freundlich和Langmuir方程拟合均能达到显著水平(P0.01);由Langmuir方程拟合得到的最大吸附量可以看出,除磷酸二氢钾促进了土壤Cd的吸附,其余肥料的添加均抑制了土壤对Pb、Cd的吸附量。在解吸过程中,Pb的解吸过程受肥料影响显著,含磷肥料能促进铅解吸率的增大,解吸率最高可达90%以上。由于添加不同类型的肥料影响了土壤对Pb、Cd的吸附和解吸过程,因此,在已经受到Pb、Cd污染的农田进行耕作时,应谨慎选择施用对Pb、Cd影响强烈的磷肥,以避免增加Pb、Cd的迁移对作物造成危害。     

Influence of the physical and chemical properties of soil on the retention process of isoxaflutole and its two main derivatives

Isoxaflutole is a new pre‐emergence herbicide for use in maize and sugarcane. Its two main derivatives are a diketonitrile derivative, the 2‐cyano‐3‐cyclopropyl‐1‐(2‐methanesulfonyl‐4‐trifluoromethylphenyl)propan‐1,3‐dione, named DKN, and a benzoic acid derivative, the 2‐methanesulfonyl‐4‐trifluoromethylbenzoic acid, named BA. The adsorption/desorption processes have never been studied for isoxaflutole (IFT) at high concentrations nor for BA, and the present work aimed at completing the knowledge of the behaviour of these three molecules in conditions close to those encountered in the context of agricultural use. The adsorption/desorption study was conducted on seven soils of different physical and chemical properties, using the batch equilibrium technique. During the experiments, IFT was chemically converted into DKN in a continuous manner. This reaction appeared to be dependent on the pH of the soil and was taken into account in the calculations of the adsorbed and desorbed amounts. The adsorption isotherms obtained were predominantly C‐shaped for IFT and DKN and S‐shaped for BA, but some differences appeared on a few soils. They fitted well the Freundlich equation, and the values of the Freundlich coefficient K_fa showed that, whatever the soil, IFT was more adsorbed than its two derivatives. The main parameter influencing the adsorption of IFT appeared to be the organic matter content, whereas this effect was not evident for DKN and BA. No correlation was found between the extent of adsorption and either clay content or pH of the soil, for the three molecules.     

热泵干燥南美白对虾品质特性与玻璃化转变关系研究

针对南美白对虾热泵干燥过程中常出现物理、化学反应导致虾肉品质下降,而其机理又尚未明确的问题,采用静态称量法研究了南美白对虾肉的解吸等温线,利用差示扫描量热仪测定了虾肉的玻璃化转变温度(Tg)。分别采用GAB模型与Gordon-Taylor方程拟合水分吸附与Tg数据。虾肉在热泵干燥温度35℃、风速1.5 m/s下进行干燥,每隔1.0 h取样,分析虾肉品质特性(色泽、收缩程度、硬度与韧性和虾青素质量比)。基于玻璃化转变理论,阐明虾肉热泵干燥品质变化机制。结果表明,虾肉热泵干燥过程中,基质处于橡胶态,体系流动性增加,导致干制品品质下降。     

Screening and identification of specific serum biomarkers of Parkinson disease

AIM：To screen the possible serum biomarkers of Parkinson’s disease. METHODS：The surface-enhanced laser desorption ionization time-of-flight mass spectrometry (SELDI-TOF-MS) was used to screen the serum samples from 44 cases of Parkinson’s disease and 60 control subjects. The differentially expressed protein peaks were selected and isolated with high-performance liquid chromatography (HPLC), and processed with enzyme before analysis by liquid chromatography-mass spectrometry tandem mass spectrometry (LC-MS/MS). The data mining was performed by Xcalibur program component BioWorks 3.2. RESULTS：Three differentially expressed protein peaks were selected as potential serum biomarkers from the patients of Parkinson’s disease: the protein at 8 937 m/z peak showed significant increase (27.47±16.58 in Parkinson’s disease group, and only 5.01±3.47 in control group), and the proteins at 6 636 and 8 697 m/z peaks showed significant decreases (5.43±2.66 and 20.22±9.57, respectively, in Parkinson’s disease group, and 18.85±7.56 and 51.13±26.22, respectively, in control group). The proteins at 6 636, 8 697 and 8 937 m/z peaks were identified as apolipoprotein C-I, apolipoprotein C-III and complement 3a,respectively. Combined use of these 3 biomarkers effectively distinguished the subjects between Parkinsons disease group and control group. The detection rate of the patients with Parkinsons disease was 90.0% (27/30), and the detection rate of the healthy sibkects was 92.5% (37/40). CONCLUSION：The apolipoprotein C-I, apolipoprotein C-III and complement component 3a identified as potential markers of Parkinson’s disease have diagnostic value in clinical application.