Nonequilibrium Conditions (nonequilibrium + condition)

Distribution by Scientific Domains


Selected Abstracts


Analytical Model for Removal of a Uniformly Distributed Single-Component NAPL Under Nonequilibrium Conditions

GROUND WATER MONITORING & REMEDIATION, Issue 3 2001
H.J.H. Brouwers
In this paper a simple analytical model is presented for the one-dimensional transport equation describing the removal of a uniformly distributed, single-component NAPL under nonequilibrium conditions. Both advective and dispersive transport are included in the model. The model describes two distinct stages: a solution for the time the amount of NAPL declines but the length of the NAPL-containing region remains constant, and a solution from the moment the front, behind which all NAPL is depleted, starts to move. The model is valid for both dissolution (i.e., by water) or volatilization (i.e., by air). Dissolution (or volatilization) is considered a firstorder rate process with a constant mass-transfer rate coefficient. As expected, the model approaches the solution for equilibrium conditions if the mass-transfer coefficient tends to infinity. Even though the model is based on some rigorous assumptions, the simplicity of the model makes it useful for obtaining an initial mass-transfer rate coefficient from experimental data, which can be used to estimate the time required to dissolve all NAPL, as shown for two data sets taken from the literature. [source]


Evaluation of the role of black carbon in attenuating bioaccumulation of polycyclic aromatic hydrocarbons from field-contaminated sediments,

ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 11 2004
Brita Sundelin
Abstract The significance of black carbon (BC) for the bioavailability of polycyclic aromatic hydrocarbons (PAHs) was examined by using historically contaminated intact sediment cores in laboratory exposure experiments with the deposit-feeding amphipod Monoporeia affinis. Log values of amphipod biota,sediment accumulation factors (BSAFs) were significantly related to log BC, whereas log BSAFs were related to log octanol,water partition coefficients only in background sediments containing less BC. In the background sediments, the BSAF for polycyclic aromatic hydrocarbons (PAHs) was 1 to 2 for phenanthrene, with lower values for more hydrophobic PAHs, indicating an increase in nonequilibrium conditions with increasing PAH molecular size. For the near-equilibrated phenanthrene and fluoranthene, higher BSAFs were measured during exposure to background sediments, with BSAF decreasing to <0.1 in contaminated sediments in the Stockholm waterways. In situ caged mussels (Dreissena polymorpha) exhibited field BSAF values (relative to sediment-trap,collected suspended matter) for polychlorinated biphenyls (PCBs) of 0.1 to 0.4, but for PAHs of similar hydrophobicity and molecular size, the field BSAFs were much lower and in the range 0.002 to 0.05. This PAH,PCB dichotomy is consistent with recently reported much stronger binding to diesel soot (a form of BC) for PAHs than for PCBs of equal hydrophobicities. Lower BSAFs for the near-equilibrated PAHs (phenanthrene and fluoranthene) in the urban sediments relative to the background sediments were consistent with the larger presence of BC in the urban sediments. This study provides the first linked BSAF,BC field data that supports a causal relationship between strong soot sorption and reduced bioavailability for PAHs. [source]


A thermodynamics-based estimation model for adsorption of organic compounds by carbonaceous materials in environmental sorbents

ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 6 2003
Paul C. M. van Noort
Abstract A model was developed to estimate Langmuir affinities for adsorption of low-polarity organic compounds from either water or air by carbonaceous sorbents. Sorption enthalpies and entropies provided the basic information for the description of sorption affinities in terms of the entropy of melting and either solubility in water or vapor pressure. For m -xylene, polycyclic aromatic hydrocarbons (PAHs) and chlorobenzenes on 10 different sorbents, 80% of the measured sorption affinities fall within a factor of four of the model estimates. Equations for the limiting distribution coefficients in terms of either octanol,air (KOA) or octanol,water partition (Kow) coefficients were derived from regressions of calculated affinities combined with an estimated relation between experimental Langmuir sorption capacities and Kow. Estimated soot,water distribution coefficients were within a factor of three of measured data for polychlorobiphenyls (PCBs) and lower molecular weight PAHs on automotive soot samples and captured the dependence of PCB distribution coefficients on the extent of ortho substitution. For higher molecular weight PAHs, sorption was underestimated. For soot in sediment,water distribution coefficients of PAHs and PCBs, estimated values captured both the trend of measured data with Kow and the dependence on sorbate planarity. Tentative application to aerosol,air distribution explained the observed independence of distribution coefficient,KOA relations for PCBs on the extent of ortho substitution and suggested nonequilibrium conditions for PAHs in comparison with recent measurements. [source]


Analytical Model for Removal of a Uniformly Distributed Single-Component NAPL Under Nonequilibrium Conditions

GROUND WATER MONITORING & REMEDIATION, Issue 3 2001
H.J.H. Brouwers
In this paper a simple analytical model is presented for the one-dimensional transport equation describing the removal of a uniformly distributed, single-component NAPL under nonequilibrium conditions. Both advective and dispersive transport are included in the model. The model describes two distinct stages: a solution for the time the amount of NAPL declines but the length of the NAPL-containing region remains constant, and a solution from the moment the front, behind which all NAPL is depleted, starts to move. The model is valid for both dissolution (i.e., by water) or volatilization (i.e., by air). Dissolution (or volatilization) is considered a firstorder rate process with a constant mass-transfer rate coefficient. As expected, the model approaches the solution for equilibrium conditions if the mass-transfer coefficient tends to infinity. Even though the model is based on some rigorous assumptions, the simplicity of the model makes it useful for obtaining an initial mass-transfer rate coefficient from experimental data, which can be used to estimate the time required to dissolve all NAPL, as shown for two data sets taken from the literature. [source]


Femtosecond electron diffraction: Direct probe of ultrafast structural dynamics in metal films

MICROSCOPY RESEARCH AND TECHNIQUE, Issue 3 2009
Shouhua Nie
Abstract Femtosecond electron diffraction is a rapidly advancing technique that holds a great promise for studying ultrafast structural dynamics in phase transitions, chemical reactions, and function of biological molecules at the atomic time and length scales. In this paper, we summarize our development of a tabletop femtosecond electron diffractometer. Using a delicate instrument design and careful experimental configurations, we demonstrate the unprecedented capability of detecting submilli-ångström lattice spacing change on a subpicosecond timescale with this new technique. We have conducted an in-depth investigation of ultrafast coherent phonon dynamics induced by an impulsive optical excitation in thin-film metals. By probing both coherent acoustic and random thermal lattice motions simultaneously in real time, we have provided the first and unambiguous experimental evidence that the pressure of hot electrons contributes significantly to the generation of coherent acoustic phonons under nonequilibrium conditions when electrons and phonons are not thermalized. Based on these observations, we also propose an innovative approach to measure the electronic Grüneisen parameter in magnetic materials at and above room temperature, which provides a way to gain new insights into electronic thermal expansion in ferromagnetic transition metals. Microsc. Res. Tech. 2009. © 2009 Wiley-Liss, Inc. [source]


Recency, range expansion, and unsorted lineages: implications for interpreting neutral genetic variation in the sharp-tailed grouse (Tympanuchus phasianellus)

MOLECULAR ECOLOGY, Issue 9 2006
A. W. SPAULDING
Abstract Both current and historical patterns of variation are relevant to understanding and managing ecological diversity. Recently derived species present a challenge to the reconstruction of historical patterns because neutral molecular data for these taxa are more likely to exhibit effects of recent and ongoing demographic processes. We studied geographical patterns of neutral molecular variation in a species thought to be of relatively recent origin, Tympanuchus phasianellus (sharp-tailed grouse), using mitochondrial control region sequences (CR-I), amplified fragment length polymorphisms (AFLP), and microsatellites. For historical context, we also analysed CR-I in all species of Tympanuchus. Within T. phasianellus, we found evidence for restricted gene flow between eastern and western portions of the species range, generally corresponding with the range boundary of T. p. columbianus and T. p. jamesi. The mismatch distribution and molecular clock estimates from the CR-I data suggested that all Tympanuchus underwent a range expansion prior to sorting of mitotypes among the species, and that sorting may have been delayed as a result of mutation-drift disequilibrium. This study illustrates the challenge of using genetic data to detect historical divergence in groups that are of relatively recent origin, or that have a history dominated by nonequilibrium conditions. We suggest that in such cases, morphological, ecological, and behavioural data may be particularly important adjuncts to molecular data for the recognition of historically or adaptively divergent groups. [source]