Nonlinear and competitive sorption of apolar compounds in black carbon-free natural organic materials

Numerous studies have reported a spectrum of sorption phenomena in soils, sediments, and organic matter isolates of those materials that are inconsistent with a partition model proposed in the late 1970s and early 1980s, a model predicated on a hypothesis that sorption is linear and noncompetitive. To explain these nonideal phenomena, prior studies have proposed a hard-soft (glassy-rubbery) model for SOM (soil and sediment organic matter), while others have attributed them singularly to BC (black carbon: soot and charcoal) particles present in topsoils and sediments. In this study, we demonstrated nonideal sorption behavior (isotherm nonlinearity, competitive effects) for a group of apolar compounds in a large set of natural and model organic materials, including a commercial lignin and humic acids from different sources. Complete oxidation of samples by an acidic dichromate method was taken to signify the absence of BC. (However, polymethylene units are stable even if functionalized on both ends, making the technique unreliable for quantifying BC.) Other samples were inferred free of BC by their source and method of preparation. Characterization by thermalanalytical methods indicated the glassy character of the organic materials. The origin of the nonideal behaviors appears to be the glassy character of these materials. Sorption nonlinearity increased or decreased by changing temperature, cosolvent content, or degree of cross-linking by metal ions as predicted for organic solids in a glassy state. We conclude that macromolecular humic substances in the environment may exhibit nonideal sorption behavior in soils and sediments, quite apart from any such behaviors attributable to BC.     

INTERFACING GIS WITH WATER RESOURCE MODELS: A STATE‐OF‐THE‐ART REVIEW1

Two distinctive, independently developed technologies, geographic information systems (GIS) and predictive water resource models, are being interfaced with varying degrees of sophistication in efforts to simultaneously examine spatial and temporal phenomena. Neither technology was initially developed to interact with the other, and as a result, multiple approaches to interface GIS with water resource models exist. Additionally, continued model enhancements and the development of graphical user interfaces (GUIs) have encouraged the development of application “suites” for evaluation and visualization of engineering problems. Currently, disparities in spatial scales, data accessibility, modeling software preferences, and computer resources availability prevent application of a universal interfacing approach. This paper provides a state‐of‐the‐art critical review of current trends in interfacing GIS with predictive water resource models. Emphasis is placed on discussing limitations to efficient interfacing and potential future directions, including recommendations for overcoming many current challenges.     

Tool for assessment of process importance at the groundwater/surface water interface

The groundwater/surface water interface (GWSWI) represents an important transition zone between groundwater and surface water environments that potentially changes the nature and flux of contaminants exchanged between the two systems. Identifying dominant and rate-limiting contaminant transformation processes is critically important for estimating contaminant fluxes and compositional changes across the GWSWI. A new, user-friendly, spreadsheet- and Visual Basic-based analytical screening tool that assists in evaluating the dominance of controlling kinetic processes across the GWSWI is presented. Based on contaminant properties, first-order processes that may play a significant role in solute transport/transformation are evaluated in terms of a ratio of process importance (P_i) that relates the process rate to the rate of fluid transfer. Besides possessing several useful compilations of contaminant and process data, the screening tool also includes 1-D analytical models that assist users in evaluating contaminant transport across the GWSWI. The tool currently applies to 29 organics and 10 inorganics of interest within the context of the GWSWI. Application of the new screening tool is demonstrated through an evaluation of natural attenuation at a site with trichloroethylene and 1,1,2,2-tetrachloroethane contaminated groundwater discharging into wetlands.     

Advanced thermal characterization of fractionated natural organic matter

This work focuses on an experimental investigation of the thermodynamic properties of natural organic matter (NOM), and whether fractions of NOM possess the same thermodynamic characteristics as the whole NOM from which they are derived. Advanced thermal characterization techniques were employed to quantify thermal expansion coefficients (alpha), constant-pressure specific heat capacities (C(p)), and thermal transition temperatures (T(t)) of several aquatic- and terrestrial-derived NOM. For the first time, glass transition behavior is reported for a series of NOM fractions derived from the same whole aquatic or terrestrial source, including humic acid-, fulvic acid-, and carbohydrate-based NOM, and a terrestrial humin. Thermal mechanical analysis (TMA), standard differential scanning calorimetry (DSC), and temperature-modulated differential scanning calorimetry (TMDSC) measurements revealed T(t) ranging from -87 degrees C for a terrestrial carbohydrate fraction to 62 degrees C for the humin fraction. The NOM generally followed a trend of increasing T(t) from carbohydrate to fulvic acid to humic acid to humin, and greater T(t) associated with terrestrial fractions relative to aquatic fractions, similar to that expected for macromolecules possessing greater rigidity and larger molecular weight. Many of the NOM samples also possessed evidence of multiple transitions, similar to beta and alpha transitions of synthetic macromolecules. The presence of multiple transitions in fractionated NOM, however, is not necessarily reflected in whole NOM, suggesting other potential influences in the thermal behavior of the whole NOM relative to fractionated NOM. Temperature-scanning X-ray diffraction studies of each NOM fraction confirmed the amorphous character of each sample through T(t).     

Fluorescence spectroscopic studies of natural organic matter fractions

Because of the well-known molecular complexity and heterogeneity of natural organic matter (NOM), an aquatic bulk NOM was fractionated into well-defined polyphenolic-rich and carbohydrate-rich subfractions. These fractions were systematically characterized by fluorescence emission, three dimensional excitation-emission matrices, and synchronous-scan excitation spectroscopy in comparison with those of the reference International Humic Substances Society soil humic acid and Suwannee River fulvic acid. Results indicate that fluorescence spectroscopy can be useful to qualitatively differentiate not only NOM compounds from varying origins but also NOM subcomponents with varying compositions and functional properties. The polyphenolic-rich NOM-PP fraction exhibited a much more intense fluorescence and a red shift of peak position in comparison with the carbohydrate-rich NOM-CH fraction. Results also indicate that synchronous excitation spectra were able to provide improved peak resolution and structural signatures such as peak positioning, shift, and intensity among various NOM components as compared with those of the emission and excitation spectra. In particular, the synchronous spectral peak intensity and its red shift in the region of about 450-480 nm may be used to indicate the presence or absence of high molecular weight and polycondensed humic organic components, or the multicomponent nature of NOM or NOM subcomponents.     

Thermal analysis of whole soils and sediment

Thermal analysis techniques were utilized to investigate the thermal properties of two soils and a lignite coal obtained from the International Humic Substances Society (IHSS), and sediment obtained from The Netherlands. Differential scanning calorimetry (DSC) revealed glass transition behavior of each sample at temperatures ranging from 52 degrees C for Pahokee peat (euic, hyperthermic Lithic Medisaprists), 55 degrees C for a Netherlands (B8) sediment, 64 degrees C for Elliott loam (fine, illitic, mesic Aquic Arguidolls), to 70 degrees C for Gascoyne leonardite. Temperature-modulated differential scanning calorimetry (TMDSC) revealed glass transition behavior at similar temperatures, and quantified constant-pressure specific heat capacity (Cp) at 0 degrees C from 0.6 J g(-1) degrees C(-1) for Elliott loam and 0.8 J g(-1) degrees C(-1) for the leonardite, to 1.0 J g(-1) degrees C(-1) for the peat and the sediment. Glass transition behavior showed no distinct correlation to elemental composition, although Gascoyne Leonardite and Pahokee peat each demonstrated glass transition behavior similar to that reported for humic acids derived from these materials. Thermomechanical analysis (TMA) revealed a large thermal expansion followed by a matrix collapse for each sample between 20 and 30 degrees C, suggesting the occurrence of transition behavior of unknown origin. Thermal transitions occurring at higher temperatures more representative of glass transition behavior were revealed for the sediment and the peat.     

Thermodynamic properties of several soil- and sediment-derived natural organic materials

Improved understanding of the structure of soil- and sediment-derived organic matter is critical to elucidating the mechanisms that control the reactivity and transport of contaminants in the environment. This work focuses on an experimental investigation of thermodynamic properties that are a function of the macromolecular structure of natural organic matter (NOM). A suite of thermal analysis instruments were employed to quantify glass transition temperatures (Tg), constant-pressure specific heat capacities (Cp), and thermal expansion coefficients (alpha) of several International Humic Substances Society (IHSS) soil-, sediment-, and aquatic-derived NOMs. Thermal mechanical analysis (TMA) of selected NOMs identified Tgs between 36 and 72 degrees C, and alphas ranging from 11 mum/m degrees C below the Tg to 242 mum/m degrees C above the Tg. Standard differential scanning calorimetry (DSC) and temperature-modulated differential scanning calorimetry (TMDSC) measurements provided additional evidence of glass transition behavior, including identification of multiple transition behavior in two aquatic samples. TMDSC also provided quantitative measures of Cp at 0 and 25 degrees C, ranging from 1.27 to 1.44 J/g degrees C. Results from TMA, DSC, and TMDSC analyses are consistent with glass transition theories for organic macromolecules, and the glass transition behavior of other NOM materials reported in previous studies. Discussion of the importance of quantifying these thermodynamic properties is presented in terms of improved physical and chemical characterization of NOM structures, and in terms of providing constraints to molecular simulation models of NOM structures.