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.     

养殖固体废物在硝酸和磷酸溶液中的水解特性

养殖固体废物掺杂磷肥工艺中养殖固体废物与酸的反应直接影响其有机组成。以鸡粪为研究对象,采用L16(45)正交试验研究了鸡粪粒径、酸浓度、鸡粪与酸溶液质量比、反应温度和反应时间对鸡粪在硝酸和磷酸溶液中水解过程的影响。结果表明,硝酸溶液中影响因素显著性依次为鸡粪与硝酸质量比、反应时间、硝酸浓度、鸡粪粒径、反应温度,最优工艺条件为鸡粪粒径0.20mm、硝酸质量分数15%、鸡粪与硝酸质量比0.2∶1.0、反应温度95℃、反应时间4h;在磷酸溶液中影响因素显著性依次为鸡粪与磷酸质量比、反应温度、鸡粪粒径、磷酸浓度、反应时间,鸡粪水解率与反应温度间呈正相关关系,最优工艺条件为鸡粪粒径0.40mm、磷酸质量分数60%、鸡粪与磷酸质量比0.1∶1.0、反应温度95℃、反应时间8h。鸡粪比表面积及其单位质量耗酸量、美拉德反应是制约鸡粪在硝酸和磷酸中水解反应的内因。研究结果为养殖固体废物掺杂有机磷肥的研发和推广提供了理论基础。     

废LCD面板有机材料水热资源化产乙酸

LCD面板主要由附着偏光片及液晶等有机材料的玻璃面板构成。有机材料的去除及资源化利用是废LCD面板处理的第一步。在水热条件下对废LCD面板进行了降解产酸研究。研究考察了反应温度、反应时间、氧化剂用量、水用量及pH值等对水热产乙酸产率及选择性的影响。通过正交实验确定了水热产乙酸的最佳操作条件：反应温度325℃,反应时间5min,氧化剂（30％H2O2）0．6mL,用水量2mL,近中性环境（pH6-6．5去离子水）。此条件下,乙酸产率及选择性分别为68．83％及70．56％。结果表明,以废LCD面板有机材料为原料,采用水热技术进行产乙酸反应,可实现其资源化再利用。     

重庆市大气污染对锌材料腐蚀的经济损失分析

简要介绍了材料大气腐蚀经济损失的估算方法,并以2002年为基准年,选择了重庆市主城中心的6个功能区作为代表性区域,运用腐蚀破坏剂量响应函数和使用寿命计算公式对锌材料的腐蚀经济损失进行了定量估算.结果表明,由大气污染腐蚀破坏锌材料造成的年直接经济损失约为4061.7万元,约为同期GDP的0.1%.其中,干沉降对经济损失总量的贡献率在71%～99%之间,均值为92%.     

不同物质对垃圾渗滤液中腐殖酸的吸附研究

垃圾渗滤液是一种有毒有害的高浓度有机废水,其中含大量腐殖酸。腐殖酸具有离子交换能力、吸附能力和脱除杂质能力,因此在很多方面有实用价值。活性碳、土壤、堆肥对废水中的有机物有一定的吸附能力。本文采用正交设计的方法,研究了活性碳、土壤、堆肥在不同温度,液／固,腐殖酸初始浓度的条件下对垃圾渗滤液中腐殖酸的吸附效果。实验结果表明：四种实验因素对吸附剂的吸附能力的影响程度为：吸附剂类型〉腐殖酸的初始浓度〉吸附反应温度〉液固比。在温度为25℃,液固比为50／0．5（mL/g）,腐殖酸初始浓度为41．99（mg／L）,吸附剂类型为活性碳时,腐殖酸吸附量最大,为40．86mg。同时分析了响应指标随因素的变化趋势。     

Photocatalytic bacterial inactivation by polyoxometalates

The photocatalytic inactivation (PCI) of Escherichia coli (Gram-negative) and Bacillus subtilis (Gram-positive) was performed using polyoxometalate (POM) as a homogeneous photocatalyst and compared with that of heterogeneous TiO₂ photocatalyst. Aqueous suspensions of the microorganisms (10⁷–10⁸ cfu ml⁻¹) and POM (or TiO₂) were irradiated with black light lamps. The POM-PCI was faster than (or comparable to) TiO₂-PCI under the experimental conditions employed in this study. The relative efficiency of POM-PCI was species-dependent. Among three POMs (H₃PW₁₂O₄₀, H₃PMo₁₂O₄₀, and H₄SiW₁₂O₄₀) tested in this study, the inactivation of E. coli was fastest with H₄SiW₁₂O₄₀ while that of B. subtilis was the most efficient with H₃PW₁₂O₄₀. Although the biocidal action of TiO₂ photocatalyst has been commonly ascribed to the role of photogenerated reactive oxygen species such as hydroxyl radicals and superoxides, the cell death mechanism with POM seems to be different from TiO₂-PCI. While TiO₂ caused the cell membrane disruption, POM did not induce the cell lysis. When methanol was added to the POM solution, not only the PCI of E. coli was enhanced (contrary to the case of TiO₂-PCI) but also the dark inactivation was observed. This was ascribed to the in situ production of formaldehyde from the oxidation of methanol. The interesting biocidal property of POM photocatalyst might be utilized as a potential disinfectant technology.