高效液相色谱法分析水稻和稻田中的氯硝柳胺乙醇胺盐残留

建立了高效液相色谱(HPLC)测定水稻和稻田中氯硝柳胺乙醇胺盐残留量的分析方法。稻田水和稻秆样品中的氯硝柳胺乙醇胺盐残留用碱性乙酸乙酯直接提取;而稻田土壤、糙米和谷壳样品则先经碱性乙醇提取,再用乙酸乙酯进行萃取。萃取物经弗罗里硅土柱净化后,经Welchrom C18柱分离,采用紫外检测器检测,外标法定量。在0.01～10.00 mg/L范围内,氯硝柳胺乙醇胺盐的峰面积与其质量浓度间呈良好的线性关系,相关系数为0.9998。在稻田水、土壤、稻秆、糙米和谷壳中添加0.01～5.00 mg/kg的氯硝柳胺乙醇胺盐,其平均回收率为93.47%～100.9%,相对标准偏差为1.46%～5.82%,符合农药残留量分析与检测的技术要求。该方法简便、快速,灵敏度高,重现性好,可用于环境系统中氯硝柳胺乙醇胺盐残留量的分析与检测。     

Distribution and behavior of long-lived radioiodine in soil

The concentration of¹²⁹I in soil in Japan was determined by neutron activation analysis. For the activation analysis, pre-irradiation chemical separation of the iodine was carried out by acid decomposition and distillation and post-irradiation treatment was performed by ion exchange and solvent extraction. The concentration of stable iodine and¹³⁷Cs were also determined and compared with the behavior of¹²⁹I in soil.Soil samples from Ibaraki, Fukui, Fukushima, and Nagasaki Prefectures were analyzed and¹²⁹I was detected in amounts ranging from 10^–7 to 10^–5 Bq/g soil in uncultivated surface soil. There are apparently small variations in the¹²⁹I concentrations in each of the regions analyzed.From depth profile studies in sandy soil, the iodide form of¹²⁹I was found to migrate downward at a relatively rapid rate while other species remain longer in the surface soil.     

Development and validation of an HPLC-DAD method for the simultaneous determination of most common rice pesticides in paddy water systems

Rice crop is mainly cultivated in large river basins which constitute unique ecosystems and their ecological quality is invaluable. However, the high loads of pesticides used in rice cultivation contribute to the contamination of the water resources in such rice-cultivated regions. To regularly monitor the quality of such water resources there is a need for a rapid and sensitive multi-residue analytical method. This study presents the development and validation of a new analytical method for the simultaneous determination of most rice pesticides including penoxsulam, tricyclazole, propanil and its main metabolite 3,4-dichloroaniline, azoxystrobin, molinate, profoxydim and deltamethrin. A solid-phase extraction (SPE) procedure followed by high performance liquid chromatography (HPLC) with diode array detection (DAD) was used. A C₁₈ RP column operated at 30°C was utilised and the analytes were separated with a mobile phase of acetonitrile/water mixture in a linear gradient. Clean-up of water samples and isolation of pesticides was performed on SPE Bakerbond octadecyl cartridges and an ethyl acetate-dichlomethane mixture (9?:?1 v/v, 2?mL) was used for elution. Method validation was performed by means of intra-day (n?=?5) and inter-day accuracy and precision (n?=?8), sensitivity and linearity. The relative recoveries of the pesticides in paddy water samples were acceptable (80.6–110.2%) and the relative standard deviation (RSD%) ranged from 1.9 to 7.6%. Limits of detection (LOD) and limits of quantification (LOQ) varied from 0.1 to 0.8?ng?mL^?1 and 0.25 to 2.0?ng?mL^?1 respectively, depending on the analyte. The method was subsequently applied for the determination of pesticide residues in paddy and canal water samples. Tricyclazole was the most frequently detected pesticide at the highest concentrations, while herbicides were less frequently detected and at lower concentrations. The method described could be a valuable tool for regular monitoring of surface water systems in rice-cultivated basins.     

A model for simulating the dynamic surface tension behavior of aqueous surfactant dispersions

A dynamic adsorption model for surface-active materials at air/liquid interfaces with the consideration of aggregate dissolution effect was developed to investigate the dynamic surface tension behavior of aqueous surfactant dispersions. Two catanionic surfactants, cetylpyridinium dodecylsulfate (CP-DS) and dodecyltrimethylammonium dodecylsulfate (DTMA-DS), with low critical aggregation concentrations were chosen as model systems. Dynamic surface tensions of aqueous CP-DS and DTMA-DS systems were measured by a drop volume tensiometer. A model with diffusion-controlled or mixed-kinetic dynamic adsorption mechanisms considering the dissolution effect of dispersed aggregates was developed to simulate the dynamic surface tension data. An analysis by comparing the model predictions with experimental data demonstrated that the dynamic surface tension behavior of aqueous CP-DS and DTMA-DS dispersions could be described with a diffusion-controlled dynamic adsorption model taking the aggregate dissolution effect into account.     

Tracer experiments on the behavior of radioiodine in the soil-plant-atmosphere system

In order to obtain information on the behavior of long-lived¹²⁹I in the soil-plant-atmosphere system, two different experiments, transfer factors and volatilization of iodine, have been conducted by radiotracer techniques using¹²⁵I. Soil-to-plant transfer factors varied very widely. Low values were found in tomato (0.0003) and rice (0.0019). The highest value for an edible part was seen in komatsuna,Brassica rapa L. (0.016), which is comparable to the IAEA recommended value of iodine for common crops (0.02). There was a tendency for older leaves to show higher concentrations than younger ones. The values for fruit, grain and beans were significantly lower than those for their leaves. Thus translocation of iodine with photosynthate from leaves into these plant organs was very small. Iodine in soil was found to be volatilized from the soil-rice plant system into the atmosphere as an organic iodine. Volatilization markedly decreased in the late cultivation period of rice plants.     

Anomalous behavior of radioiodine: Solvent extraction from acidic solution

Anomalous behavior of radioiodine was found in solvent extraction. Iodine was extracted into CS₂ from acidic solution over a wide range of iodine concentration. The distribution ratio was obtained by measuring the -rays from iodine-131. The ratio drastically changed at about 10^–5 mol l^–1. The change is readily explained by the kinetic behavior of radioiodine.     

Development and validation of an analytical method for determination of endocrine disruptor, 2,4-D, in paddy field water

The acidic herbicides are an important class of chemical compounds that are used to control a variety of weeds that threaten many crops. Owing to their low microbial activity levels, the acidic herbicides exhibit a residual activity remaining for periods of up to several months in soils and water. The principal objective of this study was to develop an analytical method based on liquid–liquid and solid‐phase extraction followed by HPLC, for the determination of 2,4‐D in paddy field water. The residues were verified via tandem mass spectrometry (MS/MS) in negative‐ion electrospray ionization (ESI) mode. Linearity was good over a concentration range of 1–100 µg/L with a correlation coefficient (r²) of 0.999. The mean recovery rates of triplicate results ranged from 85.2 to 90.85%. The limits of detection and quantitation were 0.4 and 1.0 µg/L, respectively. The method proposed herein was applied to field samples acquired from Hampyung and Sunchang counties, Republic of Korea. The analyte was detected at a concentration range of 6.8–12.8 and 3.55–24.0 µg/L, respectively. Copyright © 2010 John Wiley & Sons, Ltd.     

Effect of available phosphorus in paddy soils on phosphorus uptake of rice

Relation between available phosphorus in 6 types of paddy soil in, Human Province and its uptake by rices was studied by³²P tracing. The result indicated that the P uptake by rices varied with available P content in the paddy soils. When the content was high, the rice absorbed more P nutrient from the soil and decreased the P uptake from the P fertilizer, which showed a poor contribution of the P fertilizer to the rice yield increase, and vice versa. The recovery of the P fertilizer varied with the soil types. Ranked the first was in paddy soils derived from lacustrine deposite but little rice yield increased. While in paddy soils derived from limestone, the yield greatly increased although the recovery of P fertilizer was the lowest. Rice absorbed P nutrient during its whole growth duration. No matter the different uptake amount due to the P supply by the different soils, rice plant generally had the greatest P nutrient uptake from tillering stage to elongation stage, and along with the rise of the rices dry matter, amount of P uptake was gradually increased but the P content in unit dry matter was tended to decrease.     

Residual level of dimethachlon in rice‐paddy field system and cooked rice determined by gas chromatography with electron capture detector

In this study, a modified quick, easy, cheap, effective, rugged and safe method coupled with gas chromatography with electron capture detection was established to determine dimethachlon residues in paddy soil, rice husk, rice straw, brown rice and cooked rice. The limits of quantification of dimethachlon were 0.01 mg/kg for paddy soil, brown rice and cooked rice and 0.02 mg/kg for rice straw and rice husk. The mean recoveries were in the range 78.59–104.7% with relative standard deviation values of <10% for dimethachlon in the five matrices. For field experiments, the final residues of dimethachlon in paddy soil were < 0.05 mg/kg and were < 1.21 mg/kg in rice straw from six sites. The final residues of dimethachlon in the brown rice at 21, 28 and 35 days after spraying from six sites were 0.08–7.58 mg/kg, and 0.16–30.1 mg/kg in rice husk. Our six test sites covered the main rice–producing areas of China. The routine rice cooking process of a Chinese family could apparently increase the removal of dimethachlon in rice compared with brown rice, and the reduction ratios were > 96%.     

Effect of the vibration shear flow field in capillary dynamic rheometer on the crystallization behavior of polypropylene

The self-made capillary dynamic rheometer was adopted to study the relationship between the crystallization behavior of isotactic polypropylene (iPP) and the vibration shear conditions, namely, vibration amplitude and vibration frequency. The crystalline structure of iPP under different vibration conditions was characterized by using differential scanning calorimeter (DSC) and wide-angle X-ray diffractometer (WAXD) techniques. The samples extruded under vibration shear conditions had a higher melting temperature (from DSC). A new shoulder-shape peak appeared at ca. 162 °C under low frequency or low amplitude conditions, which was engulfed by the main melting peak with the increase of the vibration amplitude or frequency. This was probably an indication that more perfect crystals had formed [Polym Eng Sci 38 (1998) 1-20]. The WAXD demonstrated that crystalline form of iPP extruded was not changed but the average crystalline size decreased, according to the Scherrer formula [Analytical methods of polymer materials, China Petrochemical Press, Beijing, 1997]. This proved a large increase in the number of small crystals.     

Structures and dynamic behavior of catalyst model surfaces characterized by modern physical techniques

This paper reports the visualization of mobile pyridine on the terraces and site-specific adsorption of pyridine on the particular step sites on a TiO₂(110)-(1×1) surface by scanning tunneling microscopy (STM), the anisotropic structure and reactivity of molybdenum oxides dispersed on TiO₂(110)-(1×1) characterized by polarization-dependent total-reflection fluorescence x-ray absorption fine structure (PTRF-EXAFS), and the energy dispersive and real-time images of Au mesh on Si(111) recorded by a new x-ray photoemission electron miscroscopy (XPEEM).     

Photochemical aspects of the behavior of the atmospheric radioiodine after the Chernobyl accident

A hybrid stable iodine/radioiodine (¹³¹I) atmospheric photochemistry box model, including 27 reactions, has been developed and solved using algorithmic programme with the application of the Runge-Kutta method of the order 4(5). This modelling offers a clearer view of relationship among aerosol-associated (inorganic iodine compounds, mostly I₂O₂), gaseous inorganic (mostly IONO₂, HOI) and organic (CH₃I) iodine compounds in ambient atmosphere. Summing up the data of the Chernobyl accident, the problem of the standardised method for atmospheric aerosol-associated and gaseous (inorganic and organic) radioiodine activity measurements in the case of the nuclear power plant accident is discussed.     

氢化物发生原子荧光法测定稻田土中的锑形态

采用王水消解及逐级浸提技术,以氢化物发生-原子荧光法对成都东郊稻田土中的Sb形态进行了分析,方法检出限为0.108μg/L,回收率为96.9%～104.8%。加入硫脲-抗坏血酸溶液后,土壤样品中可能存在的金属离子Cu2+、Co2+、Se4+、Sn2+、Zn2+、Pb2+、As3+、As5+、Hg2+对Sb的干扰可以有效地消除;样品Sb含量在0.92～2.52 mg/kg之间波动,平均值为1.76 mg/kg,与四川省土壤Sb背景浓度(≈1.70 mg/kg,1991)相比相差不大。水平方向上,各形态Sb的浓度因所处稻田条件的不同而分布各异,大体呈以下规律:残渣态﹥有机/硫化物结合态﹥铁/锰氧化物结合态﹥碳酸盐结合态﹥可交换态,易被植物吸收利用的可交换态占的比率最小;垂直方向上,各形态随着土壤深度的增加,呈递减趋势。     

A model for transits in dynamic response theory

The first goal of vibration-transit (V-T) theory was to construct a tractable approximate Hamiltonian from which the equilibrium thermodynamic properties of monatomic liquids can be calculated. The Hamiltonian for vibrations in an infinitely extended harmonic random valley, together with the universal multiplicity of such valleys, gives an accurate first-principles account of the measured thermodynamic properties of the elemental liquids at melt. In the present paper, V-T theory is extended to nonequilibrium properties, through an application to the dynamic structure factor S(q,omega). It was previously shown that the vibrational contribution alone accurately accounts for the Brillouin peak dispersion curve for liquid sodium, as compared both with molecular-dynamics (MD) calculations and inelastic x-ray scattering data. Here it is argued that the major effects of transits will be to disrupt correlations within the normal-mode vibrational motion and to provide an additional source of inelastic scattering. We construct a parametrized model for these effects and show that it is capable of fitting MD results for S(q,omega) in liquid sodium. A small discrepancy between model and MD at large q is attributed to multimode vibrational scattering. In comparison, mode coupling theory formulates S(q,omega) in terms of processes through which density fluctuations decay. While mode coupling theory is also capable of modeling S(q,omega) very well, V-T theory is the more universal since it expresses all statistical averages, thermodynamic functions, and time correlation functions alike, in terms of the same motional constituents, vibrations and transits.     

Static and dynamic scaling behavior of a polymer melt model with triple-well bending potential

We perform molecular-dynamics simulations for polymer melts of the coarse-grained poly(vinyl alcohol) model that crystallizes upon slow cooling. To establish the properties of its high temperature, liquid state as a reference point, we characterize in detail the structural features of equilibrated polymer melts with chain lengths 5 ≤ N ≤ 1000 at a temperature slightly above their crystallization temperature. We find that the conformations of sufficiently long polymers with N > 50 obey essentially the Flory's ideality hypothesis. The chain length dependence of the end-to-end distance and the gyration radius follow the scaling predictions of ideal chains and the probability distributions of the end-to-end distance, and form factors are in good agreement with those of ideal chains. The intrachain correlations reveal evidences for incomplete screening of self-interactions. However, the observed deviations are small. Our results rule out any preordering or mesophase structure formation that are proposed as precursors of polymer crystallization in the melt. Moreover, we characterize in detail primitive paths of long entangled polymer melts and we examine scaling predictions of Rouse and the reptation theory for the mean squared displacement of monomers and polymers center of mass. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1376–1392     

Detoxification of antimony by selenium and their interaction in paddy rice under hydroponic conditions

Antimony (Sb) contamination has become a growing concern in recent years. Strategies for reducing Sb contamination and its related health risks are urgently desired. This study was conducted to explore the possibility of selenium (Se) detoxification on Sb toxicity in paddy rice in order to find a feasible method to reduce the health risk of Sb pollution. Seedlings of paddy rice were exposed to 5 mg L⁻¹ Sb (KSbC₄H₄ O₇·1/2H₂O), in the presence of Se (Na₂SeO₃) at 0.1, 1, 5 mg L⁻¹ in culture solution, with no Sb and Se addition as the control. Paddy rice took up Sb greatly and the highest Sb contents measured among all treatments in this experiment in the leaves, stems and roots were 65.5, 298.5 and 195.7 mg kg⁻¹, respectively. Without Sb addition in the solution, single exposure to 0.1 mg L⁻¹ Se remarkably reduced the malondialdehyde (MDA) formation in paddy rice,demonstrating the beneficial effect of Se at low dosages. The addition of 5 mg L⁻¹ Sb was found to generate toxicity to paddy rice, showing as decreased biomass and increased leaf MDA content in paddy rice, while addition of 1 mg L⁻¹ Se mitigated the toxicity of Sb, as seen with the decreased leaf MDA content and increased biomass, indicating antidotal role of Se to Sb. In addition, the presence of 0.1, 1, 5 mg L⁻¹ Se generally decreased the accumulation of Sb in the leaves, stems and roots in paddy rice. Toxicity was also seen when paddy rice was exposed to single Se at 1 and 5 mg L⁻¹ levels, however, 5 mg L⁻¹ Sb addition was found to decrease the contents of Se in the leaves/stems whereas increased them in roots, accompanied with decreased MDA contents and increased biomass in paddy rice, indicating a possible detoxification role of Sb to Se too. Therefore, Sb, although toxic, could also be an antitoxin to Se in paddy rice at certain condition. Our results showed that Se could alleviate Sb toxicity efficiently in paddy rice through two effects as antagonism and antioxidation.