红壤中矿物表面对腐殖质吸附萘的影响

矿物表面可改变土壤腐殖质对疏水性有机污染物的结合能力。采用红壤和高岭石分别与胡敏酸结合制备得到的两种复合体对萘的吸附等温线非线性显著,其n=0.76或0.74,并且有机碳归一化吸附分配系数的实验值Koacds是采用Kow计算得出的理论值Koc的5倍以上,表明红壤、高岭石均对腐殖质吸附萘有强化作用,且红壤较之高岭石对腐殖质吸附萘的影响稍强些。主要原因是,红壤中除了高岭石外,还有与腐殖质结合力很强的铁氧化物,而且很可能是吸附态腐殖质组成结构形态发生了有利于对萘吸附的改变。     

The association of organic molecules with clay minerals in aqueous solutions

The uptake of dissolved organic molecules by kaolinite and montomorillonite clay minerals was measured in distilled water and saltwater solutions. Glucose and valine exhibited low affinities for both clay minerals over a wide range of concentrations in distilled water and seawater solutions. Stearic acid was efficiently removed by both clay minerals from all solutions over the concentration range 10–1000 ppb. These experiments suggest that some dissolved organic molecules may be preferentially removed by clay minerals in natural waters. It is unlikely, however, that the partitioning of simple organic molecules between natural waters and suspended clay minerals could produce the high concentrations of organic matter that occur in most fine-grained sediments.     

有机组分土-水分配系数的确定(英文)

有机组分的土水分配系数(Kd)是描述有机组分在地下系统中吸附特征的重要参数。同时,它也是物质运移模拟和环境评价中的主要参数之一。影响Kd的因素可概括为三个方面:土壤性质、有机组分本身特征及水相的物理化学性质。一般而言,对于非极性和弱极性有机组分,土壤中的有机质含量(foc )是影响Kd的最主要因素。但是,对于极性有机组分(POCs), 特别是在土壤有机质含量较低的情况下,土壤中矿物的种类和含量、水化学组分特征(pH、离子力等)经常在吸附过程中起重要作用。实验室内测定Kd的方法包括批实验和柱实验方法。批实验法适用于研究Kd较高情况下的吸附。在Kd较低的情况下,如低有机质土壤对极性有机污染物的吸附,土柱色谱法(SCC)是更适宜的选择。另外,可用土柱色谱法快速了解各种因素对吸附过程的影响,并获取详细的吸附和解吸信息。应用土柱色谱法时应当注意非平衡吸附和可能的柱堵塞问题。很多文献中提到结合柱实验和已有的吸附数据来预测土壤有机碳标准化的分配系数Koc(=Kd/foc)。但是,如果没有考虑吸附中特定的作用过程(如矿物吸附),对极性有机组分Koc的预测将会产生很大的误差。在环境评价中,将从一种土壤测定的Koc 应用到不同性质的土壤中,可能会导致错误的认识。在进行室内实验时,应把标准土(如Eurosoi     

Chemical weathering in the drainage basin of a tropical watershed (Nsimi-Zoetele site, Cameroon) : comparison between organic-poor and organic-rich waters

This study deals with the weathering processes operating at the scale of a small catchment (Nsimi-Zoetele, Cameroon) and is focused on the role of organic colloids on mineral weathering and transport of elements in natural waters. Samples of river, spring and groundwaters from Nsimi-Zoetele were filtered through membranes of decreasing pore size (0.22 μm, 0.025 μm, or: 300,000 Da, 5000 Da) to separate colloidal fractions from the truly dissolved one. Major and trace elements and dissolved organic carbon (DOC) were analysed in each fraction. Two kinds of waters can be distinguished in the catchment: clear and coloured waters. Clear waters exhibit low concentrations of major and trace elements and DOC. Elements are carried in these solutions in a true dissolved form except Al and rare earth elements (REEs). By contrast, the higher abundances of Al, Fe and trace elements in coloured waters are controlled by the colloidal fraction. Thermodynamic equilibrium calculations show that clear waters are in equilibrium with kaolinite and iron oxi-hydroxide which are major minerals in the weathered soil. For coloured waters, the aqueous speciation of Ca, Mg, Cu, Fe, Al, La and Th was calculated taking into account the complexes with humic acids. Speciation calculations for Cu, Fe, Al, La, Th show a strong complexation with humic acids, in good agreement with the results of the filtration experiments. By contrast, although filtration experiments show a strong control of major cations by organic matter (for example 75% for Ca), speciation calculations reveal that their complexes with humic ligands do not exceed a few percent of total dissolved elements. This discrepancy is explained as an artefact induced by the organic colloids and occurring during the filtration procedure. Finally, both filtration experiments and speciation calculations show that organic matter plays an important role in natural DOC-rich waters. Organic acids increase significantly the dissolution rates of silicates and oxi-hydroxides and thus the amounts of solutes and of complexed elements leaving the catchment.     

内蒙古西胡里吐盆地有机质特征及其与铀矿化的关系

在砂岩型铀矿床中 ,有机质与铀矿化之间有着较为密切的关系。西胡里吐盆地的有机质主要是以松柏类和蕨类等高等植物残体为母质的腐殖型有机质。通过镜质体反射率、有机质碎屑的颜色、粘土矿物X 衍射和古地温恢复等分析测试发现 ,有机质的成熟度较低 ,处于未成熟—低成熟早期阶段。有机质的类型和成熟度决定了其在热演化中产生了大量腐殖酸并保存在地层中。褐煤、腐殖酸、残余植物碎屑和地沥青等是现存有机质的主要类型。除大量产出的煤层外 ,有机质主要呈碎屑状和细分散状分布于地层之中。 70 %的岩石中有机质的丰度在 0 1 %～ 3 % ,对铀矿化的形成较为有利。铀与有机质的紧密共生以及二者之间的正相关性 ,表明了有机质在西胡里吐盆地铀矿化形成中所起的重要作用。有机质中的腐殖酸与铀矿化的关系最为密切 ,有机粘土复合体、蚀变岩屑、植物碎屑和地沥青等吸附剂对铀的吸附均与腐殖酸有关。腐殖酸吸附铀后可以将铀还原 ,还可以与铀酰离子等进行络 (鳌 )合形成铀酰腐殖酸盐 ,并最终引起铀的沉淀富集。     

土壤和水体环境中矿物-腐殖质交互作用的研究进展

矿物-腐殖质间的交互作用是土壤和水体沉积物及悬浮颗粒物中环境物质的重要界面过程。不管是氮、磷植物性营养元素还是有毒的重金属、有机物，它们在表生环境中的迁移转化与归趋受到矿物、腐殖质及其复合体的表面活性和迁移性的调控。矿物-腐殖质体系的界面作用研究是前沿性的研究领域，主要目的是揭示矿物-腐殖质复合体的结构特性(例如颗粒物的圈层结构与表面微形貌)及其与颗粒物表面活性的关系，进而揭示土壤和水体环境中矿物-腐殖质间的交互作用规律。本文对该领域的研究现状进行评述，并提出未来可能的发展趋势。     

Preparation and characterization of humic acid cross-linked with organic bridging groups

Cross-linking of humic substances with organic bridging groups is thought to contribute to the humification of soil organic matter. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid, applying procedures established for cross-linking of polymers and textile fabrics. Products of the cross-linking reactions were analyzed by FTIR and ¹³C CPMAS NMR. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and ¹³C CPMAS NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. The reactions investigated in this study can be regarded as models for reactions occurring in natural soils to test the significance of cross-linking reactions in the humification process of soil organic matter and the physico-chemical properties and ecological function of organic matter in geosolids.     

淤泥固化处理中有机物成分的影响

针对有机质对疏浚淤泥固化处理效果产生的影响,研究有机质的主要成分腐殖酸对水泥固化的影响。研究表明,腐殖酸对水泥的水化具有抑制作用,腐殖酸含量对淤泥固化土的无侧限抗压强度和破坏应变的影响存在一个极限含量（3.62 %）,超过这一极限含量,随腐殖酸含量的增加固化土的强度和破坏应变几乎不再变化。同时,研究结果表明,随着腐殖酸含量的增加,固化土塑性增强。     

不同有机酸对矿物溶解的动力学实验研究

用石英、微斜长石和方解石混合颗粒模拟碎屑组分分别与不同有机酸水溶液进行溶蚀实验,以比较储集层内不同矿物在含低分子量有机酸地层水中溶解的速率,并试图探讨矿物溶蚀的微观机理。结果表明：①所有矿物颗粒都发生了不同程度的溶解,表现为颗粒失重,溶液中SiO2和金属阳离子含量增加,pH值上升。②优先溶解的是方解石,其次是硅酸盐矿物。③温度增加,硅酸盐矿物在水中的溶解度明显增加,而方解石的溶解度基本不变。④由于不同有机酸与二氧化硅和金属阳离子生成的络合物稳定性不同,因此,在不同有机酸水溶液中,矿物的溶蚀速率有较大差别。多官能团有机酸的水溶液中,不同矿物有更大的溶解;但在含有丰富Ca2＋的草酸水溶液中,由于矿物颗粒表面难溶草酸钙的沉淀,方解石的溶解变得更加困难。⑤多官能团有机酸与SiO2形成的多环螯合物由于完全取代了硅氧四面体的氧原子,在水中具有高度稳定性,可能有助于(铝)硅酸盐的溶蚀和硅元素的迁移     

Acid neutralizing processes in an alpine watershed front range, Colorado, U.S.A.—1: Buffering capacity of dissolved organic carbon in soil solutions

Soil interstitial waters in the Green Lakes Valley, Front Range, Colorado were studied to evaluate the capacity of the soil system to buffer acid deposition. In order to determine the contribution of humic substances to the buffering capacity of a given soil, dissolved organic carbon (DOC) and pH of the soil solutions were measured. The concentration of the organic anion, Ai⁻, derived from DOC at sample pH and the concentration of organic anion, Ax⁻ at the equivalence point were calculated using car☐yl contents from isolated and purified humic material from soil solutions. Subtracting Ax⁻ from Ai⁻ yields the contribution of humic substances to the buffering capacity (A_equiv.⁻). Using this method, one can evaluate the relative contribution of inorganic and organic constituents to the acid neutralizing capacity (ANC) of the soil solutions. The relative contribution of organic acids to the overall ANC was found to be extremely important in the alpine wetland (52%) and the forest-tundra ecotone (40%), and somewhat less important in the alpine tundra sites (20%). A failure to recognize the importance of organic acids in soil solutions to the ANC will result in erroneous estimates of the buffering capacity in the alpine environment of the Front Range, Colorado.     

红壤酸化过程中铁铝氧化物矿物形态变化及其环境意义

铁铝矿物对土壤中有机质的稳定保持具有十分重要的作用。酸化作用的研究表明,随着浸泡时间的增加,红壤中铁铝总量降低,铝溶蚀较严重;红壤中铁铝氧化物的矿物形态变化表现为:游离态晶质铁铝氧化物大量溶出,而无定形和络合态变化不大。酸性条件下有机质溶出显著,说明除了可能发生水解作用外,游离态铁铝的溶出也起着关键性作用。此外,SEM观察也表明酸化作用引起了土壤团聚体结构的破坏。     

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Weathering of the New Albany Shale, Kentucky: II. Redistribution of minor and trace elements

During weathering, elements enriched in black shale are dispersed in the environment by aqueous and mechanical transport. Here a unique evaluation of the differential release, transport, and fate of Fe and 15 trace elements during progressive weathering of the Devonian New Albany Shale in Kentucky is presented. Results of chemical analyses along a weathering profile (unweathered through progressively weathered shale to soil) describe the chemically distinct pathways of the trace elements and the rate that elements are transferred into the broader, local environment. Trace elements enriched in the unweathered shale are in massive or framboidal pyrite, minor sphalerite, CuS and NiS phases, organic matter and clay minerals. These phases are subject to varying degrees and rates of alteration along the profile. Cadmium, Co, Mn, Ni, and Zn are removed from weathered shale during sulfide-mineral oxidation and transported primarily in aqueous solution. The aqueous fluxes for these trace elements range from 0.1 g/ha/a (Cd) to 44 g/ha/a (Mn). When hydrologic and climatic conditions are favorable, solutions seep to surface exposures, evaporate, and form Fe-sulfate efflorescent salts rich in these elements. Elements that remain dissolved in the low pH (<4) streams and groundwater draining New Albany Shale watersheds become fixed by reactions that increase pH. Neutralization of the weathering solution in local streams results in elements being adsorbed and precipitated onto sediment surfaces, resulting in trace element anomalies.Other elements are strongly adsorbed or structurally bound to solid phases during weathering. Copper and U initially are concentrated in weathering solutions, but become fixed to modern plant litter in soil formed on New Albany Shale. Molybdenum, Pb, Sb, and Se are released from sulfide minerals and organic matter by oxidation and accumulate in Fe-oxyhydroxide clay coatings that concentrate in surface soil during illuviation. Chromium, Ti, and V are strongly correlated with clay abundance and considered to be in the structure of illitic clay. Illite undergoes minimal alteration during weathering and is concentrated during illuvial processes. Arsenic concentration increases across the weathering profile and is associated with the succession of secondary Fe(III) minerals that form with progressive weathering. Detrital fluxes of particle-bound trace elements range from 0.1 g/ha/a (Sb) to 8 g/ha/a (Mo). Although many of the elements are concentrated in the stream sediments, changes in pH and redox conditions along the sediment transport path could facilitate their release for aqueous transport.     

Sorptive removal of ibuprofen from water using selected soil minerals and activated carbon

Pharmaceuticals have gained significant attention in recent years due to the environmental risks posed by their versatile application and occurrence in the natural aquatic environment. The transportation and distribution of pharmaceuticals in the environmental media mainly depends on their sorption behavior in soils, sediment?Cwater systems and waste water treatment plants, which varies widely across pharmaceuticals. Sorption of ibuprofen, a non-steroidal anti-inflammatory drug, onto various soil minerals, viz., kaolinite, montmorillonite, goethite, and activated carbon, as a function of pH (3?C11), ionic strength (NaCl concentration: 0.001?C0.5?M), and the humic acid concentration (0?C1,000?mg/L) was investigated through batch experiments. Experimental results showed that the sorption of ibuprofen onto all sorbents was highest at pH 3, with highest sorption capacity for activated carbon (28.5?mg/g). Among the minerals, montmorillonite sorbed more ibuprofen than kaolinite and goethite, with sorption capacity increasing in the order goethite (2.2?mg/g)?<?kaolinite (3.1?mg/g)?<?montmorillonite (6.1?mg/g). The sorption capacity of the selected minerals increased with increase in ionic strength of the solution in acidic pH condition indicating that the effect of pH was predominant compared to that of ionic strength. An increase in humic acid concentration from low to high values made the sorption phenomena very complex in the soil minerals. Based on the experimental observations, montmorillonite, among the selected soil minerals, could serve as a good candidate to remove high concentrations of ibuprofen from aqueous solution.     

吉林西部土壤铁形态分布及其与土壤性质的关系研究

对吉林西部三个主要农牧区(洮南市、通榆县和乾安县)50个表层土样进行测试,探究其土壤铁形态分布及其与土壤性质的关系。研究结果表明,其土壤铁形态的含量分布为:残渣态铁(A)铁锰结合态铁(B)腐植酸结合态铁(C)碳酸盐态铁(D)强有机结合态铁(E)水溶态铁(F)离子交换态铁(G),主要以A形式存在,且全铁平均含量均低于中国铁元素背景值。A与阳离子交换量(CEC)呈极显著正相关,B与p H值呈极显著正相关,C、E与有机质呈极显著正相关。A与土壤矿质元素的关系最为密切,C、D、G次之。各形态铁之间,B、C、D两两呈极显著正相关,其他形态铁彼此间关系不大。     

Influence of natural organic acids on the Mg/Ca ratio in the bottom sediments of highly mineralized lakes

Thermodynamic modeling of equilibria in the system water–rock–organic acids was used to study the influence of organic acids on Ca and Mg redistribution between a solution and a solid phase in connection with the use of calcites of variable composition Ca_xMg_1–xCO₃ as indicators of paleoclimatic environments. In the thermodynamic model, high-molecular humic substances (fulvic + humic acids) were represented by a set of independent metal-binding centers. Therefore, their number was preset based on the given density of proton- or metal-binding sites. The numerical implementation of several geochemical situations involving the dissolution/deposition of calcites with different Mg contents showed that the main effect of fulvic and humic acids is the acidification of solutions and the reduction of carbonate stability. Although humic substances can play an important role in fixing Ca and Mg and removing them from solution, their actual concentrations in natural media (<<1 g/L) do not cause significant changes in the composition of Ca_xMg_1–xCO₃ phases. On the other hand, there is quantitative evidence that variations in the Mg/Ca ratio in a solution and a solid phase are significantly influenced by the evaporative concentration of Mg-oversaturated solutions, alkalization/acidification during their evolution, or CO₂ content variations owing to changes in climate and lake activity.     

碱溶液预降解淤泥有机质的效果与机制讨论

淤泥富含大量有机质,受微生物作用,有机质会逐步分解出腐殖酸;同时,腐殖酸又会影响有机质降解,进而影响淤泥固化效果。为此,通过维持恒定的碱性缓冲溶液环境（pH=9.0）,将淤泥浸泡其中,观测其有机质含量的变化过程。结果表明,碱性缓冲溶液既能加快有机质分解,也能消耗腐殖酸,使溶液保持为碱性状态;当有机质分解完成,腐殖酸也释放结束,降解过程大约持续28 d。通过掺入水泥和石灰固化淤泥,发现含有机质的固化淤泥,其强度随养护时间会先增长后衰减,但预降解有机质的固化淤泥强度不会衰减。由此说明,通过碱性缓冲溶液预降解淤泥有机质,可以提升固化土耐久性。     

Detailed investigation of organic matter components in extracts and drainage waters from a soil under long term cultivation

Aqueous solutions of increasing pH (7.0, 10.6 and 12.6) were used to extract exhaustively the organic matter (OM) from a pelo-stagnogley (heavy clay) soil in long term cultivation. OM yield was 1.7 times greater when the extracts were processed using an XAD-8 and XAD-4 resin-in-tandem procedure than that from the procedure of the International Humic Substances Society (IHSS). The substantial difference can be attributed to the amount retained by the XAD-4 resin, which is lost in the IHSS process. Elemental, δ¹³C, δ¹⁵N, cation exchange capacity, neutral sugars, amino acids and solid state CPMAS ¹³C NMR analyses indicated significant, but rational similarities and differences between the various fractions isolated. There was strong NMR evidence for material derived from lignin in all the humic and fulvic acid isolates. The signals were attenuated in the more transformed/oxidized fractions isolated at lower pH. Novel humic acid fractions enriched in carbohydrate/peptide functionalities were isolated from the more hydrophobic extracts at pH 10.6 and 12.6. Isolates from XAD-4, of microbial origin, were enriched in neutral sugars but not in amino acids, and had minimal aromaticity. Components isolated from the cultivated soil were broadly similar to those from a comparable soil in long term grassland. The compositions of fractions isolated from the drainage water were similar to those extracted from the soil but had higher carboxyl content. The amount and composition of the various organic fractions in grassland and the continuously cropped soil are discussed in terms of their potential to contribute to carbon sequestration by soil under similar management regimes.     

桂林毛村岩溶区自然植被土壤团聚体中腐殖质组成初步研究

探索土壤有机碳物理保护与化学保护的关系,有助于揭示土壤固碳和培肥机理,明确不同粒级团聚体和不同腐殖物质组分对土壤固碳和肥力的贡献。本研究对岩溶区自然植被土壤团聚体中腐殖质含量进行了研究,结果表明:(1)灌丛和林地土壤团聚体中有机碳含量总体上均表现为随着土层深度的增加逐渐下降,而在不同土层深度随着团聚体粒径范围的变化则有机碳含量的变化规律则不同,无明显一致的规律;(2)两种土地利用方式各粒径团聚体中胡敏酸和富里酸均比全土小。这可能是由于在湿筛分离团聚体的过程中溶于水的那部分胡敏酸和富里酸成分被损失掉;(3)各腐殖质组分随着团聚体粒径范围的减小在两种自然植被上均无明显一致的规律,但胡敏酸和富里酸总量则基本表现为随着团聚体粒径范围的减小而逐渐升高,即在0.25mm和0.5~0.25mm粒径范围团聚体中最大;(4)两种自然植被土壤各土层中和各团聚体中胡敏酸/富里酸(HA/FA)基本上表现为小于1,这主要是因为研究区温度相对较高,湿度较大,植被覆盖度大,微生物降解作用强所致。     

土壤水分与溶质运移机制的分形理论研究进展

土壤中水分和溶质运移一直是土壤-水环境系统中的研究热点,也是目前仍未得到很好解决的问题.将分形理论应用于土壤水分溶质运移机制的研究,探讨其领域中的众多复杂问题,是一种全新的思路和方法.在对土壤结构定量化的分形表征进行简要阐述的基础上,重点介绍了分形理论在水分特征曲线和水力传导度等土壤水分运动基本参数的分形模型、土壤水分运移过程模拟、土壤溶质运移的非费克现象、弥散度的尺度效应以及溶质运移机制研究方面所取得的一系列成果,并就分形理论今后在土壤水分、溶质运移研究中的应用作了展望.