Investigation of metal ions binding of humic substances using fluorescence emission and synchronous‐scan spectroscopy

Abstract

The binding site interactions of IHSS humic substances, Suwannee River Humic Acid, Suwannee River Fulvic Acid, Nordic Fulvic Acid, and Aldrich Humic Acid with various metals ions and a herbicide, methyl viologen were investigated using fluorescence emission and synchronous‐scan spectroscopy. The metal ions used were, Fe(III), Cr(III), Cr(VI), Pb(II), Cu(II) and Ni(II). Stern‐Volmer constants, K_SV for these quenchers were determined at pH 4 and 8 using an ionic strength of 0.1M. For all four humic substances, and at both pH studied, Fe(III) was found to be the most efficient quencher. Quenching efficiency was found to be 3–10 times higher at pH 8. The bimolecular quenching rate constants were found to exceed the maximum considered for diffusion controlled interactions, and indicate that the fluorophore and quencher are in close physical association. Synchronous‐scan spectra were found to change with pH and provided useful information on binding site interactions between humic substances and these quenchers.     

基于经济发展阶段理论的土地利用变化研究——以广西江州区为例

土地利用在不同的经济发展阶段表现出不同特点。广西江州区属于我国西部经济欠发达地区,经济发展正处于工业化初期的起步阶段,土地利用变化特点主要表现为:以农业生产用地和生态用地竞争为主,耕地变化是土地利用变化的主要内容;建设用地低效、缓慢增长,农村居民点增长面积占较大比重;人均农村居民点面积逐渐增加。以1978-2002年的统计数据为基础,用主成分分析和回归分析相结合,对耕地面积变化的驱动力进行了研究,结果表明:人口增长、经济发展和土地管理使得耕地面积不断增长,收入和消费的提高以及农业产业结构调整导致耕地面积减少。发达地区的发展历程表明,经济高速发展必然引起农地快速非农化,江州区在土地利用中,必须注意节约用地,保护耕地,减少土地资源浪费,防止环境污染,实现区域土地的可持续利用。     

自制新型液相色谱柱同时测定土壤中两种农药

用自制的新型N-苄氧羰基-(-)-L-苯甘氨酰-(-)-L-苯甘氨酰基键合硅胶液相色谱固定相(简称BCPGPG色谱固定相)在正相条件下对土壤中氰戊聚酯和氯氰菊酯两种农药进行了分析与测定,建立了可同时测定土壤中的氰戊菊酯和氯氰菊酯含量的正相高效液相色谱方法。样品用流动相(正己烷/二氯甲烷=8/1,V/V)溶解,过滤,然后以BCPGPG固定相柱进行色谱分离,在254nm处进行测定。结果表明,氰戊菊酯和氯氰菊酯的质量浓度为0～2.0mg/L时其峰面积与质量浓度的线形关系良好;批间(n=4)测定的平均相对偏差(RSD)分别为5.70%和5.5%;回收率分别为81.0%～96%和88.0%～96.7%。该方法适合于测定氰戊聚酯和氯氰菊酯两种农药的含量测定,方法准确,操作简便。     

Aniline removal by Photocatalytic reaction of iron(iii) mediated with dissolved organic matter

When light (> 370 nm) was allowed to interact with an aqueous solution containing dissolved organic matter (DOM) and Fe(III), removal of aniline (AN) was observed. This was due to the photocatalytic reaction of Fe(III) mediated by DOM. Syringic acid (SYA) and humic acid (HA) were used as DOM in the present study. The ¹⁵N‐NMR spectrum of the product mixture from the light irradiation of the SYA/Fe(III) system demonstrated that AN was covalently bound to SYA. The kinetics of AN removal were, therefore, interpreted by assuming covalent binding between DOM and AN. The amounts of covalent binding sites and the apparent second‐order rate constants could be evaluated, and the amounts of covalent binding sites decreased with the increases of the concentration of DOM. This is attributed that the polymerization of DOM by the photo‐oxidation competed with the covalent binding between AN and DOM.     

锦州湾沉积物芯样中重金属污染及变化动态

研究了锦州湾海域底质沉积物中重金属（Zn,Pb,Cd,Fe,Mn）的含量分布,并以一个代表性的水平剖面和一个垂直剖面（J06号芯样）分析了重金属含量变化动态。通过回归计算得出几种金属在水平距离上的变化方程;在分析该湾沉积理化环境基础上,探讨了重金属地球化学相的垂向含量变化,Fe、Mn二元素的垂直剖面的成岩演变。认为沉积物中金属元素释放出来而污染上覆海水,最后得出该湾金属的污染程度及环境现状的结论。     

持久性有机污染物在环境中相的划分及相平衡的泛逸度模型设想

鉴于持久性有机物在环境中的结合和承载机制,作者认为,对于持久性有机物,环境可以抽象为气相、水相、有机碳相和脂相等四个均质、同结合作用的环境相,为描述持久性有机物在环境相间的平衡分配行为,引入了“泛逸度”的概念,建立了环境相间相平衡酌泛逸度模型,并以DDT为例尝试了模型的应用。     

约束混凝土梁的升降温全过程弯矩分析

利用SAFIR程序,开展了约束混凝土梁的升降温全过程梁端弯矩分析;考察了转动约束刚度比、轴向约束刚度比、截面尺寸、荷载比、全截面配筋率和升温时间等参数对梁端弯矩的影响规律,并与单调升温时的相应规律进行对比,给出了梁端弯矩的实用计算方法。研究结果表明:对于先升温、后降温的约束混凝土梁梁端弯矩的变化,总体表现出与单调升温类似的特征,主要区别在于后期因降温作用而呈现出缓慢降低的趋势;转动约束刚度比对梁端弯矩的影响集中在升温前期,在此时段内,梁端弯矩随着转动约束刚度比的增加而增大,但增幅逐渐趋缓;升温后30 min以内,轴向约束刚度比的改变对梁端弯矩几乎没有影响;之后,梁端弯矩随着轴向约束刚度比的增加而逐渐减小。     

土壤固相吸附砷的研究进展

砷是一种常见的有毒元素,土壤砷污染与修复问题已引起世界范围的广泛关注。土壤原位修复是消除土壤砷污染的有效方法,其中砷在土壤固相上的吸附也是近年来的研究热点。土壤固相广泛存在于土壤中,并具有表面积大和表面电荷等理化性质,它可通过与砷酸根阴离子发生表面配位反应,形成内外层配位体等方式来固定土壤中的砷,以降低金属离子的迁移能力和有效性,是一种有效的原位减轻砷污染的方法。文中简单介绍了砷污染的现状、危害和赋存状态,重点介绍了铁铝锰的氧化物和氢氧化物、粘土矿物、有机质等土壤固相对砷的吸附机理及其影响因素,旨在更好地掌握砷的吸附行为。     

Characterization of binding site heterogeneity for copper within dissolved organic matter fractions using two-dimensional correlation fluorescence spectroscopy

The heterogeneity of copper binding characteristics for dissolved organic matter (DOM) fractions was investigated based on the fluorescence quenching of the synchronous fluorescence spectra upon the addition of copper and two-dimensional correlation spectroscopy (2D-COS). Hydrophobic acid (HoA) and hydrophilic (Hi) fractions of two different DOM (algal and leaf litter DOM) were used for this study. For both DOM, fluorescence quenching occurred at a wider range of wavelengths for the HoA fractions compared to the Hi fractions. The combined information of the synchronous and asynchronous maps derived from 2D-COS provided a clear picture of the heterogeneous distribution of the copper binding sites within each DOM fraction, which was not readily recognized by a simple comparison of the changes in the synchronous fluorescence spectra upon the addition of copper. For the algal DOM, higher stability constants were exhibited for the HoA versus the Hi fractions. The logarithms of the stability constants ranged from 4.8 to 6.1 and from 4.5 to 5.0 for the HoA and the Hi fractions of the algal DOM, respectively, depending on the associated wavelength and the fitted models. In contrast, no distinctive difference in the binding characteristics was found between the two fractions of the leaf litter DOM. This suggests that influences of the structural and chemical properties of DOM on copper binding may differ for DOM from different sources. The relative difference of the calculated stability constants within the DOM fractions were consistent with the sequential orders interpreted from the asynchronous 2D-COS. It is expected that 2D-COS will be widely applied to other DOM studies requiring detailed information on the heterogeneous nature and subsequent effects under a range of environmental conditions.     

Modelling the conversion of Colombian lowland ecosystems since 1940: drivers, patterns and rates

In biologically mega-diverse countries that are undergoing rapid human landscape transformation, it is important to understand and model the patterns of land cover change. This problem is particularly acute in Colombia, where lowland forests are being rapidly cleared for cropping and ranching. We apply a conceptual model with a nested set of a priori predictions to analyse the spatial and temporal patterns of land cover change for six 50-100 km(2) case study areas in lowland ecosystems of Colombia. Our analysis included soil fertility, a cost-distance function, and neighbourhood of forest and secondary vegetation cover as independent variables. Deforestation and forest regrowth are tested using logistic regression analysis and an information criterion approach to rank the models and predictor variables. The results show that: (a) overall the process of deforestation is better predicted by the full model containing all variables, while for regrowth the model containing only the auto-correlated neighbourhood terms is a better predictor; (b) overall consistent patterns emerge, although there are variations across regions and time; and (c) during the transformation process, both the order of importance and significance of the drivers change. Forest cover follows a consistent logistic decline pattern across regions, with introduced pastures being the major replacement land cover type. Forest stabilizes at 2-10% of the original cover, with an average patch size of 15.4 (+/-9.2)ha. We discuss the implications of the observed patterns and rates of land cover change for conservation planning in countries with high rates of deforestation.