长期规律耕作土壤腐殖质的高分辨核磁共振研究

利用高分辨核磁共振波谱技术对来自长期规律耕作土壤中的腐殖质进行研究，根据所测核磁共振谱粗略探讨了土壤腐殖质的化学基团组成，及不同耕作模式对土壤腐殖质化学基团构成的影响，及部分土壤腐殖质化学基团之间的偶联关系。     

有机污染物水解速度常数与腐殖质浓度定量关系的建立及验证

水解是有机污染物转化降解的重要途径.天然水体中的腐殖质影响有机化合物的水解速度常数,使之与蒸馏水缓冲系统中的测定值有较大差别.本文推导并验证了腐殖质浓度与水解速度常数的定量关系,测定了腐殖质与有机化合物的缔合系数.     

天然水体中腐殖质的光化学研究进展

本文综述了近年来天然水体中腐殖质的光化学研究进展,重点讨论腐殖质以及相关活性氧的光化学反应机理,并分析了影响腐殖质光解的主要因素,最后,针对水体腐殖质光化学研究中面临的问题,提出了今后的重点研究方向.     

锑胁迫下腐殖质对头花蓼体内锑形态及生化特性影响

锑(Sb)是一种无延展性的有色金属,具有潜在毒性和致癌性,对心血管、呼吸系统和肝脏等都会造成危害。并且,随着近几年锑资源的持续开发,土壤中的Sb污染被广泛关注。腐殖质具有复杂结构并包含有羧基、醇羟基等多种活性官能团,对重金属在土壤中的形态转化、迁移能力以及生物可利用性具有重要影响。头花蓼作为民间常用草药并且也是贵州省特色苗药,在土壤Sb背景值极高的独山锑矿区不仅能大量生长,并且在其体内Sb含量远高于其他未受污染的陆生植物时,仍然可以表现出良好的生长状态。为了探究腐殖质对独山矿区内Sb污染土壤中头花蓼植物有效性的影响。选取贵州省独山县东峰Sb区附近Sb污染土壤与头花蓼种子作为试验样品,通过三种不同腐殖质富里酸、胡敏素、胡敏酸对Sb污染土壤进行30d的培育实验后种植头花蓼。结果表明：(1)腐殖质添加后使得头花蓼叶绿素总量整体呈现上升的趋势,加强了头花蓼光合作用。(2)头花蓼的逆境生理现象表现为：在低添加量下,胡敏素实验组与胡敏酸实验组中丙二醛含量下降,SOD酶活性升高,CAT酶活性下降;说明胡敏素和的胡敏酸在低添加量下能够有效缓解头花蓼所受到的Sb毒害;而高添加量富里酸对头花蓼有一定损害。(3)低添加量的胡敏酸能够有效缓解头花蓼植株所受到的重金属Sb、As、Cd、Cu胁迫。(4)相比于胡敏素和胡敏酸,富里酸更容易促进头花蓼体内残渣态Sb向更活跃的赋存形态转化;胡敏酸对头花蓼中的Sb赋存形态表现出了低浓度活化而高浓度钝化的现象;胡敏素则能够有效降低头花蓼体内Sb活性。     

腐殖质与铀和超铀元素相互作用的研究进展

腐殖质是一类广泛存在于自然界中的高分子有机化合物,能与放射性核素相互作用,从而影响其在自然环境中的化学形态、迁移沉降、氧化还原行为等。本文介绍了目前国内外关于腐殖质与铀和超铀元素相互作用的研究现状和进展,并对存在的问题及今后的发展方向进行了初步讨论。     

近边X射线吸收精细结构光谱法研究土壤腐殖质组分含碳官能团组成及磷酸根影响

应用同步辐射近边X射线吸收精细结构(NEXAFS)光谱技术研究了土壤腐殖质各组分(富里酸、胡敏酸及胡敏素等)的含碳官能团组成信息,并通过分析PO43-存在条件下胡敏酸、胡敏素的官能团组成变化特征,探讨了PO43-与土壤腐殖质之间的微观作用机制。结果表明,土壤腐殖质不同组分的官能团分布具有类似的光谱特征,但组成比例存在明显差异。随着腐殖质组分的酸不溶性增加,胡敏酸、胡敏素疏水性脂肪基官能团比例显著高于富里酸,芳构化程度也明显增加,而亲水性羧基官能团比例趋于降低;PO43-通过静电作用、取代反应可以选择性释放胡敏酸中部分小分子羧基官能团,从而改变胡敏酸官能团的组成特征。此研究结果对于应用NEXAFS研究有机碳官能团形态、结构及理解PO43-在土壤微界面上的反应机制具有重要意义。     

前言:有机分析研究进展专刊

正有机分析是对有机化合物的组成和结构进行定性和定量分析,研究内容涵盖分离、纯化、鉴定和测定等,是分析化学在有机化学领域中的延展,更是人们认识有机世界的重要手段之一.有机分析可溯源到18世纪末,科学家利用有机分析方法研究有机物,发现仅由碳、氢、氧和氮等少数几种元素就组成了数目庞大的有机化合物,奠定了有机分析的基础.20世纪初,分析化学逐步发展成为一门学科,并建立了经典化学分析方法,应用于有机元素的微量分析.20世纪40年代,随着近代物理学和电子学的发展和渗透,有机分析突破了以经典化学     

土壤/沉积物吸附有机污染物机理研究的进展

有机污染物与土壤、沉积和以及地表水中悬浮物（如腐殖质）之间的相互作用——吸咐与解吸是决定它们环境行为最重要的因素之一。自60年代末期以来,经各国科学院们的共同努力,该项工作取得了一些非常重要的研究成果,本文将对该领域的研究现状进行评述,并对其未来可能的发展方向提出自己的见解。     

量子化学在分析试剂反应性能中的应用

本文对量子化学方法应用于分析化学的有机显色反应能作一综述，重点从量子化学在生色理论，在试剂络合性能研究中，在试剂质子化及其酸碱平衡和存在形成研究中以及在取代基效应的中的应用四个方面进行了论述，重点介绍我国在这一方面的工作。认为用量子化学方法预测试剂和络合物的某些性质成为可能。参考文献６０篇。     

稀土的电分析化学

本文介绍了稀土元素的电分析化学，举例简述三大类染料及一些有机试剂与稀封土离子的络合吸附波、络合物组成、电还原机理及其在稀土农用中的分析应用，具有我国对稀土电分析化学研究的特点。     

Electrospray ionization mass spectrometry of terrestrial humic substances and their size fractions

Electrospray ionization mass spectrometry (ESI-MS) was used to evaluate the average molecular mass of terrestrial humic substances, such as humic (HA) and fulvic (FA) acids from a soil, and humic acid from a lignite (NDL). Their ESI mass spectra, by direct infusion, gave average molecular masses comparable to those previously obtained for aquatic humic materials. The soil HA and FA were further separated in size-fractions by preparative high performance size exclusion chromatography (HPSEC) and analyzed with ESI-MS by both direct infusion and a further on-line analytical HPSEC. Unexpectedly, their average molecular mass was only slightly less than for the bulk sample and, despite different nominal molecular size, did not substantially vary among size-fractions. The values increased significantly (up to around 1200 Da) after on-line analytical HPSEC for the HA bulk sample, at both pH 8 and 4, and for the HA size-fractions when pH was reduced from 8 to 4. It was noticed that HA size-fractions at pH 8 were separated by on-line HPSEC in further peaks showing average masses which progressively increased with elution volume. Furthermore, when the HA and NDL bulk samples were sequentially ultracentrifuged at increasing rotational speed, their supernatants showed mass values which were larger than bulk samples and increased with rotational speed. These variations in mass values indicate that the electrospray ionization is dependent on the composition of the humic molecular mixtures and increases when their heterogeneity is progressively reduced. It is suggested that the dominance of hydrophobic compounds in humic supramolecular associations may inhibit the electrospray ionization of hydrophilic components. Our results show that ESI-MS is reasonably applicable to humic substances only after an extensive reduction of their chemical complexity.     

Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

Membrane filtration studies of aquatic humic substances and their metal species: a concise overview Part 1. Analytical fractionation by means of sequential-stage ultrafiltration

A concise overview (75 references) of the analytical fractionation of aquatic humic substances using sequential-stage ultrafiltration is presented. First, humic substances in aquatic environments and actual problems connected with their fractionation and analysis are briefly considered. The molecular size classification of dissolved humic substances by means of multistage ultrafiltration, with special emphasis on on-line techniques, is the focal point of the discussion. In particular, the capabilities of ultrafiltration for the size fractionation and characterization of species formed between colloidal humic substances and pollutants (e.g. metals) are stressed.     

Advances in humeomics: Enhanced structural identification of humic molecules after size fractionation of a soil humic acid

We size fractionated a soil humic acid (HA) by preparative high performance size exclusion chromatography (HPSEC) and evaluated the analytical capacity of humeomics to isolate and identify humic molecular components in the separated size-fractions. HA and its three size-fractions were chemically fractionated to extract non-covalently bound organosoluble compounds (ORG1), weakly ester-bound organosoluble (ORG2) and hydrosoluble constituents (AQU2), strongly ester-bound organosoluble components (ORG3), and final unextractable residues (RES4). According to their solubility, the extracts were characterized by either GC–MS or on-line thermochemolysis/GC–MS techniques. The humeomic sequence showed that the analytical yields of identified compounds in either ORG or AQU extracts of size-fractions were invariably larger than for the unfractionated HA. This was attributed to a weaker conformational stability of humic suprastructures obtained by HPSEC fractionation, thereby enabling an improved separation and identification of single humic molecules. In line with the supramolecular understanding of humic substances, we found that hydrophobic compounds were mainly distributed in the largest size-fraction, while hydrophilic components were eluted in the smallest size-fraction. Furthermore, compounds with linear chains or stackable aromatic rings associated in regular structures were more abundant in the former fraction, whereas irregularly shaped compounds, that hindered association in larger size, were mostly found in the latter fraction. Thus the structural characteristics of single humic molecules determined their mutual association in humic suprastructures, as well as their conformational strength and shape. The lack of de novo synthesized macropolymers in the unfractionated soil humic matter was confirmed by the absence of RES4 fractions in the separated size-fractions. Our results indicate that humeomics capacity to reveal the complex molecular composition of humic suprastructures was significantly improved by subjecting humic matter to a preliminary HPSEC fractionation.     

Capillary zone electrophoresis of natural organic matter

This paper presents an in-depth look at the use of capillary electrophoretic (CE) techniques for the fingerprinting and characterization of humic substances and natural organic matter. These materials are highly heterogeneous in structure and show all characteristics of mixtures unliked in analytical chemistry. The electrophoretic approach, however, allows the determination of mobility distributions in different solution conditions, representative of the effective charge and size distribution status of the components present. A tabulated review covers over 50 references on the subject and highlights the possibilities and problems encountered in the analysis of such polydisperse materials with CE methods. In a second part of the article the consequences of experimental and buffer parameters on the behavior of humic materials in CE are presented.     

Hyphenated techniques of thermal analysis for characterisation of soil humic substances

Our aim was to investigate the thermal behaviour of humic substances extracted from temperate and tropical soils by means of hyphenated techniques of thermal analysis (e. g. simultaneous thermal analysis DSC/TG coupled with mass spectrometry, MS, for the analysis of evolved gas, EGA) in order (i) to verify whether the chemical composition of isolated humic substances also reflected the differences in microbial parameters previously measured in related soil samples and (ii) to identify suitable indices of thermal stability. Our results show that the investigation of humic substances by thermal methods can provide information on soil organic matter dynamics. Differences in thermal behaviour between the two groups of soils were found. The indices of thermal stability here proposed, IR (index of thermal recalcitrance), and ID (index of thermal decomposability) clearly showed that in humic substances from tropical soils the thermally recalcitrant organic fraction dominated, whilst in temperate humic substances the opposite held. This agrees with previous results on the microbial dynamics and organic matter turnover of the respective soils and indicates that these indices of thermal stability could represent a useful tool in soil environmental quality investigations.     

Tangential-flow ultrafiltration: a versatile methodology for determination of complexation parameters in refractory organic matter from Brazilian water and soil samples

In this work the copper(II) complexation parameters of aquatic organic matter, aquatic and soil humic substances from Brazilian were determined using a new versatile approach based on a single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods. The results regarding the copper(II) complexation capacity and conditional stability constants obtained for humic materials were compared with those obtained using direct potentiometry with a copper-ion-selective electrode. The analytical procedure based on ultrafiltration is a good alternative to determine the complexation parameters in natural organic material from aquatic and soil systems. This approach presents additional advantages such as better sensibility, applicability for multi-element capability, and its possible to be used under natural conditions when compared with the traditional ion-selective electrode.     

Fractionation analysis of trace metals in humic substances of soils irrigated with wastewater in Central Mexico by particle induced X-ray emission

The Mezquital Valley in Central Mexico has received wastewater from Mexico City for nearly 100 years. Wastewater brings in organic matter and nutrients but also trace metals. Humic substances, the main components of organic soil matter, are responsible for retaining and regulating the mobility of trace metals in soils. In this study, humic substances were extracted from the soil and separated into distinct fractions (humic acids, fulvic acids and humins). The particle induced X-ray emission (PIXE) technique was applied to determine the metal content in bulk soil as well as in humic acids and fulvic acids not soluble in H₃PO₄. In order to assess whether the long-term input of organic matter and metals modifies the metal association with these humic substances, parcels irrigated for three time periods (5, 47 and 89 years) were selected for this study. It was observed that metals such as Zn and Cu are mainly associated with the humic acids. Fulvic acids retain mainly Cr while Pb is distributed among humic and fulvic acids. It was also observed that in general, metal retention by humic substances increases with irrigation time. Depth also affects metal association with the humic substances.     

Sampling of Natural Water Using the Ultrasonic and Ultraviolet Decomposition of Humic Substances

It was shown that the time dependences of the degree of decomposition of humic substances under exposure to ultrasound and UV radiation exhibit identical maxima. It was found that ultrasonic and ultraviolet treatments enhance the analytical signal even in the absence of humic substances. It was proposed to use the ultrasonic pretreatment before the extraction–X-ray fluorescence analysis of water to eliminate the effect of humic substances on the recovery of elements.