Evaluation of sorption-desorption processes for metalaxyl in natural and artificial soils

The main process controlling soil-pesticide interaction is the sorption-desorption as influenced by active soil surfaces. The sorption phenomena can influence translocation, volatility, persistence and bioactivity of a pesticide in soil. The present investigation was conducted on natural and artificial soils in order to enumerate the effect of soil components such as montmorillonite and ferrihydrite on the sorption behaviour of the fungicide metalaxyl and if sorption-desorption of the chiral pesticide affects the enantiomeric ratio. The sorption-desorption characteristics of metalaxyl were investigated by batch equilibration technique in a natural soil, two artificial soils, and in pure montmorillonite and ferrihydrite. After extraction, pesticide residues were analyzed by conventional and chiral chromatography using tandem mass spectrometry. A K_dSorp (2.3–6.5) suggests low level sorption of metalaxyl with an appreciable risk of run-off and leaching. Thus, metalaxyl poses a threat to surface and ground water contamination. Furthermore, desorption tests revealed a hysteretic effect (H ≤ 0.8) in natural and artificial soils. Significant amount of metalaxyl was found tightly bound to the adsorbents without desorbing readily after desorption cycle. Desorption of 22–56% of the total amount of the retained metalaxyl was determined. This study reveals that an artificial soil derived from different soil constituents can be used to assess their influence on sorption/desorption processes. The present investigation showed that both montmorillonite and ferrihydrite play a significant role in the sorption of metalaxyl. The sorption doesn't influence the enantiomeric ratio of racemic metalaxyl.     

沸石负载羟基氧化铁对铬（VI）吸附的固体浓度效应研究

本文利用沸石负载羟基氧化铁作吸附剂对六价铬进行吸附和解吸附实验。探讨了沸石负载羟基氧化铁对六价铬的吸附机制和固体浓度效应。实验结果表明：当吸附剂的用量从0.05g增加到0.2g时,在实验条件下,六价铬的吸附量从27999.493μg/g降低到8930.610μg/g,吸附剂对Cr6＋的吸附存在明显的固体浓度（Cs）效应。吸附滞后角随着Cs的增加而减小,吸附反应的可逆性增大。将实验数据分别用Languir和Freundlich吸附模型进行拟合,发现Freundlich吸附模型对实验数据拟合效果较好,表明该吸附反应以单分子层吸附为主。     

Thermal failure of 2/3 PCP in high temperature environment and optimization analysis of stator and rotor meshing parameters

Progressive cavity pump (PCP), which has problems such as invalid and leakage of rubber bushings, is employed in heavy oil field exploitation. In this paper, based on the thermal aging mechanical test of rubber and the fitting precision evaluation result of the constitutive model, the rubber constitutive model is optimized; the finite element model of PCP is established; the deformation law of stator bushing inner wall is quantitatively analyzed by numerical simulation method; and the phenomenon that temperature field distribution and thermal aging failure of stator rubber bushings is revealed. As results: The increase in well depth, which leads to the increase in the overall temperature of the stator bushing and the decrease of the thermal hysteresis, have greatest influence on the temperature of the stator bushing; the interference, which leads the maximum temperature increases first and then decreases, has a great impact on the thermal hysteresis; and the eccentricity have little effect on the thermal hysteresis of the stator bushing. The research results provide theoretical support to optimize stator and rotor parameter matching, recommending applicable working conditions, improving invalid of stator bushing, pump leakage and other issues.     

热效应对焦煤甲烷解吸迟滞特征的影响研究*

为揭示煤中甲烷气体的储运机制,选取井下煤样研究不同温度条件下甲烷气体的等温吸附解吸实验。基于Langmuir模型、等量吸附热计算模型和解吸迟滞系数对实验数据进行分析,研究煤中甲烷气体解吸迟滞现象的热力学特征。结果表明:随温度升高,Langmuir模型得到的吸附常数均呈下降趋势;甲烷解吸迟滞现象明显,迟滞程度随温度升高缓慢下降;受解吸迟滞效应影响,相邻温度区间内吸附曲线的等量吸附热较为相近,不同温度区间内解吸曲线的等量吸附热高于吸附曲线,差异显著;解吸迟滞现象影响煤层甲烷含量预测的准确性,并且解吸曲线的热力学特征规律性较差。     

Effects of temperature on sorption-desorption processes of imidacloprid in soils of Croatian coastal regions

Sorption-desorption behavior of imidacloprid in six soils collected from five coastal regions in Croatia at 20, 30 and 40°C was investigated using batch equilibrium technique. Isothermal data were applied to Freundlich, Langmuir and Temkin equations, and the thermodynamic parameters ΔH°, ΔG°, ΔS° were calculated. The sorption isotherm curves were non-linear and may be classified as L-type, suggesting a relatively high sorption capacity for imidacloprid. Our results showed that the K ^sor _F values decreased for all the tested soils as the temperature increased, indicating that the temperature strongly influences the sorption. Values of ΔG° were negative (?4.65 to ?2.00 kJ/mol) indicating that at all experimental temperatures the interactions of imidacloprid with soils were spontaneous processes. The negative and small ΔH° values (?19.79 to ?8.89 kJ/mol) were in the range of weak forces, such as H-bonds, consistent with interactions and partitioning of the imidacloprid molecules into soil organic matter. The ΔS° values followed the range of ?57.12 to ?14.51 J/molK, suggesting that imidacloprid molecules lose entropy during transition from the solution phase to soil surface. It was found that imidacloprid desorption from soil was concentration and temperature-dependent, i.e. at lower imidacloprid concentrations and temperature, lower desorption percentage occurred. Desorption studies revealed that hysteretic behavior under different temperature treatments existed, and it was more pronounced at 20°C in the soils with higher OC content. The study results emphasize the importance of thermodynamic parameters in controlling soil pesticide mobility in different geographical locations, seasons and greenhouse conditions.     

Rate-Limited Desorption of Volatile Organic Compounds from Soils and Implications for the Remediation of a Louisiana Superfund Site

The rates of desorption of trichloroethylene (TCE) and 1,3-dichlorobenzene (DCB) from a silty soil at a Superfund site and a silty-clayey soil from an uncontaminated bottomland hardwoodswamp in Baton Rouge, Louisiana were studied in laboratory batchsystems. The effect of the age of soil contamination was studiedusing a laboratory-spiked soil incubated for 3 days, 3 months and5 months. An empirical non-linear model was used to describe thebi-phasic nature of desorption with one fraction (labile) beingreleased in relatively short periods of time (typically 24–100 hr) and a second fraction (non-labile or irreversible) beingresistant to desorption. The non-linear model parameters, viz.,the fraction of the chemical released rapidly (F), and the firstorder desorption rate coefficients, k ₁ and k ₂respectively for the labile and slowly released fractions weredetermined by fitting the experimental data to the model. Thedata fit the model well as indicated by the high r ² values.The estimate of k ₁ was good. However, the values of k ₂are known with less precision due to the limited duration of theexperiment and number of samples taken at long times. In addition, desorption kinetics of 3 and 5-month old contaminatedsoils showed that progressively less amount of contaminant was available for facile desorption (lower F) compared to freshly contaminated soil. The labile fraction had desorption rate constants of the order of 10^-1 h^-1, whereas the slowlyreleased fraction had rate constants of the order of 10^-4 h^-1 in accord with literature reported values for a varietyof other compounds and soils. Possible mechanisms describing these rates and implications for the site clean up are discussed.     

沙土不同粒级微团聚体可解吸态磷释放通量

流失的水土是污染物的重要载体,为了估算随水土流失的沙土中可解吸态磷对上覆水体的影响,采用平衡解吸法研究了沙土不同粒级微团聚体可解吸态磷的释放通量.结果表明,不同粒级沙土微团体吸附态磷的解吸比例为黏粒(0.21)＜粉粒(0.29)＜细砂(0.60)＜粗砂(0.96).主要原因有二:细粒级中腐殖质含量显著高于粗粒级;细粒级中有机质是通过可溶有机质与黏土矿物相互结合形成复合体而富集(黏粒和粉粒级微团聚体的稳结态腐殖质所占比例显著高于其它粒级).磷在稳结态和紧结态腐殖质所形成的团聚体结构中引起的团聚体结构不可逆形变是导致黏粒级(解吸比例Dr =0.21,解吸迟滞性指数TⅡ=0.47)和粉粒级(Dr=0.29,TⅡ=0.45)微团聚体磷的解吸比例降低,解吸迟滞性指数增大的根本原因.沙土黏粒和粉粒级微团聚体携载的可解吸态磷对上覆水体的释放通量可分别按(99.52±3.54) mg·kg-和(72.48±2.62) mg·kg-1进行估算.     

理化性质对土壤吸附-解吸苄嘧磺隆的影响

为探讨土壤理化性质对其吸附-解吸BSM(苄嘧磺隆)的影响,采用批量平衡法研究了采自我国东南沿海和中部14个省区的21个土壤样品对BSM的吸附-解吸行为,以及BSM吸附-解吸行为与土壤pH、w(有机质)、w(TN)、w(黏粒)、CEC(阳离子交换量)等理化性质的关系. 结果表明:BSM在土壤中的等温吸附线可用Freundlich方程进行拟合,不同土壤对BSM的吸附强度差异较大,K_f (Freundlich常数)介于0.52~24.05之间. 土壤pH、w(有机质)是影响BSM吸附的主要因素,二者对K_f的解释率为58.1%;土壤对BSM的吸附还受w(TN)、w(黏粒)等的影响. 土壤对BSM的吸附-解吸存在滞后现象,HI(迟滞系数)与土壤pH呈极显著负相关,与w(黏粒)呈显著正相关,其中土壤pH对HI的解释率为33.0%. 吸附平衡溶液pH与K_d (分配系数)呈极显著负相关,对其进行调节可显著改变土壤对BSM的分配能力.      

PATTERNS OF SUSPENDED SEDIMENT TRANSPORT IN A COASTAL ALASKA STREAM1

Suspended sediment data from a 154 ha watershed on northeast Chichagof Island, Alaska, were collected over three fall storm seasons from 1980 to 1982. Sediment rating curves for nine pooled storms explained less than 34 percent of the variation in total suspended solids (TSS). Significantly higher concentrations of suspended sediment occurred during the rising limb of storm hydrographs than for similar flows on the falling limb, accounting for hysteresis loops in TSS versus streamflow plots for individual storms. These hysteresis loops were wider during early season storms, indicating that easily transportable fine sediment may have been flushed from the upper portion of channel banks and from behind large organic debris during early season peak flows. Regression relationships (TSS versus Q) developed for the highest stormflows (> 1 m³/s) had steeper slopes than the lower stormflows (< 1 m³/s). Turbidity correlated well (r=0.94) with TSS for all storm-flow data combined. Organic matter constituted an average of 35 percent (by weight) of TSS for all water quality samples.     

突变理论在研究南方丘陵山区水土流失发展过程中的应用——以江西省兴国县为例

本文试图用突变理论和突变模型解释和描述水土流失过程的特点和规律,提出水土流失过程是突变过程,并以江西省兴国县为例应用尖点型突变模型对水土流失的现状及发展过程进行模拟。根据尖点型突变模型的性质,文中提出水土流失过程具有滞后性、发散性、双模态性和突变性,最后用得到的确定性模型将水土流失分为三种状态类型,即非流失稳定状态,稳定流失状态及潜在突变状态并提出在人力和财力有限的情况下,水土保持的重点应放在轻度和中度流失区。