Oxidation of organophosphorus pesticides with chloroperoxidase enzyme in the presence of an ionic liquid as co-solvent

Effects of selected ionic liquids on the efficiency of CPO oxidation of methyl-parathion were studied. In general, the activity of CPO decreases with the increased concentration of ionic liquid. For ionic liquids with the same cation, those with PF₆ ^? exhibit strongest inhibition toward CPO, while those with either BF₄ ^? or metSO₄ ^? show relatively lesser inhibition. It was further demonstrated that even for buffer solutions containing up to 30% concentration of ionic liquids such as EAN, BMIMmetSO₄, and EtPyTFA, CPO still can retain high activity (70–100% compared to that in citrate buffer) for oxidation of methyl-parathion. Photothermal enhancement factors of 3.5 times and corresponding improvements of sensitivity in the determination of organophosphates by the FIA-TLS method are predicted in 30% ionic liquids.     

Estimating spatially-variable first-order rate constants in groundwater reactive transport systems

Numerical reactive transport models are often used as tools to assess aquifers contaminated with reactive groundwater solutes as well as investigating mitigation scenarios. The ability to accurately simulate the fate and transport of solutes, however, is often impeded by a lack of information regarding the parameters that define chemical reactions. In this study, we employ a steady-state Ensemble Kalman Filter (EnKF), a data assimilation algorithm, to provide improved estimates of a spatially-variable first-order rate constant λ through assimilation of solute concentration measurement data into reactive transport simulation results. The methodology is applied in a steady-state, synthetic aquifer system in which a contaminant is leached to the saturated zone and undergoes first-order decay. Multiple sources of uncertainty are investigated, including hydraulic conductivity of the aquifer and the statistical parameters that define the spatial structure of the parameter field. For the latter scenario, an iterative method is employed to identify the statistical mean of λ of the reference system. Results from all simulations show that the filter scheme is successful in conditioning the λ ensemble to the reference λ field. Sensitivity analyses demonstrate that the estimation of the λ values is dependent on the number of concentration measurements assimilated, the locations from which the measurement data are collected, the error assigned to the measurement values, and the correlation length of the λ fields.     

阳离子聚丙烯酰胺-TiO2复配絮凝剂的合成及性能

以甲基丙烯酰氧乙基三甲基氯化铵(DMC)和丙烯酰胺(AM)为单体,K2S2O8-NaHSO3为引发剂,采用水溶液聚合法合成了阳离子聚丙烯酰胺P(DMC-AM),将表面处理后的纳米TiO2与P(DMC-AM)复配,得到P(DMC-AM)-TiO2复配絮凝剂.考察了原料配比、反应条件对P(DMC-AM)黏度的影响,结果表明:在m(DMC):m(AM)=0.18、引发剂加入量为0.5%(质量分数,下同)、聚合反应时间3 h、聚合溶液pH=4.0条件下,P(DMC-AM)絮凝剂的特性黏度最佳;纳米TiO2加入量为5%时,复配絮凝剂对酸性黑10B染料模拟废水的脱色性能最好.     

一株碱性脱除硫酸盐细菌的筛选及其生长特性研究

生化铁碱溶液催化法气体脱硫方法（简称DDS法）具有良好脱硫效果,但是DDS溶液在脱硫后会导致脱硫能力降低,为了达到使DDS脱硫残液得到再生的目的,从自然环境中筛选能够使DDS脱硫残液得到再生的微生物并对其进行了研究。通过富集培养及纯化,从黑龙江省五大连池火山口附近土样中筛选出一株碱性条件下脱除硫酸盐的菌株WT-1。对该菌株的生长曲线进行了测定,培养4～6 h菌株进入对数期,20 h左右到达稳定期。并研究了温度、pH值和摇床转速对其生长特性和活性的影响,结果表明,该菌株的最适生长条件为：温度35～45℃,pH值8,摇床转速120 r/min。同时,脱硫试验表明WT-1确实具有脱除硫酸盐的能力。     

Diurnal variability of total ozone column over Madrid (Spain)

In recent years, research on ozone variability has mainly focused on the analysis of its trend. Additionally some studies have analyzed the annual, seasonal and day-to-day ozone variations. However, intra-diurnal total ozone variations are notably less explored. Thus, the main objective of this paper is to analyze the diurnal variability of total ozone column (TOC) as recorded by a Brewer spectrophotometer in Madrid (Spain). The results show that about 90% of days present non-negligible diurnal variability, indicating that, in general, it should not be assumed that TOC remains constant throughout a particular day in urban areas. In addition, this variability has a notable seasonal behavior which should be considered (the spring and summer months show higher diurnal TOC variations than autumn and winter months). This pattern is likely caused by the diurnal photochemical processes in the lower troposphere related to the formation of tropospheric ozone near the earth’s surface at populated urban locations. Thus, these diurnal fluctuations in tropospheric ozone could explain part of diurnal TOC variations (between 20% and 70% depending on the mixing layer height).     

Evaluation of genotoxic variations in plant model systems in a case of metal stressors

This study was designed to assess the effects of long term, high metal exposition (cadmium, lead, copper, nickel and zinc) on DNA damage in four plant model systems [Taraxacum officinale (Asteraceae), Matricaria recutita L. (Asteraceae), Robinia pseudoacacia L. (Fabaceae), and Urtica dioica (Urticaceae)]. DNA stability was investigated by a Random Amplified Polymorphic DNA (RAPD) technique. Agarose-gel electrophoresis revealed total of 37 bands with different molecular weights ranging from 1250 to 5000 bp. It generated distinctive polymorphism value of 72.97% (27 bands) total in four plant species investigated. The dendrogram constructed using NTSYSpc programme showed that there is grouping in separate clusters of the same plant model collected from two different areas (metal-exposed and control samples). The study concluded that the long term metal-exposing periods had genotoxic stress on macromolecules of plant model systems investigated and biomarkers used should be augmented for reliable estimates of genotoxicity after exposure of plants to metal stressors.     

Implication of zinc excess on soil health

This study was undertaken to evaluate zinc's influence on the resistance of organotrophic bacteria, actinomyces, fungi, dehydrogenases, catalase and urease. The experiment was conducted in a greenhouse of the University of Warmia and Mazury (UWM) in Olsztyn, Poland. Plastic pots were filled with 3 kg of sandy loam with pH_KCl – 7.0 each. The experimental variables were: zinc applied to soil at six doses: 100, 300, 600, 1,200, 2,400 and 4,800 mg of Zn²⁺ kg^?1 in the form of ZnCl₂ (zinc chloride), and species of plant: oat (Avena sativa L.) cv. Chwat and white mustard (Sinapis alba) cv. Rota. Soil without the addition of zinc served as the control. During the growing season, soil samples were subjected to microbiological analyses on experimental days 25 and 50 to determine the abundance of organotrophic bacteria, actinomyces and fungi, and the activity of dehydrogenases, catalase and urease, which provided a basis for determining the soil resistance index (RS). The physicochemical properties of soil were determined after harvest. The results of this study indicate that excessive concentrations of zinc have an adverse impact on microbial growth and the activity of soil enzymes. The resistance of organotrophic bacteria, actinomyces, fungi, dehydrogenases, catalase and urease decreased with an increase in the degree of soil contamination with zinc. Dehydrogenases were most sensitive and urease was least sensitive to soil contamination with zinc. Zinc also exerted an adverse influence on the physicochemical properties of soil and plant development. The growth of oat and white mustard plants was almost completely inhibited in response to the highest zinc doses of 2,400 and 4,800 mg Zn²⁺ kg^?1.     

Degradation of the herbicide 2,4-DP by anodic oxidation, electro-Fenton and photoelectro-Fenton using platinum and boron-doped diamond anodes

This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.     

Acceleration of selenium volatilization in seleniferous agricultural drainage sediments amended with methionine and casein

Phytoremediation is potentially effective for managing excessive selenium (Se) in drainage sediment residing in the San Luis Drain in central California. This 2-year field study examined the feasibility of amending drainage sediment (containing 4.78microgSeg(-1)) with methionine and casein to enhance volatilization without or with vegetation of Sporobolus airoides. Results show that without organic amendments, rates of Se volatilization were less than 25microgm(-2)d(-1) in all plots. After amending the sediment with 71.4mgmethioninekg(-1) soil, Se volatilization rates were 434+/-107microgm(-2)d(-1) in vegetated plots and 289+/-117microgm(-2)d(-1) in irrigated bare plots. With the amendment of 572mgcaseinkg(-1) soil, rates increased to 346+/-103microgm(-2)d(-1) in irrigated bare plots and to 114+/-55microgm(-2)d(-1) in vegetated plots. Both methionine and casein promoted biological remediation of Se via volatilization most effectively during the warmest months.     

Implementation of Neural Networks for Classification of Moss and Lichen Samples on the Basis of Gamma-Ray Spectrometric Analysis

Mosses and lichens have an important role in biomonitoring. The objective of this study is to develop a neural network model to classify these plants according to geographical origin. A three-layer feed-forward neural network was used. The activities of radionuclides ((226)Ra, (238)U, (235)U, (40)K, (232)Th, (134)Cs, (137)Cs and (7)Be) detected in plant samples by gamma-ray spectrometry were used as inputs for neural network. Five different training algorithms with different number of samples in training sets were tested and compared, in order to find the one with the minimum root mean square error. The best predictive power for the classification of plants from 12 regions was achieved using a network with 5 hidden layer nodes and 3,000 training epochs, using the online back-propagation randomized training algorithm. Implementation of this model to experimental data resulted in satisfactory classification of moss and lichen samples in terms of their geographical origin. The average classification rate obtained in this study was (90.7 +/- 4.8)%.