Polymerization of humic substances by an enzyme-catalyzed oxidative coupling

 A novel understanding of the structural features of humic substances supports the self-assembly supramolecular association of relatively small molecules rather than their polymeric nature. An increase in the conformational stability of humus may thus be achieved through promotion of intermolecular covalent bondings between heterogeneous humic molecules by an enzyme-catalyzed oxidative reaction. We present evidence from high performance size exclusion chromatography (HPSEC) and diffuse reflectance infrared spectrometry (DRIFT) that oxidation of a humic material catalyzed by horseradish peroxidase stabilizes the humic structure by the formation of aryl and alkyl ethers and permanently enhances its molecular size. Received: 15 May 2000 / Accepted in revised form: 14 July 2000     

Effect of natural aquatic humic substances on the photodegradation of bisphenol A

The photochemical degradation of bisphenol A (BPA) was studied in the presence of natural humic substances from different origins under simulated solar irradiation. BPA underwent insignificant direct photolysis in neutral water, but rapid photosensitized degradation in four humic substances solutions via pseudo-first-order reaction occurred. The photo-degradation rate of BPA was insensitive to the different initial BPA concentrations and was inhibited in aerated solution compared with the deoxygenated medium. The reactive oxygen species (ROS) such as ·OH and ¹O₂ produced from excitation of humic substances under irradiation was determined from the quenching kinetic experiment using molecular probe. The five main intermediate photoproducts of BPA in Nordic lake fulvic acid (NOFA) were tentatively identified using gas chromatography/mass spectrometer (GC/MS). Based on the identification of ROS and the analysis of photoproduct formation, the possible phototransformation pathways of BPA were proposed, involving the direct photolysis due to the energy transfer from the triplet state humic substance (³HS*) to BPA molecules and hydroxyl radical addition and oxidation as well. Translated from Acta Scientiae Circumstantiae, 2005, 25(6): 816–820 [译自: 环境科学学报]     

Non-random distribution of many terrestrial so-called impact structures and its implication

Criteria used to identify crypto-explosive structures as of impact origin imply only shock. Geographical distribution of many localities is non-random and relates to distribution of carbonatites and other igneous rocks. The implications are important and numerous. One is that some “meteorites” are almost certainly Earth material, another that tektites are entirely terrestrial.     

膜分离腐殖质前后晚期渗滤液可生化性的变化

晚期渗滤液由于含有大量难降解有机物腐殖质,可生化性差,较难处理。采用特定分子量的超滤膜对晚期渗滤液中的腐殖质进行有效的分离,研究了膜分离腐殖质前后渗滤液的可生化性的变化：渗滤液中腐殖质类物质去除率为90．7％,BOD5/COD值提高了6倍,可生物降解的有机物在总有机物中所占比率提高了约4倍。结果表明,分离腐殖质可提高渗滤液的可生化性。     

Evaluation of oxidation stability of lignite humic substances by DSC induction period measurement

The stability of lignite humic acids and four regenerated humic acids was estimated by employing differential scanning calorimetry. Induction period for the oxidative decomposition of humic matter was calculated from non-isothermal measurements at six different rates of heating. To simulate the gradual evolution history of humic acids, different intensities of oxidation attack by nitric acid on the original lignite was used. Experimental data showed higher stability of natural humic acids in the temperature range where the decomposition step occurred. On the other hand, extrapolation to lower temperatures and calculated kinetic parameters did not correspond to the order observed at higher temperatures. An oscillating trend of calculated parameters of the two proposed parts of stability was observed, which agreed with data concerning regenerated humic acids production. The approach applied in this work represents a rapid and useful method for evaluation of organic matter stability.     

边缘海环境中陆源有机质的化学生物标志物研究进展

边缘海是陆地和大洋的连接带,是陆源物质向开阔海输送的主要途径,在全球碳循环过程发挥着重要的作用。示踪边缘海沉积有机碳的来源,可以为有机碳的分布、降解、迁移和转化等研究提供基础。本文从高等植物类脂化合物(如长链正构烷烃、正构烷醇、脂肪酸、甾醇等)、维管植物木质素和土壤有机质支链和类异戊二烯四醚(BIT)等几个方面,介绍了基于化学生物标志物示踪边缘海陆源有机质来源的研究进展。指出以包含木质素、BIT等指标在内的多重示踪方法和多端元模型是指示边缘海沉积有机质来源的良好方法,能够提供比单指标方法更为准确可靠的结果。     

大鹏澳养殖海域表底层水环境及浮游动物群落结构的比较研究

2007年5月～2008年4月对大鹏澳鱼类养殖区、贝类养殖区、自然海区(对照区)进行了每月一次的调查,分析比较了不同站点表底层水环境因子和浮游动物种类组成、数量变动的季节差异.结果表明:3个站点表层溶解氧年均值分别为5.46、7.26和8.10 mg/L,表层高于底层,表底层差异极显著(p＜0.01);总氮(TN)、总...     

Selenium in agriculture and the environment

Selenium occurs naturally in the soil environment in amounts which may cause nutritional toxicity or deficiency to livestock in areas throughout the world. Normal soils contain between 0.1 and 2.0 μg g^?1 selenium compared with 30–324 μg g^?1 (dry weight) or above from a seleniferous area. Plant selenium concentrations can generally be used as an indicator of the soil selenium status. Selenium accumulator plants may contain thousands of μg g^?1 selenium and grow healthily on highly seleniferous soils. Most plants contain small amounts of selenium; less than 1 μg g^?1 when growing on normal soils. A third group of plants, containing large amounts of sulphur, contain higher amounts of selenium when growing on normal soils.Animals consuming plants containing unusually small or large amounts of selenium over a prolonged period may develop nutritional selenium disorders. Development of sensitive analytical techniques has permitted detection of the very low amounts of selenium present in livestock suffering from selenium deficiency and associated problems. Required amounts of selenium necessary for animal nutrition range from 0.04 to 0.10 μg g^?1 depending on the animal species and the level of vitamin E in the diet. Amounts of selenium causing nutritional toxicity are usually an order of magnitude higher than those producing deficiency.Factors affecting selenium absorption in animals include the form of selenium in the diet and the type of animal. Ruminants moderate their dietary intake by reducing selenium to insoluble forms, which they excrete. Monogastric animals, by contrast, may absorb up to 80% or more of their dietary selenium intake, depending on its biological availability.Although there are areas where livestock poisoning occurs, much evidence has been accumulated to indicate that agricultural livestock is deficient, or bordering on selenium deficiency, in many areas of the world. Overt selenium deficiency in man has been reported in China, indicating the possibility of widespread non-overt sub-clinical selenium deficiency in humans. No definite evidence for human selenium toxicity has been reported.Although anthropogenic selenium contributes to the total selenium in the soil environment, most of it is biologically unavailable. Organisms such as bacteria and fungi reduce biologically available selenium to elemental insoluble forms, whilst others produce volatile organic forms of selenium which are lost to the atmosphere. Some bacteria are able to oxidise colloidal selenium so that it becomes biologically available. Whether the overall amount of biologically available selenium is increasing or decreasing in the soil environment is of vital consequence to agricultural productivity. It is recommended that work should be carried out to quantify amounts of available selenium that are lost from soil systems, and to identify the forms and amounts of selenium that enter the soil environment from natural and anthropogenic sources. Tests to indicate the presence of non-overt selenium deficiency in animals, such as blood selenium measurements, are recommended for areas under suspicion from soil and crop analyses.     

Effect of environmental factors on the complexation of iron and humic acid

A method of size exclusion chromatography coupled with ultraviolet spectrophotometry and off-line graphite furnace atomic absorption spectrometry was developed to assess the complexation properties of iron(Fe) and humic acid(HA) in a water environment. The factors affecting the complexation of Fe and HA, such as ionic strength, p H, temperature and UV radiation, were investigated. The Fe–HA complex residence time was also studied. Experimental results showed that p H could influence the deprotonation of HA and hydrolysis of Fe, and thus affected the complexation of Fe and HA. The complexation was greatly disrupted by the presence of Na Cl. Temperature had some influence on the complexation. The yield of Fe–HA complexes showed a small decrease at high levels of UV radiation, but the effect of UV radiation on Fe–HA complex formation at natural levels could be neglected. It took about 10 hr for the complexation to reach equilibrium, and the Fe–HA complex residence time was about 20 hr.Complexation of Fe and HA reached a maximum level under the conditions of p H 6, very low ionic strength, in the dark and at a water temperature of about 25°C, for 10 hr. It was suggested that the Fe–HA complex could form mainly in freshwater bodies and reach high levels in the warm season with mild sunlight radiation. With changing environmental parameters, such as at lower temperature in winter or higher p H and ionic strength in an estuary, the concentration of the Fe–HA complex would decrease.     

镉铅在粘土上的吸附及受腐殖酸的影响

试验研究了镉和铅2种重金属在蒙脱土和高岭土上的吸附,以及外加腐殖酸的3种组分（富里酸、棕色胡敏酸和灰色胡敏酸）的影响。镉铅在粘土上的吸附随着介质pH的升高而增加。在pH4-8范围内的任意pH点,镉在高岭土上的吸附量因富里酸而降低,因2种胡敏酸而升高;当pH值高于6时,吸附量急剧增加。外加富里酸使得铅在粘土上的吸附在pH＞6时意外出现随着介质pH而降低的趋势。     

海洋沉积物中腐殖酸的提取与紫外吸收光谱特征

采用NaOH碱提法提取和纯化了海洋沉积物中的腐殖酸,研究了腐殖酸的紫外吸收光谱特征,考察了pH、盐度和溶解有机质对腐殖酸吸光度的影响。结果显示,pH对腐殖酸的吸光度有显著的影响,在pH<6.5的酸性和pH>8.5的碱性条件下吸光度随pH的增大而增强,但pH在6.5～8.5范围内对吸光度的影响不大。盐度和溶解有机质对腐殖酸的吸光度影响较小。     

腐植质与有机污染物作用研究进展

综述了腐殖质的结构特性、与有机污染物的结合性质以及腐殖质对有机污染物毒性和生物可利用率的影响。已有的研究表明:腐殖质与有机污染物的结合能力受到下列因素的影响———腐殖质的结构、腐殖质的分子量和浓度、有机物的结构、水环境条件以及光化学降解作用等;腐殖质的存在通常降低了有机污染物的毒性,但在少数情况下例外,其推测性的机理还有待于实验进一步验证;有机污染物的生物可利用率不仅与腐殖质的浓度和组成有关,还受水体PH值的影响。本文同时对腐殖质的结构和多样性的研究、腐殖质对极性有机污染物的迁移、毒性和生物可利用率的研究、腐殖质增强某些有机物毒性的机理的研究进行了展望。     

Synthesis and characterization of agricultural controllable humic acid superabsorbent

Humic acid superabsorbent polymer (P(AA/AM-HA)) and superabsorbent polymer (P(AA/AM)) were synthesized by aqueous solution polymerization method using acrylic acid (AA), acrylamide (AM) and humic acid (HA) as raw material. The effects of N,N'-methylenebisacrylamide (MBA) crosslinking agent, potassium peroxydisulfate (KPS) initiator, reaction temperature, HA content, ratio of AA to AM, concentration of monomer and neutralization of AA on water absorption were investigated. Absorption and desorption ratios of nitrogen fertilizer and phosphate fertilizer were also investigated by determination of absorption and desorption ratio of NH₄⁺, PO₄^3? on P(AA/AM-HA) and P(AA/AM). The P(AA/AM-HA) and P(AA/AM) were characterized by Fourier translation infrared spectroscopy, biological photomicroscope and scanning electron microscopy (SEM). The optimal conditions obtained were as follows: the weight ratio of MBA to AA and AM was 0.003; the weight ratio of KPS to AA and AM was 0.008; the weight ratio of HA to AA was 0.1; the mole ratio of AM to AA is 0.1; the mole ratio of NaOH to AA is 0.9; the reaction temperature was 60°C. P(AA/AM-HA) synthesized under optimal conditions, has a good saline tolerance, its water absorbency in distilled water and 0.9 wt.% saline solution is 1180 g/g and 110 g/g, respectively. P(AA/AM-HA) achieves half saturation in 6.5 min. P(AA/AM-HA) is superior to P(AA/AM) on absorption of NH₄⁺, PO₄^3?. The SEM micrograph of P(AA/AM-HA) shows a fine alveolate structure. The biological optical microscope micrograph of P(AA/AM-HA) shows a network structure. Graft polymerization between P(AA/AM) and HA was demonstrated by infrared spectrum. The P(AA/AM-HA) superabsorbent has better absorbing ability of water and fertilizer, electrolytic tolerance and fewer cost than P(AA/AM) superabsorbent.