改性蚁酸木质素的制备与应用

采用加拿大一枝黄花茎杆为原料提取蚁酸木质素,通过氧化或接枝复合的方法对蚁酸木质素进行改性,对改性产物进行了FTIR和SEM表征。实验结果表明：接枝复合改性产物中存在-CONH的接枝复合链,氧化改性产物基本保持了蚁酸木质素原来的吸收峰;采用接枝复合改性产物处理初始质量浓度为50 mg/L的亚甲基蓝废水,在废水pH 7、吸附时间4 h、改性产物加入量22 mg/mL的条件下,亚甲基蓝去除率为90.94%;采用氧化改性产物处理相同亚甲基蓝废水,在废水pH 10、吸附时间12 h、改性产物加入量22 mg/mL的条件下,亚甲基蓝去除率为81.93%。     

交联壳聚糖/沸石复合吸附剂的制备及性能

用沸石负载由缩水甘油基三乙基氯化铵交联的壳聚糖,制得了性能良好的交联壳聚糖/沸石复合吸附剂。研究了该吸附剂应用性能的影响因素,探讨了该吸附剂的吸附性、沉降性和重复使用性,利用FTIR仪和高倍透射电子显微镜对该吸附剂的结构进行了表征。实验结果表明:壳聚糖的交联度为0.93、交联壳聚糖与沸石的质量比为0.045时,制得的交联壳聚糖/沸石复合吸附剂对腐殖酸的去除率可达81.4%,吸附量为4.07mg/g;交联壳聚糖/沸石复合吸附剂对腐殖酸的吸附性能较沸石有显著提高,沉降时间较交联壳聚糖明显缩短;经二次洗脱后腐殖酸去除率仍可达80.2%,腐殖酸吸附量为4.01mg/g。     

紫外辐照-催化湿式过氧化氢氧化技术处理酸性大红GR染料废水

采用自制的负载型CuO-ZnO-CeO2/γ-Al2O3催化剂,常温常压下通过紫外辐照-催化湿式氧化技术处理酸性大红GR模拟染料废水。考察了催化剂加入量、H2O2加入量、废水pH、反应时间、初始酸性大红GR质量浓度等对废水脱色率的影响。实验得到最佳工艺条件为初始酸性大红GR质量浓度200mg/L,催化剂加入量10.0g/L,H2O2加入量2.0mL/L,废水pH4,反应时间2h。最佳工艺条件下废水脱色率达99.33%。     

盐析分相微萃取—高效液相色谱法测定水中含氯除草剂

采用盐析分相微萃取—高效液相色谱法同时测定水中3种含氯除草剂,建立并优化了反相离子对液相色谱条件,考察了萃取剂种类、盐析剂的种类和加入量及试样pH对萃取效果的影响。对氯苯氧乙酸、2,4-二氯苯氧乙酸和2,4-滴丁酯的质量浓度在0.1~100.0mg/L内与色谱峰面积呈良好的线性关系,相关系数不低于0.9992。平均回收率分别为96.29%、79.16%和70.21%,相对标准偏差小于5.3%。该方法操作简便、绿色环保,适合于水中含氯除草剂的测定。     

Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

Sorption–desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions

Sorption–desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption–desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd_ads, varied according to its initial concentration and was ranged 40–84 for HA, 14–58 for clay and 1.85–4.15 for bulk soil. Freundlich sorption coefficient, Kf_ads, values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ～800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n_ads values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.     

Electrochemical Monitoring of Methylparathion Degradation in an Acid Aqueous Medium in Presence of Cu(II)

Abstract

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o, 4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2–7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH ≤ 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 × 10^?3 s^?1 at pH 2, 5.5 × 10^?3 s^?1 at pH 4 and 9.0 × 10^?3 s^?1 at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

TOTAL ARSENIC ACCUMULATION IN EDIBLE PODS AND SEEDS OF PHASEOLUS VULGARIS

The main objective of this study was to evaluate whether arsenic accumulated in the edible pods and seeds of Phaseolus vulgaris, cv. Helda, above the Spanish maximum recommended concentration for food crops, 1 mg kg^?1 on a fresh weight basis. Only organic arsenicals were used because they are: a) the only arsenic species allowed for agricultural applications and b) more mobile than inorganic species. Selection of French beans, a sensitive plant to arsenic, was based on the fact that arsenic upward translocation is higher in sensitive than in tolerant plants. A 2 × 3 factorial experiment was conducted with two organic arsenic species: methylarsonic acid (MAA) or dimethylarsinic acid (DMAA) and three arsenic concentrations: 0.2, 0.5, or 1.0 mg L^?1. Arsenic phytotoxicity was primarily determined by soluble arsenic concentration. Experimental results showed that the low bean plant tolerance to arsenic is possibly due to the high arsenic upward transport to shoots, which could result in profound negative metabolic consequences. Even under extremely adverse conditions, arsenic residues in edible beans were below the maximum statutory limit set by the Spanish legislation. It can be concluded that the major danger of organic arsenical herbicides is that of decreased productivity rather than high arsenic uptake by consumers.     

珠江三角洲蔬菜基地蔬菜中邻苯二甲酸酯的含量特征

邻苯二甲酸酯是一类重要的环境激素类污染物。本文以气相色谱/质谱(GC/MS)联用检测技术,对珠江三角洲地区典型蔬菜生产基地蔬菜中6种邻苯二甲酸酯化合物进行测试分析。结果发现:(1)珠江三角洲地区典型蔬菜生产基地的蔬菜样品中,多数样品检测出6种邻苯二甲酸酯,总含量为0.46～12.02mg/kg。(2)基地蔬菜中单个邻苯二甲酸酯化合物的种类和含量因蔬菜种类、品种、部位和生长环境等因素而异。(3)同种类蔬菜在不同基地或同一基地不同种类蔬菜中邻苯二甲酸酯的含量分布不同。(4)大部分蔬菜中以邻苯二甲酸正二丁酯(DnBP)和邻苯二甲酸双(2-乙基己基)酯(DEHP)为主。     

Development and application of LC–APCI–MS method for biomonitoring of animal and human exposure to imidacloprid

Imidacloprid (IMI) is a relatively new neuro-active neonicotinoid insecticide and nowadays one of the largest selling insecticides worldwide. In the present study a LC–APCI–MS based method was developed and validated for the quantification of imidacloprid and its main metabolite 6-chloronicotinic acid (6-CINA) in urine and hair specimens. The method was tested in biomonitoring of intentionally exposed animals and subsequently applied for biomonitoring of Cretan urban and rural population.