土壤和沉积物中NOM稳定性矿物学机制研究的理论与方法

土壤和沉积物中天然有机质(NOM)稳定性问题受到关注,主要是因为NOM的稳定性直接影响到大气中CO2的平衡与全球气候变化。此外,天然有机质还影响着土壤和沉积物中矿物的表面反应性、污染物的环境行为与生物有效性。因此,本综述在详细介绍土壤和沉积物中NOM稳定性矿物学机制研究的理论与方法的同时,也简略介绍了NOM的组成结构与反应性,并着重强调NOM/矿物微界面过程作用机制的重要性。许多研究表明,土壤和沉积物中NOM稳定性的矿物学机制主要包括矿物表面吸附和物理包裹。本综述目的是,介绍矿物保护的稳定NOM的分离、特性及其分析测定方法与技术,并且强调NOM稳定性矿物学保护机制系统性研究的重要性,以搞清矿物学保护机制在土壤和沉积物中NOM稳定保持中的贡献与重要性以及矿物学保护机制对天然有机质稳定性的调控作用,从而提高对土壤和沉积物环境生态的地球化学、矿物学的认识水平。     

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.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

Sorption kinetics of naphthalene and phenanthrene in loess soils

A laboratory study was executed to investigate the effect of surfactants to enhance sorption of polycyclic aromatic hydrocarbon (PAH) contaminants in loess soil. Phenanthrene and naphthalene were chosen as organic contaminant indicators in loess soil modified by the cation surfactant hexadecyltrimethylammonium (HDTMA) bromide. The kinetic behavior of sorption during transport in natural and modified loess soil was studied. The results indicated that sorption rate in the cation surfactant modified loess soils was at least 3 times faster than that of the natural soil. A first-order kinetics model fitted the sorption data well for both soils. The sorption rates of the two organic compounds were related to their primary residual quantity on the soils. The experiments showed that sorption amounts approached constant values approximately within 30 and 90 min for naphthalene and phenanthrene at 298–318 K, respectively. The rate constants, however, displayed negative correlation with increasing temperature. With changing temperature, the activation energy was calculated at –6.196–1.172 kJ/mol for naphthalene and –28.86–15.70 kJ/mol for phenanthrene at 298–318 K. The results can be used to predict the sorption kinetics of phenanthrene and naphthalene in loess soils, and in a wider perspective, be used to better understand the transport of petroleum contaminants in the soil environment.     

Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

天然有机质与矿物间的吸附及其环境效应的研究进展

本文综述了天然有机质与矿物间吸附行为的研究进展.具体介绍了天然有机质与矿物间的吸附机理,包括配位交换、范德华力、静电引力、疏水作用、离子交换及阳离子桥;阐述了不同分子大小及亲疏水性组分的天然有机质在矿物上的吸附行为;讨论了影响吸附行为的环境条件（pH,离子强度）及天然有机-矿物体系对全球碳循环、重金属和有机污染物产生的环境效应,并提出了研究展望.     

CBs在沉积物上的吸附-解吸行为

采用批量平衡实验,研究了氯苯、1,4-二氯苯、1,2,4-三氯苯和1,2,4,5-四氯苯4种氯苯类化合物（CBs）在含不同特性的自然有机质（NOM）的5种沉积物上的吸附．解吸行为。研究结果表明,所有吸附等温线均表现出明显的非线性和吸附-解吸滞后现象。1,2,4-三氯苯在不同沉积物上吸附等温线的非线性程度以及在沉积物上解吸滞后效应都随着沉积物NON聚合度的增加而增大。另外,CBs溶质分子本身的性质也影响着其在沉积物上的吸附．解吸性能。4种CBs在同一种沉积物上吸附等温线的非线性程度及其解吸滞后系数按氯苯、1,4-二氯苯、1,2,4-三氯苯、1,2,4,5-四氯苯的顺序依次减弱,说明CBs的分子尺寸越大,其在沉积物上的吸附非线性程度和解吸滞后现象也越弱。     

Enhanced microbial reduction of Cr(VI) and U(VI) by different natural organic matter fractions

Although direct microbial reduction of Cr(VI) and U(VI) is known, few studies have examined the kinetics and the underlying mechanisms of the reduction of these contaminants by different natural organic matter (NOM) fractions in the presence or absence of microorganisms. In this study, NOM was found to chemically reduce Cr(VI) at pH 3, but the reduction rates were negligible at pH ∼7. The abiotic reduction of U(VI) by NOM was not observed, possibly because of the presence of small amounts of nitrate in the reactant solution. However, all NOM fractions, particularly the soil humic acid (HA), enhanced the bioreduction of Cr(VI) or U(VI) in the presence of Shewanella putrefaciens CN32. The reduction rates varied greatly among NOM fractions with different chemical and structural properties: the polyphenolic-rich NOM-PP fraction appeared to be the most reactive in abiotically reducing Cr(VI) at a low pH, but soil HA was more effective in mediating the microbial reduction of Cr(VI) and U(VI) under anaerobic, circumneutral pH conditions. These observations are attributed to an increased solubility and conformational changes of the soil HA with pH and, more importantly, its relatively high contents of polycondensed and conjugated aromatic organic moieties. An important implication of this study is that, depending on chemical and structural properties, different NOM components may play different roles in enhancing the bioreduction of Cr(VI) and U(VI) by microorganisms. Polycondensed aromatic humic materials may be particularly useful in mediating the bioreduction and rapid immobilization of these contaminant metals in soil.     

Response of hepatic trace element concentrations in fish exposed to elemental and organic contaminants

Multivariate analysis of contaminant data from a multi-year monitoring program demonstrates alterations in the hepatic chemistry of metals in fish exposed to organic contaminants. Metals (Ag, As, Cd, Cu, Fe, Hg, Mn, Ni, Pb, Se, Sn, Zn) and organic chemicals (PCBs, DDTs, chlordanes, dieldrins, PAHs) were measured in liver and associated sediments for winter flounder (Pleuronectes americanus) from 23 sites along the northeast Atlantic coast and for Atlantic croaker (Micropogonias undulatus) from 30 sites along the southeast Atlantic and Gulf of Mexico coasts of the United States. Concentrations of habitat contaminants varied from nil to levels signifying important anthropogenic inputs and thus provided a range in chronic exposures and related contaminant stress levels with which to investigate the response of hepatic chemistry in fish representative of viable populations. The data, analyzed by principal component, principal component regression, and biplot procedures, demonstrated an opposing relationship between micronutrient elements, principally Zn, and exposure to organic contaminants in winter flounder. This relationship was not present in Atlantic croaker that were resident in less contaminated habitats. Based on median concentrations in sediment, exposure of winter flounder to important organic contaminants (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, DDTs) exceeded that for Atlantic croaker by 7 to 50 times. Coincident with depletion of hepatic Zn and Cd in winter flounder was accumulation of Hg and Ag. My results, in agreement with those of others, implicate the negative effects of hepatic detoxification of organic contaminants on metal binding in liver, which can cause depletion of essential elements while contaminant and potentially toxic elements accumulate.     

Characterization of natural organic matter in bentonite clays for potential use in deep geological repositories for used nuclear fuel

The Nuclear Waste Management Organization (NWMO) is developing a Deep Geological Repository (DGR) to contain and isolate used nuclear fuel in a suitable rock formation at a depth of approximately 500 m. The design concept employs a multibarrier system, including the use of copper-coated used fuel containers, surrounded by a low-permeability, swelling clay buffer material within a low permeability, stable host rock environment. The natural organic matter (NOM) composition of the bentonite clays being considered for the buffer material is largely uncharacterized at the molecular-level. To gain a better understanding of the NOM in target clays from Wyoming and Saskatchewan, molecular-level methods (biomarker analysis, solid-state ¹³C NMR and solution-state ¹H nuclear magnetic resonance (NMR)) were used to elucidate the structure and sources of NOM. Organic carbon content in three commercially available bentonites analyzed was low (0.11–0.41%). The aliphatic lipid distribution of the clay samples analyzed showed a predominance of higher concentration of lipids from vascular plants and low concentrations of lipids consistent with microbial origin. The lignin phenol vanillyl acid to aldehyde ratio (Ad/Al) for the National sample indicated an advanced state of lignin oxidation and NOM diagenesis. The ¹³C NMR spectra were dominated by signals in the aromatic and aliphatic regions. The ratio of alkyl/O-alkyl carbon ranged from 7.6 to 9.7, indicating that the NOM has undergone advanced diagenetic alteration. The absence lignin-derived phenols commonly observed in CuO oxidation extracts from contemporary soils and sediments as well as the lack of amino acids suggests that the material corresponding to the aromatic signal is not composed of lignin or proteins but may be derived from another source such as black carbon or some other non-extractable aromatic-rich NOM. The aliphatic signal appears to correspond to long-chain compounds with little side branching based on the results of the one-dimensional (1D) and two-dimensional (2D) solution-state ¹H NMR analyses. Overall, the organic geochemical analyses suggest that the NOM is composed mainly of plant-derived waxes and highly aromatic carbon with low contributions from small molecules. The compounds identified by the molecular-level analysis of NOM in the clay samples are hypothesized to be recalcitrant but future studies should examine if these compounds may serve as a microbial substrate to further test the observations of this study. Furthermore, our study suggests that the NOM has undergone diagenesis and that marine NOM signatures are no longer recognizable or detectable. As such, future work may also examine the diagenesis of these deposits to further understand the NOM geochemistry and paleoenvironmental conditions in bentonite deposits.     

Combining advanced NMR techniques with ultrahigh resolution mass spectrometry: A new strategy for molecular scale characterization of macromolecular components of soil and sedimentary organic matter

Molecular level characterization of complex biopolymers in nature is a key element to understanding the composition of natural organic matter (NOM) and fossil organic matter formation, such as kerogen and coal. Characterization of such geopolymers is difficult due to their heterogeneity and insolubility in common aqueous or organic solvents. Here, a strategy for extracting a representative sample is presented using the combined techniques of nuclear magnetic resonance (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) for chemical analysis and characterization of NOM. A variety of NOM samples (wood, kerogen, bitumen, whole sediments) are shown as examples for implementing the strategy, which include solvent extractions using pyridine. For most samples, the extracts are confirmed to be chemically representative of the insoluble solid, by comparing the liquids NMR spectrum of the extract to that of the whole, unfractionated NOM utilizing high resolution magic angle spinning (HRMAS) NMR. To assist in unambiguous peak assignment, a technique for post acquisition spectral denoising, using wavelet transformation (WT), is also employed on the 1D and 2D NMR spectra. The findings from the NMR data lay a foundation for the subsequent electrospray ionization FTICR-MS analysis of the pyridine extracts, since this instrument has the limitation of only analyzing liquid samples. The FTICR-MS analyses can, therefore, be used to molecularly represent the structural components of the NOM. Various compositional insights have been obtained on these samples, indicating the efficacy of the analytical techniques used.     

Sorption and desorption of dissolved organic phosphorus onto iron (oxyhydr)oxides in seawater

Sorption of phosphorus (P) onto particulate surfaces significantly influences dissolved P concentrations in aquatic environments. We present results of a study contrasting the sorption behavior of several dissolved organic phosphorus (DOP) compounds and phosphate onto three commonly occurring iron (oxyhydr)oxides (Fe_ox): ferrihydrite, goethite, and hematite. The DOP compounds were chosen to represent a range of molecular weights and structures, and include: adenosine triphosphate (ATP), adenosine monophosphate (AMP), glucose-6-phosphate (G6P), and aminoethylphosphonic acid (AEP).All P compounds displayed decreasing sorption as a function of crystallinity of the Fe_ox substrate, with ferrihydrite adsorbing the most, hematite the least. In general, maximum sorption density decreased with increasing molecular weight of P compound; sorption of G6P onto goethite and hematite excepted. P compound size and structure, and the nature of the Fe_ox substrate all appear to play a role dictating relative sorption capacity. Failure of a simple, 1-step sorption-desorption model to describe the data suggests that P sorption cannot be explained by a simple balance between sorption and desorption. Instead, the data are consistent with a 2-step sorption model consisting of an initial rapid surface sorption, followed by a slow, solid-state diffusion of P from surface sites into particle interiors. Desorption experiments provide additional support for the 2-step sorption model.Without exception, DOP compounds showed less efficient sorption than did orthophosphate. This suggests that in aquatic systems enriched in reactive Fe_ox, whether as suspended particulates in the water column or in benthic sediments, DOP bioavailability may exceed that of orthophosphate. Since biological uptake of P from DOP requires enzymatic cleavage of orthophosphate, a system enriched in DOP relative to orthophosphate may impact ecosystem community structure.     

CCL吸附特性及孔隙率降低对污染物运移的影响

假定孔隙均匀地分布于土体的物质空间内和土骨架对污染物的吸附特性服从平衡线性,对基本体积质量关系进行分析,提出了由于土体对污染物的吸附而引起的孔隙率降低的估算公式。在考虑土体孔隙率变化的条件下,建立了污染物一维运移的控制方程,并考虑垃圾生物降解效应、压实黏土衬里（CCL）防渗层、下覆有限厚度含水层等实际情况,确定了初始条件和边界条件。对所建立的初边值问题进行了数值求解,且对某假想填埋场情况进行了变动参数与对比计算,结果表明,由于土颗粒对污染物的吸附所引起的孔隙率降低,显著地降低了污染物对压实黏土衬里的穿透能力。与常孔隙率情况相比,CCL中污染物的峰值浓度降低近10 %,含水层中污染物浓度降低更显著。当考虑土体孔隙率变化时,弥散对污染物运移具有控制作用,分布系数对污染物的运移具有重要影响。     

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     

Sorptive stabilization of organic matter in soils by hydrous iron oxides

Strong correlations between iron oxides (FeOx) and organic matter (OM) in soils have implied the importance of the former in stabilizing the latter. One mechanism thought to be important in this stabilization is sorption. We tested this possibility by reductively dissolving FeOx in a wide variety of soils and measuring the organic carbon (OC) that was solubilized. The OC dissolved from non-FeOx phases via anion exchange was corrected for by parallel control extractions. The resultant pool, reductively soluble OC, made up a minor amount of total soil OC in all but one of these soils, indicating that simple sorption reactions do not stabilize the bulk of soil OC in most mineral soils. OC:Fe ratios in the extracts from 2/3 of these soils were less than 0.22 (wt/wt), consistent with a sorbed state for this OC and showing that OC sorption by FeOx in these soils is limited by the amount of FeOx. The remaining soils had low pH and high OM concentrations; their higher OC:Fe ratios indicate inclusion of precipitated organo-Fe complexes in the extracts, which are likely only partially extracted by our method. The high volumetric ratios of OM to FeOx found in correlations between them from the literature are inconsistent with a dominant sorption control and point instead to stabilization to other mechanisms such as organo-Fe complexes or ternary associations among FeOx, OM and other minerals.     

Influence of humic acid on the sorption of pentachlorophenol by aged sediment amended with rice-straw biochar

Black carbon (BC), especially biochar, is a potential material for the remediation of hydrophobic organic compounds (HOCs) pollution in soils and sediments. Recent studies have reported that the adsorption capability of BC in sediment was reduced as time increased. It was hypothesised that this behaviour was caused by the presence of natural organic matter (NOM), but few systematic studies have examined the influence of NOM on the sorption ability of BC in sediment (S). The results of this study revealed that a humic acid (HA) coating changed the surface properties, blocked the micropores, and decreased the sorption capacity of rice-straw biochar (RBC) towards pentachlorophenol. With increasing aging time, the reductions in the sorption capacity of the S + RBC and S + HA + RBC systems occurred more rapidly than in the S + HA/RBC (HA-coated RBC) system, and the sorption curves became closer to that of the S + HA/RBC system, indicating that HA may play a primary role in reducing the sorption capacity of RBC in the sediment. With higher HA contents, the sorption capacity of the complex sediments was lower and decreased more rapidly.     

Cs and Cl NMR spectroscopy and molecular dynamics modeling of Cs and Cl complexation with natural organic matter

Interaction of dissolved aqueous species with natural organic matter (NOM) is thought to be important in sequestering some species and enhancing the transport of others, but little is known about these interactions on a molecular scale. This paper describes a combined experimental ¹³³Cs and ³⁵Cl nuclear magnetic resonance (NMR) and computational molecular dynamics (MD) modeling study of the interaction of Cs⁺ and Cl⁻ with Suwannee River NOM. The results provide a detailed picture of the molecular-scale structure and dynamics of these interactions. Individual NOM molecules are typically hundreds to thousands of Daltons in weight, and on the molecular scale their interaction with small dissolved species can be investigated in ways similar to those used to study the interaction of dissolved aqueous species with mineral surfaces. As for such surface interactions, understanding both the structural environments and the dynamics over a wide range of frequencies is essential. The NMR results show that Cs⁺ is associated with NOM at pH values from 3.4 ± 0.5 (unbuffered Suwannee River NOM solution) to 9.0 ± 0.5. The extent of interaction increases with decreasing CsCl concentration at constant pH. It also decreases with increasing pH at constant CsCl concentration due to pH-dependent negative structural charge development on the NOM caused by progressive deprotonation of carboxylic and phenolic groups. The presence of NOM has little effect on the ¹³³Cs chemical shifts, demonstrating that its local coordination environment does not change significantly due to interaction with the NOM. Narrow, solution-like line widths indicate rapid exchange of Cs⁺ between the NOM and bulk solution at frequencies of >10² Hz. The MD simulations support these results and show that Cs⁺ is associated with the NOM principally as outer sphere complexes and that this interaction does not reduce the Cs⁺ diffusion coefficient sufficiently to cause NMR line broadening. The ³⁵Cl NMR data and the MD results are consistent in demonstrating that there is no significant complexation between Cl⁻ and NOM in the pH range investigated, consistent with negative structural charge on the NOM.     

Structural environments of carboxyl groups in natural organic molecules from terrestrial systems. Part 1: Infrared spectroscopy

Carboxyls play an important role in the chemistry of natural organic molecules (NOM) in the environment, and their behavior is dependent on local structural environment within the macromolecule. We studied the structural environments of carboxyl groups in dissolved NOM from the Pine Barrens (New Jersey, USA), and IHSS NOM isolates from soils and river waters using attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. It is well established that the energies of the asymmetric stretching vibrations of the carboxylate anion (COO⁻) are sensitive to the structural environment of the carboxyl group. These energies were compiled from previous infrared studies on small organic acids for a wide variety of carboxyl structural environments and compared with the carboxyl spectral features of the NOM samples. We found that the asymmetric stretching peaks for all NOM samples occur within a narrow range centered at 1578 cm⁻¹, suggesting that all NOM samples examined primarily contain very similar carboxyl structures, independent of sample source and isolation techniques employed. The small aliphatic acids containing hydroxyl (e.g., d-lactate, gluconate), ether/ester (methoxyacetate, acetoxyacetate), and carboxylate (malonate) substitutions on the α-carbon, and the aromatic acids salicylate (ortho-OH) and furancarboxylate (O-heterocycle), exhibit strong overlap with the NOM range, indicating that similar structures may be common in NOM. The width of the asymmetric peak suggests that the structural heterogeneity among the predominant carboxyl configurations in NOM is small. Changes in peak area with pH at energies distant from the peak at 1578 cm⁻¹, however, may be indicative of a small fraction of other aromatic carboxyls and aliphatic structures lacking α-substitution. This information is important in understanding NOM-metal and mineral-surface complexation, and in building appropriate structural and mechanistic models of humic materials.     

Organic Contamination of Soil and Goundwater in the Piedimont Plain of the Taihang Mountains

The risk of groundwater contamination following the infiltration of waste surface water, is of great interest, particularly in areas experiencing water shortage. In this study, the distribution characteristics of contaminants along the Cihe River, in the piedimont plain of the Taihang Mountains, China, was investigated by measuring the soil and water samples. The main organic contaminants detected in different media include hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and pesticides. The main contaminants found in different media are mostly derived from the river water, which can be seen from the results of waste water from the river and groundwater, from the soil samples from different depth and distance of the profiles along the river. The distribution characteristics showed that there has been a natural attenuation of the contaminants from the river during their transportation through the soils and groundwater. The sorption of organic compounds to soil organic matter is thought to be a main mechanism of natural attenuation.     

Sulfate reducing bioreactor dependence on organic substrates for remediation of coal-generated acid mine drainage: Field experiments

Field experiments were conducted over a 460-day period to assess the efficiency of different mixtures of organic substrates to remediate coalmine-generated acid mine drainage (AMD). Five pilot-scale, flow-through bioreactors containing mixtures of herbaceous and woody organic substrates along with one control reactor containing only limestone were constructed at the Tab-Simco site and exposed to AMD in situ. Tab-Simco is an abandoned coal mine near Carbondale, Illinois that produces AMD with pH ∼2.5 and notably high average concentrations of SO₄ (5050 mg/L), Fe (950 mg/L), Al (200 mg/L), and Mn (44 mg/L). Results showed that the sequestration of SO₄ and metals was achieved in all reactors; however, the presence and type of organic carbon matrix impacted the overall system dynamics and the AMD remediation efficiency. All organic substrate-based reactors established communities of sulfate reducing microorganisms that contributed to enhanced removal of SO₄, Fe, and trace metals (i.e., Cu, Cd, Zn, Ni) via microbially-mediated reduction followed by precipitation of insoluble sulfides. Additional mechanisms of contaminant removal were active in all reactors and included Al- and Fe-rich phase precipitation and contaminant surface sorption on available organic and inorganic substrates. The organic substrate-based reactors removed more SO₄, Fe, and Al than the limestone-only control reactor, which achieved an average removal of ∼19 mol% SO₄, ∼49 mol% Fe, 36 mol% Al, and 2 mol% Mn. In the organic substrate-based reactors, increasing herbaceous content correlated with increased removal efficiency of SO₄ (26–35 mol%), Fe (36–62 mol%), Al (78–83 mol%), Mn (2–6 mol%), Ni (64–81 mol%), Zn (88–95 mol%), Cu (72–85 mol%), and Cd (90–92 mol%), while the diversity of the intrinsic microbial community remained relatively unchanged. The extrapolation of these results to the full-scale Tab-Simco treatment system indicated that, over the course of a 460-day period, the predominantly herbaceous bioreactors could remove up to 92,500 kg SO₄, 30,000 kg Fe, 8,950 kg Al, and 167 kg Mn, which represents a 18.3 wt%, 36.8 wt%, 4.1 wt% and 82.3 wt% increase in SO₄, Fe, Al, and Mn, respectively, removal efficiency compared to the predominantly ligneous bioreactors.The results imply that anaerobic organic substrate bioreactors are promising technologies for remediation of coal-generated AMD and that increasing herbaceous content in the organic substrate matrix can enhance contaminant sequestration. However, in order to improve the remediation capacity, future designs must optimize not only the organic carbon substrate but also include a pretreatment phase in which the bulk of dissolved Fe/Al-species are removed from the influent AMD prior to entering the bioreactor because of 1) seasonal variations in temperature and redox gradients could induce dissolution of the previously formed redox sensitive compounds, and 2) microbially-mediated sulfate reduction activity may be inhibited by the excessive precipitation of Al- and Fe-rich phases.