Variations in the composition and adsorption behavior of dissolved organic matter at a small, forested watershed

This study investigated the properties and sorption by goethite of bulk (unfractionated) dissolved organic matter (DOM) from surface and shallow groundwaters at McDonalds Branch, a small freshwater fen in the New Jersey Pine Barrens (USA). Water samples were collected in the spring and fall seasons from two surface-water sampling sites, an upstream potential recharge area and a downstream discharge area, as well as from a set of in-stream nested wells in the upstream potential recharge area. Changes in DOM concentration, molecular weight distribution, and molar absorptivity at 280 nm were measured. Surface and shallow (1.6 m below land surface) groundwater samples collected in spring 1997 in the potential recharge zone (actual recharge impeded by an extensive clay lens) were found to be very similar in terms of DOM concentrations and physicochemical properties and is believe to originate from a common source. Samples taken in fall 1997 yielded no surface water because of drought conditions, and the shallow groundwater DOM collected from the recharge well contained significantly less and chemically altered DOM. This change in chemical properties is believed to be caused in part by fractionation resulting from sorption to mineral phases. Batch isotherm experiments show that sorption by goethite of the DOM from both spring surface and shallow groundwaters in the potential recharge area were similar, whereas the fall groundwater possessed a much lower affinity for the sorbent. This study demonstrated that shallow groundwaters collected under different climatic and hydrologic conditions (spring, high flow versus fall, drought conditions) resulted in different physicochemical properties and adsorption affinities.     

水溶性有机质对土壤中镉吸附行为的影响

水溶性有机质 (DOM)是陆地生态系统和水生生态系统中的一种很活跃的组分 .本文以赤红壤、水稻土和褐土作为供试土壤 ,研究了来源于稻秆和底泥的DOM对土壤中Cd吸附行为的影响 .DOM对土壤中Cd的吸附行为具有明显的抑制作用 .这种抑制作用与土壤类型和DOM种类有关 .在 3种供试土壤中 ,无论添加稻秆DOM还是底泥DOM ,都会使Cd的最大吸附容量和吸附率明显降低 ,其下降幅度为17 3%～ 93 9%.在添加同一种DOM的前提下 ,DOM对Cd吸附的抑制作用均为 :赤红壤 >水稻土 >褐土 .如果不添加DOM ,则土壤对Cd的最大吸附容量主要取决于土壤固相的吸附特性 ,添加DOM后土壤对Cd的最大吸附容量则主要取决于液相中的DOM .由此推断 ,传统的看法 ,通过施用有机肥来固定土壤中的Cd并达到治理重金属污染土壤的观点值得商榷 .     

Mechanism of ammonium adsorption from wastewater by modified bentonite and optimization by response surface

Three modified bentonites, dry alkali modification, thermal modification, and acid modification, were prepared and characterized by XRD and FTIR. Batch experiments were performed to evaluate their efficiency as adsorbent for ammonium removal. Multi-variables interaction effects were evaluated by Response Surface Methodology. The results showed that the adsorption efficiency of ammonium by dry alkali modification bentonite was the best in three modified methods; the next was that of thermal modification. The crystalline structure of bentonite was significantly changed with dry alkali modification. Na₂SiO₃ and Na₂AlSi₃O₈(OH) were achieved by bentonite with powder NaOH modification. The increase in the mole ratio of exchangeable cations indicated that the adsorption efficiency of ammonium increased; while the layer spacing of bentonite expanded with the amount of the adsorbed water and hydrated water increased by thermal modification. In multi-variables interaction effects (holding time, calcination temperature, pH, dosage), the most significant factors were calcination temperature and dosage.     

有机污染物在表层土壤中光降解的研究进展

土壤是承载有机污染物的重要介质,而光降解是降解土壤表层有机污染物的一种非常重要的非生物转化途径。研究土壤表层有机物的光降解对认识污染物土壤环境行为有非常重要的意义。20世纪90年代以来对土壤中有机污染物的光降解研究有了大量报道。本文阐述了土壤组成和质地、土壤湿度、土壤pH值和土壤厚度等因素对光解影响的研究现状;介绍了目前研究土壤光降解所采用的研究方法：土壤表层直接光解、土壤悬浮液光解、溶剂萃取与光降解联合处理,及其研究土壤光降解应用的动力模型;对不同农药和其它有机污染物在土壤中的光降解研究进行了综述,并对今后的研究作了展望。     

土地利用方式对土壤有机质的影响

通过对地带性常绿阔叶林、杉木人工林、农田、竹林等不同土地利用方式下土壤有机质总量、活性有机质及其组分的研究,发现土地利用方式对土壤有机质和活性有机质各组分的影响差异显著,其中阔叶林含量最高,杉木人工林低于阔叶林,竹林和农田最低。这些差别主要是由于凋落物的数量、质量以及各种管理措施不同所致。     

Application of solid surface fluorescence EEM spectroscopy for tracking organic matter quality of native halophyte and furrow-irrigated soils

Solid surface fluorescence excitation-emission matrix (EEM) is developed a potential method to characterize soil organic matter (SOM). Solid surface EEM spectroscopy with parallel factor analysis (PARAFAC) and hierarchical cluster analysis (HCA) is used to extract fluorescent components, to seek latent factors, and to investigate spatial distribution of SOM. Soil samples were collected from four native halophyte and two furrow-irrigated soil profiles, i.e. Comm. Salicornia europaea (CSE), Comm. Suaeda glauca (CSG), Comm. Kalidium cuspidatum (CKC), Comm. Sophora alopecuroides (CSA), corn fields (CFD), and wheat fields (WFD). SOM contained six fluorescent components: microbial/terrestrial fulvic-like fluorescent components (C1), tryptophan-like/lignin-derived phenol fluorescent components (C2), terrestrial humic-like fluorescent component (C3), lignin oxidative degradation by-products (C4 and C5), and amino acids (C6). The C 4 and C5 were the representative components of SOM within the CSE, CSG, CKC, CSA and CFD soil profiles, while the C2 and C6 were dominated within the WFD soil profile. The C4, C5, C1 and C2 were latent factors, and they could roughly distinguish SOM within the whole saline soil profiles except the CFD. A humification index (H/L) deduced from the fluorescent components, was very suitable to indicate humification levels of SOM. Humification levels of SOM within the halophyte soil profiles decreased with soil depth, but the opposite trends within the furrow-irrigated soil profiles. The H/L was closely correlated with exchangeable sodium percentage (ESP), and humification levels increased with the decreasing ESP. Soil surface EEM may not only indicate organic matter fractions of saline soils, but may be transferred to other types of landscape.     

Formation of the nanostructure on a silica surface as mercury(II) ions adsorption sites

The present work investigates the adsorptive interactions of Hg(II) ions with hydroxylated silica, aminopropylsilica and silica chemically modified by β-cyclodextrin in aqueous medium. Batch adsorption studies were carried out with various agitation time and mercury(II) concentration. The maximum adsorption was observed within 15-30 min of agitation. The kinetics of the interactions, tested with model of Lagergren for pseudo-first and pseudo-second order equations, showed better agreement with first order kinetics (k₁ = 3.4 ± 0.2 to 5.9 ± 0.3 min⁻¹). The adsorption data gave good fits with Langmuir isotherms. The results have shown that β-cyclodextrin-containing adsorbent has the largest adsorption specificity to Hg(II) : K_L = 14 400 ± 700 L/mg. “β-Cyclodextrin-” inclusion complexes with ratio 1:1 and super molecules with composition С₄₂H₇₀O₃₅ · 3Hg(NO₃)₂ are formed on the surface of β-cyclodextrin-containing silica.     

Dynamics of organic matter in soils

Summary Dynamics of C, N, S, and to some extent P are expressed by a knowledge of the size and turnover rates of plant constituents such as soluble C and N components, cellulose and hemicellulose, and lignin. Soil organic matter constituents include: the microbial biomass as determined chemically or microscopically, non-biomass active components determined by isotopic dilution, stabilized N constituents for which good techniques are not yet available, and resistant or old C and associated N determined by carbon dating. The processes involved in the nutrient transformations and transfers are reasonably well understood. The control mechanisms require further elucidation to be able to extrapolate from the laboratory to the field, and between field sites. Major control mechanisms requiring further insight include the effects of C availability on transformations of C and N. The other control for which every little is known is that of spatial compartmentalization. Compartmentalization ranges from landscape or management sequences to pedogenic layers, rhizosphere-mycorrhizal effects, clay-sesquioxide surfaces, aggregation, localized enzymes, and microbial effects such as membrane boundaries. Control mechanisms for concurrent mineralization-immobilization, the stabilization of microbial products, and the relative role of the biomass as a catalyst rather than as a source-sink for nutrients, must be understood. There is potential for combining a knowledge of microbial production and turnover with that of the roles of the soil organic active fraction as a temporary storehouse for nutrients. This, in conjunction with management techniques such as zero tillage and crop rotation, should make it possible to better utilize soil and fertilizer N, especially in areas of the world where the cost of nutrients is high relative to the value of the crop grown.Introductory lecture     

表层水体中典型小分子有机氮的光铵化反应

地表水体中溶解性有机氮(DON)向无机氮的光化学转化是氮循环的重要过程之一。本文以自然水体中典型小分子DON(如氨基酸、核苷酸、尿素等)为对象,通过检测不同条件下的光铵化速率,探究小分子DON的结构、光源及水质条件对其光铵化过程的影响。结果表明:模拟自然光下,含有芳香环结构的氨基酸可以发生不同程度光铵化反应,酪氨酸和色氨酸的光铵化速率最大,6 h转化率可达约50%,而尿素和核苷酸则无明显光铵化反应发生;自然光下,酪氨酸和色氨酸在缓冲液中发生明显光铵化反应,而自然水样中组氨酸和苯丙氨酸也可生成NH4+;可见光波段对DON的光铵化几乎没有贡献,说明DON的光铵化速率受光源与水质组分影响。分子结构也影响DON的光铵化反应,如组氨酸分子中的氮可以完全转化为NH4+,而一个色氨酸分子中则仅有一个氮原子可以发生转化。基于密度泛函理论计算发现,氨基酸光铵化速率与其分子轨道能隙值有较好的负相关性。系列实验表明了水体中DON光化学转化的复杂性,应当在氮循环、水质变化和生态环境的评估中得到重视。     

Effect of pH and aluminum on surface properties of barley roots as determined from water vapor adsorption

Water vapor adsorption isotherms were used for the estimation of surface areas and adsorption energy distribution functions of roots of barley grown at different pH levels and at a toxic Al level (10 mg·dm⁻³), induced at tillering and shooting stages of plants growth. Values of surface area as well as energy distributions were the same for the roots grown at all pH values studied: 2, 4 and 7 and not dependent on the age of the plants indicating that the protons do not alter the physicochemical build-up of the surface of roots. However, significant changes of the root surface properties under the influence of aluminum: increase of surface area, average adsorption energy and amount of highly energetic adsorption sites together with a decrease of low energetic sites were observed.     

Adsorption and structure of benzene confined in disordered porous carbons: effect of pore heterogeneity and surface chemistry

Molecular simulations are used to study the adsorption of benzene at 300?K in atomistic models of disordered nanoporous carbons. These models, named as CS400, CS1000 and CS1000a, differ in density and chemical compositions, and reproduce the morphological and topological features present in real nanoporous carbons. We found that the adsorption phenomena depend upon the local structure of nanoporous carbons. To understand the effect of surface chemistry on adsorption and structure of confined benzene, functional groups (–COOH and –C=O) were added to these models. The presence of functional groups led to the onset of adsorption process at a low pressure. The carboxyl groups (–COOH) have a greater impact on adsorption as compared to carbonyl (–C=O) groups. The CS1000a models have wide micropores and thus it exhibits a jump in adsorption isotherm. The jump shifts towards lower pressure on the addition of functional groups, with –COOH groups showing a larger shift. The presence of functional groups also increases the isosteric heat of adsorption, with –COOH groups showing higher values. The coulombic contribution to total fluid–wall interaction energy is higher for –COOH functional groups and decreases on increasing pressure. Benzene confined in CS1000a models exhibit a liquid-like structure.     

Loss-on-ignition estimates of organic matter and relationships to organic carbon in fluvial bed sediments

Fluvial bed sediments represent an important sink and source for a variety of organic and inorganic compounds. Their most important constituent is organic matter (OM) and its primary component organic carbon (OC). Few studies have been conducted in fluvial environments examining bed-associated OM or OC. This is surprising given the recent interest in global carbon cycling and the importance of bed-associated organics as ecosystem energy sources. The objective of this study was to examine the relationship between OM, determined by loss-on-ignition (LOI), and OC in fluvial bed sediments determined by a dry combustion analyzer. The wide adoption of the LOI method in soil science reflects its ease of use, it is inexpensive, it is rapid, requires no specialized training, and strong statistical relationships commonly exist between OM and OC estimated by standard dry combustion procedures. Regression models were developed between OC and OM for six bed sediment size fractions (≤2.0 mm) for 113 sample sites in a tropical stream on Oahu, Hawaii. All models were highly significant (p < 0.0001), with coefficients of determination ranging from 35 to 79%. Measurement of LOI explained 64% of the variation in OC for all grouped data. The black-box LOI approach may be useful for rapid reconnaissance surveys of drainage systems. Examination of OM to OC conversion factors for Manoa bed sediments indicates that values typically observed in the soils literature (1.7–2.2) are far too low. Values of OM/OC were found to increase with increasing grain size, and decrease with increasing LOI percentage. Conversion factors obtained for grouped data had a mean of 14.9, a coefficient of variation of 21%, and a range of values between 6.2 and 27.4. It is suggested that these high conversion factors reflect significant water loss by dehydration of Fe, Al, and Mn oxides at a muffle furnace temperature of 450 °C. Therefore, the blind application of conversion factors developed from soils should be avoided when converting from OM to OC for fluvial bed sediments. This revised version was published online in July 2006 with corrections to the Cover Date.     

Influence of organic matter and solute concentration on nitrate sorption in batch and diffusion-cell experiments

Nitrate sorption potentials of three surface soils (soils-1-3) were evaluated under different solute concentrations, i.e. 1-100 mg L⁻¹. Batch and diffusion-cell adsorption experiments were conducted to delineate the diffusion property and maximum specific nitrate adsorption capacity (MSNAC) of the soils. Ho’s pseudo-second order model well fitted the batch adsorption kinetics data (R² > 0.99). Subsequently, the MSNAC was estimated using Langmuir and Freundlich isotherms; however, the best-fit was obtained with Langmuir isotherm. Interestingly, the batch adsorption experiments over-estimated the MSNAC of the soils compared with the diffusion-cell tests. On the other hand, a proportionate increase in the MSNAC was observed with the increase in soil organic matter content (OM) under the batch and diffusion-cell tests. Therefore, increasing the soil OM by the application of natural compost could stop nitrate leaching from agricultural fields and also increase the fertility of soil.     

A simulation model of organic matter and nutrient accumulation in mangrove wetland soils

The distribution and accumulation of organic matter, nitrogen (N) and phosphorus (P) in mangrove soils at four sites along the Shark River estuary of south Florida were investigated with empirical measures and a process-based model. The mangrove nutrient model (NUMAN) was developed from the SEMIDEC marsh organic matter model and parameterized with data from mangrove wetlands. The soil characteristics in the four mangrove sites varied greatly in both concentrations and profiles of soil carbon, N and P. Organic matter decreased from 82% in the upstream locations to 30% in the marine sites. Comparisons of simulated and observed results demonstrated that landscape gradients of soil characteristics along the estuary can be adequately modeled by accounting for plant production, litter decomposition and export, and allochthonous input of mineral sediments. Model sensitivity analyses suggest that root production has a more significant effect on soil composition than litter fall. Model simulations showed that the greatest change in organic matter, N, and P occurred from the soil surface to 5 cm depth. The rapid decomposition of labile organic matter was responsible for this decrease in organic matter. Simulated N mineralization rates decreased quickly with depth, which corresponded with the decrease of labile organic matter. The increase in organic matter content and decrease in soil bulk density from mangrove sites at downstream locations compared to those at upstream locations was controlled mainly by variation in allochthonous inputs of mineral matter at the mouth of the estuary, along with gradients in mangrove root production. Research on allochthonouns sediment input and in situ root production of mangroves is limited compared to their significance to understanding nutrient biogeochemistry of these wetlands. More accurate simulations of temporal patterns of nutrient characteristics with depth will depend on including the effects of disturbance such as hurricanes on sediment redistribution and biomass production.     

Effects of wildfire and permafrost on soil organic matter and soil climate in interior Alaska

The influence of discontinuous permafrost on ground‐fuel storage, combustion losses, and postfire soil climates was examined after a wildfire near Delta Junction, AK in July 1999. At this site, we sampled soils from a four‐way site comparison of burning (burned and unburned) and permafrost (permafrost and nonpermafrost). Soil organic layers (which comprise ground‐fuel storage) were thicker in permafrost than nonpermafrost soils both in burned and unburned sites. While we expected fire severity to be greater in the drier site (without permafrost), combustion losses were not significantly different between the two burned sites. Overall, permafrost and burning had significant effects on physical soil variables. Most notably, unburned permafrost sites with the thickest organic mats consistently had the coldest temperatures and wettest mineral soil, while soils in the burned nonpermafrost sites were warmer and drier than the other soils. For every centimeter of organic mat thickness, temperature at 5 cm depth was about 0.5°C cooler during summer months. We propose that organic soil layers determine to a large extent the physical and thermal setting for variations in vegetation, decomposition, and carbon balance across these landscapes. In particular, the deep organic layers maintain the legacies of thermal and nutrient cycling governed by fire and revegetation. We further propose that the thermal influence of deep organic soil layers may be an underlying mechanism responsible for large regional patterns of burning and regrowth, detected in fractal analyses of burn frequency and area. Thus, fractal geometry can potentially be used to analyze changes in state of these fire prone systems.     

Comparative effects of soil organic matter fractions on phosphatase activities in wheat roots

Summary Soil organic matter was obtained from two agricultural soils using alkali extraction followed by acidification to produce humic and fulvic acids which were further fractionated by adsorption and gel chromatography.All the products inhibited the activity of phosphatase prepared from wheat roots, but to different extents. Humic acids produced a greater inhibition of enzyme activity than either the fulvic acids or water extracts of soil. Aspergillin, fromAspergillus niger, had a similar C, H and N content to humic acid and produced a similar inhibition of phosphatase activity.The inhibitions produced by corresponding fractions derived from the two soils were slightly different, but the trends between similar fractions from different soils were comparable. The lower mol. wt. components of humic acid inhibited phosphatase activity to a greater extent than higher mot. wt. fractions. Although fulvic acid comprised only low mol. wt. components it was less effective in inhibiting enzyme activity than those components of comparable mol. wt. present in the corresponding humic acid. Synthetic polymaleic acid, produced an inhibition of phosphatase activity similar to that caused by fulvic acid.     

The retention of organic matter in soils

The turnover of C in soils is controlled mainly by water regimes and temperature, but is modified by factors such as size and physicochemical properties of C additions in litter or root systems, distribution of C throughout the soil as root systems, or addition as litter, distribution of C within the soil matrix and its interaction with clay surfaces.Soil factors which retard mineralization of C in soils are identified from correlations of C contents of soils with other properties such as clay content and base status. The rate and extent of C mineralization depends on the chemistry of the added organic matter and interaction with clays of the microbial biomass and metabolites.The organomineral interactions are shown to depend on cation bridges involving mainly Ca in neutral to alkaline soils, Al in acid soils and adsorption of organic materials on iron oxide surfaces. The various organomineral interactions lead to aggregations of clay particles and organic materials, which stabilizes both soil structure and the carbon compounds within the aggregates.     

Partitioning of habitable pore space in earthworm burrows

Earthworms affect macro-pore structure of soils. However, some studies suggest that earthworm burrow walls and casts themselves differ greatly in structure from surrounding soils, potentially creating habitat for microbivorours nematodes which accelerate the decomposition and C and N mineralization. In this study aggregates were sampled from the burrow walls of the anecic earthworm Lumbricus terrestris and bulk soil (not altered by earthworms) from mesocosm incubated in the lab for 0, 1, 3, 5 and 16 weeks. Pore volumes and pore sizes were measured in triplicate with Mercury Intrusion Porosimetry (MIP). This method is well suited to establish pore size structure in the context of habitat, because it measures the stepwise intrusion of mercury from the outside of the aggregate into ever smaller pores. The progress of mercury into the aggregate interior thus resembles potential paths of a nematode into accessible habitable pore spaces residing in an aggregate. Total specific pore volume, V(s), varied between 0.13 and 0.18 mL/g and increased from 3 to 16 weeks in both burrow and bulk soil. Differences between total V(s) of bulk and burrow samples were not significant on any sampling date. However, differences were significant for pore size fractions at the scale of nematode body diameter.     

Microbial transformation of labile dissolved organic matter into humic-like matter in seawater

Abstract Microbial transformation of labile, low molecular weight dissolved organic matter (DOM) into dissolved humic matter (DHM) was studied in seawater. Surface water samples were amended with [¹⁴C into ¹⁴CO₂, TO¹⁴C (total organic ¹⁴C), and PO¹⁴C (particulate organic ¹⁴C), was measured over time in confined samples. The humic and non-humic fractions of DO¹⁴C (dissolved organic ¹⁴C) were separated according to a common operational definition of DHM based on adsorption on XAD-8 macroporous resin. Both TO¹⁴C and non-humic DO¹⁴C decreased during the experiments. However, ¹⁴C-labelled DHM increased during the first week of the incubations, to a level where it comprised 15% of the TO¹⁴C remaining in the samples, or 3% of the initially added ¹⁴C. Towards the end of experiments (ca 70 days), the humic fraction of DO¹⁴C gradually approached the background level of poisoned control samples. Provided that the XAD-8 operational definition of DHM is accepted, this study indicates that humic matter may be formed in seawater within days from labile monomers such as glucose.