Distribution and partitioning of heavy metals in estuarine sediment cores and implications for the use of sediment quality standards

Directory of Open Access Journals (Sweden)

K. L. Spencer

2002-01-01

Full Text Available Total metal concentrations in surface sediments and historically contaminated sediments were determined in sediment cores collected from three estuaries (Thames, Medway and Blackwater in south-east England. The partitioning behaviour of metals in these sediments was also determined using a sequential extraction scheme. These data were then compared with sediment quality values (SQVs to determine the potential ecotoxicological risk to sediment dwelling organisms. When total metal concentrations in surface sediments are examined, no risk to biota in any of the estuaries is indicated. However, when historically contaminated sediments at depth are also considered, risks to biota are apparent and are greatest for the Thames, followed by the Medway and then the Blackwater. This suggests that regulatory authorities should examine vertical metal profiles, particularly in estuaries that are experiencing low sediment accumulation rates where historically contaminated sediments are in the shallow sub-surface zone and where erosion or dredging activities may take place. When metal partitioning characteristics are also considered, the risk to biota is comparable for the Medway and the Blackwater with the potentially bioavailable fraction presenting no ecotoxicological risk. Conversely, over 70% of metals are labile in the Thames Estuary sediments and toxic effects are probable. This suggests that the application of SQVs using total sediment metal concentrations may over- or under-estimate the risk to biota in geochemically dissimilar estuarine sediments. Keywords: sediment quality values, estuarine sediments, metal contamination, partitioning, sequential extraction

Equilibrium partitioning of macromolecules in confining geometries: Improved universality with a new molecular size parameter

DEFF Research Database (Denmark)

Wang, Yanwei; Peters, Günther H.J.; Hansen, Flemming Yssing

2008-01-01

structures (CABS), allows the computation of equilibrium partition coefficients as a function of confinement size solely based on a single sampling of the configuration space of a macromolecule in bulk. Superior in computational speed to previous computational methods, CABS is capable of handling slits...... parameter for characterization of spatial confinement effects on macromolecules. Results for the equilibrium partition coefficient in the weak confinement regime depend only on the ratio ofR-s to the confinement size regardless of molecular details....

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

International Nuclear Information System (INIS)

You, Zhi-Qiang; Herbert, John M.; Mewes, Jan-Michael; Dreuw, Andreas

2015-01-01

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents

Comparison of the Marcus and Pekar partitions in the context of non-equilibrium, polarizable-continuum solvation models

Energy Technology Data Exchange (ETDEWEB)

You, Zhi-Qiang; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu [Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210 (United States); Mewes, Jan-Michael; Dreuw, Andreas [Interdisciplinary Center for Scientific Computing, Ruprechts-Karls University, Im Neuenheimer Feld 368, 69120 Heidelberg (Germany)

2015-11-28

The Marcus and Pekar partitions are common, alternative models to describe the non-equilibrium dielectric polarization response that accompanies instantaneous perturbation of a solute embedded in a dielectric continuum. Examples of such a perturbation include vertical electronic excitation and vertical ionization of a solution-phase molecule. Here, we provide a general derivation of the accompanying polarization response, for a quantum-mechanical solute described within the framework of a polarizable continuum model (PCM) of electrostatic solvation. Although the non-equilibrium free energy is formally equivalent within the two partitions, albeit partitioned differently into “fast” versus “slow” polarization contributions, discretization of the PCM integral equations fails to preserve certain symmetries contained in these equations (except in the case of the conductor-like models or when the solute cavity is spherical), leading to alternative, non-equivalent matrix equations. Unlike the total equilibrium solvation energy, however, which can differ dramatically between different formulations, we demonstrate that the equivalence of the Marcus and Pekar partitions for the non-equilibrium solvation correction is preserved to high accuracy. Differences in vertical excitation and ionization energies are <0.2 eV (and often <0.01 eV), even for systems specifically selected to afford a large polarization response. Numerical results therefore support the interchangeability of the Marcus and Pekar partitions, but also caution against relying too much on the fast PCM charges for interpretive value, as these charges differ greatly between the two partitions, especially in polar solvents.

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

International Nuclear Information System (INIS)

Zhong Huan; Wang Wenxiong

2009-01-01

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments. - Mercury-particle sorption was more important than mercury-organic matter and organic matter-particle sorption in controlling the partitioning of Hg or MeHg in sediments

The role of sorption and bacteria in mercury partitioning and bioavailability in artificial sediments

Energy Technology Data Exchange (ETDEWEB)

Zhong Huan [Atmospheric, Marine and Coastal Environment Program and Department of Biology, Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon (Hong Kong); Wang Wenxiong [Atmospheric, Marine and Coastal Environment Program and Department of Biology, Hong Kong University of Science and Technology (HKUST), Clear Water Bay, Kowloon (Hong Kong)], E-mail: wwang@ust.hk

2009-03-15

This study compared the relative importance of three types of sorption (organic matter-particle, mercury-organic matter and mercury-particle) in controlling the overall mercury partitioning and bioavailability in sediments. We found that all three types of sorption were important for both inorganic mercury (Hg) and methylated mercury (MeHg). Mercury-particle sorption was more important than mercury-fulvic acid (FA) sorption in increasing the mercury concentrations with increasing aging. Bioavailability (quantified by gut juice extraction from sipunculans) was mainly controlled by mercury-particle sorption, while FA-particle and mercury-FA sorption were not as important, especially for MeHg. Bacterial activity also increased the partitioning of Hg or MeHg in the sediments and was further facilitated by the presence of organic matter. The bioavailability of Hg or MeHg from sediments was only slightly influenced by bacterial activity. This study highlights the importance of sorption from various sources (especially mercury-particle sorption) as well as bacteria in controlling the partitioning and bioavailability of Hg or MeHg in sediments. - Mercury-particle sorption was more important than mercury-organic matter and organic matter-particle sorption in controlling the partitioning of Hg or MeHg in sediments.

Effect of Sediment Availability in Bedload-Dominated Rivers on Fluvial Geomorphic Equilibrium

Science.gov (United States)

Marti, M.

2016-12-01

Channels are known to compensate for changes in sediment supply via covariate changes in channel properties, yet the timescale for adjustment remains poorly constrained. We propose that reductions in sediment flux inhibit equilibrium re-establishment and thus impact the timescale of system adjustment. Using run-of-river dams as natural experiments, this study quantifies the geomorphic response of channels to sediment supply reduction. Channel traits that facilitate increased sediment trapping behind the dam, such as large reservoir storage capacity relative to annual inflow and low slope, were expected to inhibit a channel's ability to re-establish equilibrium following impoundment, lengthening the equilibrium establishment timescale to tens or hundreds of years. Reaches associated with increased trapping were therefore anticipated to exhibit non-equilibrium forms. Channel equilibrium was evaluated downstream of 8 ROR dams in New England with varying degrees of sediment trapping. Sites cover a range of watershed sizes (3-155 km2), channel slopes (.05-5%), 2-year discharges (1.5-60 m3/s) and storage capacity volumes. Because equilibrium channel form is just sufficient to mobilize grains under bankfull conditions in bedload-dominated rivers, the Shields parameter was used to assess equilibrium form. Unregulated, upstream Shields values and regulated, downstream values were calculated at 14 total cross-sections extending 300-450 m upstream and downstream of each dam. Sediment trapping was estimated using Brune's curve (1953). On the Charles Brown Brook (VT), a marginally significant (p=0.08) increase in Shields values from a mean of 0.14 upstream to 0.41 downstream of a 100+ year old dam was observed. In contrast, reaches downstream of the 100+ year old Pelham dam (MA) exhibit significantly lower Shields values. This suggests that trapping behind the dam inhibits the downstream channel from reaching an equilibrium state, but not always in the same way. Better

PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM ...

Science.gov (United States)

This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for the varying biological availability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms. EqP can be used to calculate ESBs for any toxicity endpoint for which there are water-only toxicity data; it is not limited to any single effect endpoint. For the purposes of this document, ESBs for 32 nonionic organic chemicals, including several low molecular weight aliphatic and aromatic compounds, pesticides, and phthalates, were derived using Final Chronic Values (FCV) from Water Quality Criteria (WQC) or Secondary Chronic Values (SCV) derived from existing toxicological data using the Great Lakes Water Quality Initiative (GLI) or narcosis theory approaches. These values are intended to be the concentration of each chemical in water that is protective of the presence of aquatic life. For nonionic organic chemicals demonstrating a narcotic mode of action, ESBs derived using the GLI approach specifically for fres

Application of Equilibrium Partitioning Theory to Soil PAH Contamination (External Review Draft)

Science.gov (United States)

In March 2004, ORD's Ecological Risk Assessment Support Center (ERASC) received a request from the Ecological Risk Assessment Forum (ERAF) to provide insight into the issue of whether equilibrium partitioning (EqP) techniques can be used to predict the toxicity of polycyclic arom...

Cross validation of two partitioning-based sampling approaches in mesocosms containing PCB contaminated field sediment, biota, and activated carbon amendment

DEFF Research Database (Denmark)

Nørgaard Schmidt, Stine; Wang, Alice P.; Gidley, Philip T

2017-01-01

with multiple thicknesses of silicone and in situ pre-equilibrium sampling with low density polyethylene (LDPE) loaded with performance reference compounds were applied independently to measure polychlorinated biphenyls (PCBs) in mesocosms with (1) New Bedford Harbor sediment (MA, USA), (2) sediment and biota......, and (3) activated carbon amended sediment and biota. The aim was to cross validate the two different sampling approaches. Around 100 PCB congeners were quantified in the two sampling polymers, and the results confirmed the good precision of both methods and were in overall good agreement with recently...... published silicone to LDPE partition ratios. Further, the methods yielded Cfree in good agreement for all three experiments. The average ratio between Cfree determined by the two methods was factor 1.4±0.3 (range: 0.6-2.0), and the results thus cross-validated the two sampling approaches. For future...

Water-Sediment Partition of Polycyclic Aromatic Hydrocarbons (PAHs) in Nansi Lake

Science.gov (United States)

Zhang, Guizhai; Diao, Youjiang

2018-06-01

Based on field data of polycyclic aromatic hydrocarbons (PAHs) in water and sediment in Nansi Lake. The concentrations and the partitioning characteristic of PAHs in the water and sediment were studied. The lgKd of high molecular weight PAHs were higher than the low molecular weight PAHs. The most of PAHs Kd values were negligible correlated with TOC, soluble salt, clay and pH of the sediment in Nansi Lake.

Composition and partition functions of partially ionized hydrogen plasma in Non-Local Thermal Equilibrium (Non-LThE) and Non-Local Chemical Equilibrium (Non-LChE)

International Nuclear Information System (INIS)

Chen Kuan; Eddy, T.L.

1993-01-01

A GTME (Generalized MultiThermodynamic Equilibrium) plasma model is developed for plasmas in both Non-LThE (Non-Local Thermal Equilibrium) and Non-LChE (Non-Local Chemical Equilibrium). The model uses multitemperatures for thermal nonequilibrium and non-zero chemical affinities as a measure of the deviation from chemical equilibrium. The plasma is treated as an ideal gas with the Debye-Hueckel approximation employed for pressure correction. The proration method is used when the cutoff energy level is between two discrete levels. The composition and internal partition functions of a hydrogen plasma are presented for electron temperatures ranging from 5000 to 35000 K and pressures from 0.1 to 1000 kPa. Number densities of 7 different species of hydrogen plasma and internal partition functions of different energy modes (rotational, vibrational, and electronic excitation) are computed for three affinity values. The results differ from other plasma properties in that they 1) are not based on equilibrium properties; and 2) are expressed as a function of different energy distribution parameters (temperatures) within each energy mode of each species as appropriate. The computed number densities and partition functions are applicable to calculating the thermodynamic, transport, and radiation properties of a hydrogen plasma not in thermal and chemical equilibria. The nonequilibrium plasma model and plasma compositions presented in this paper are very useful to the diagnosis of high-speed and/or low-pressure plasma flows in which the assumptions of local thermal and chemical equilibrium are invalid. (orig.)

Purification of biomaterials by phase partitioning

Science.gov (United States)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Different partition of polycyclic aromatic hydrocarbon on environmental particulates in freshwater: Microplastics in comparison to natural sediment.

Science.gov (United States)

Wang, Wenfeng; Wang, Jun

2018-01-01

Microplastics pollution in the aquatic ecosystems has aroused increasing concerns in recent years. Though microplastics are known to sorb organic contaminants from water, the interaction mechanisms between microplastics and organic chemicals are not yet well understood. Here we investigated the partition characteristics of phenanthrene (Phe) in three mass-produced plastic particles, including polyethylene (PE), polystyrene (PS) and polyvinylchloride (PVC)， and one natural sediment, as a comparison. The sorption kinetics of Phe onto microplastics and natural sediment were successfully described by the pseudo-second-order model (R 2 > 0.992), while the equilibrium data were best-fitted to the Langmuir isotherm (R 2 > 0.995). Compared with natural sediment, microplastics exhibited higher capacities for Phe which followed an order of PE > PS > PVC. As the aqueous concentration of pyrene (Pyr) increased, both uptakes and distribution coefficients (K d ) of Phe within the solids decreased, with natural sediment giving the largest decline. Although proportions of Phe desorbed from the contaminated microplastics were low, due to the high Phe uptake, microplastics released larger amounts of the sorbed Phe to water than the natural sediment during the desorption process. Given their minimal abundance relative to natural sediment, microplastics may play a less important role in the transport of organic pollutants in a natural aquatic environment. Copyright © 2017 Elsevier Inc. All rights reserved.

Sedimentation dynamics and equilibrium profiles in multicomponent mixtures of colloidal particles

International Nuclear Information System (INIS)

Spruijt, E; Biesheuvel, P M

2014-01-01

In this paper we give a general theoretical framework that describes the sedimentation of multicomponent mixtures of particles with sizes ranging from molecules to macroscopic bodies. Both equilibrium sedimentation profiles and the dynamic process of settling, or its converse, creaming, are modeled. Equilibrium profiles are found to be in perfect agreement with experiments. Our model reconciles two apparently contradicting points of view about buoyancy, thereby resolving a long-lived paradox about the correct choice of the buoyant density. On the one hand, the buoyancy force follows necessarily from the suspension density, as it relates to the hydrostatic pressure gradient. On the other hand, sedimentation profiles of colloidal suspensions can be calculated directly using the fluid density as apparent buoyant density in colloidal systems in sedimentation–diffusion equilibrium (SDE) as a result of balancing gravitational and thermodynamic forces. Surprisingly, this balance also holds in multicomponent mixtures. This analysis resolves the ongoing debate of the correct choice of buoyant density (fluid or suspension): both approaches can be used in their own domain. We present calculations of equilibrium sedimentation profiles and dynamic sedimentation that show the consequences of these insights. In bidisperse mixtures of colloids, particles with a lower mass density than the homogeneous suspension will first cream and then settle, whereas particles with a suspension-matched mass density form transient, bimodal particle distributions during sedimentation, which disappear when equilibrium is reached. In all these cases, the centers of the distributions of the particles with the lowest mass density of the two, regardless of their actual mass, will be located in equilibrium above the so-called isopycnic point, a natural consequence of their hard-sphere interactions. We include these interactions using the Boublik–Mansoori–Carnahan–Starling–Leland (BMCSL

Sorption kinetics of TNT and RDX in anaerobic freshwater and marine sediments: Batch studies.

Science.gov (United States)

Ariyarathna, Thivanka; Vlahos, Penny; Tobias, Craig; Smith, Richard

2016-01-01

Examination of the partitioning of explosives onto sediment in marine environments is critical to predict the toxicological impacts of worldwide explosive-contaminated sites adjacent to estuaries, wetlands, and the coastal ocean. Marine sediments have been identified as sites of enhanced munitions removal, yet most studies addressing these interactions focus on soils and freshwater sediments. The present study measured the kinetics of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sorption onto 2 marine sediments of varying grain sizes (silt vs sand) and organic carbon (OC) content. Abiotic sediment sorption tests were performed at 23 °C, 15 °C, and 4 °C by spiking TNT and RDX solutions directly into anaerobic sediment slurries. Marine sediments showed significantly higher compound uptake rates (0.30-0.80 h(-1) ) than freshwater silt (0.0046-0.0065 h(-1) ) for both compounds, probably because of lower compound solubilities and a higher pH in marine systems. Equilibrium partition constants are on the same order of magnitude for marine silt (1.1-2.0 L kg(-1) sediment) and freshwater silt (1.4-3.1 L kg(-1) sediment) but lower for marine sand (0.72-0.92 L kg(-1) sediment). Total organic carbon content in marine sediments varied linearly with equilibrium partition constants for TNT and was moderately linear for RDX. Uptake rates and equilibrium constants of explosives are inversely correlated to temperature regardless of sediment type because of kinetic barriers associated with low temperatures. © 2015 SETAC.

Use of JANAF Tables in Equilibrium Calculations and Partition Function Calculations for an Undergraduate Physical Chemistry Course

Science.gov (United States)

Cleary, David A.

2014-01-01

The usefulness of the JANAF tables is demonstrated with specific equilibrium calculations. An emphasis is placed on the nature of standard chemical potential calculations. Also, the use of the JANAF tables for calculating partition functions is examined. In the partition function calculations, the importance of the zero of energy is highlighted.

The effect of activated carbon on partitioning, desorption, and biouptake of native polychlorinated biphenyls in four freshwater sediments.

Science.gov (United States)

Sun, Xueli; Ghosh, Upal

2008-11-01

The present study evaluated the effect of activated carbon amendment in four freshwater sediments from the Great Lakes (North America) areas of concern with a wide range of sediment geochemical characteristics (0.83-5.1% total organic carbon) and polychlorinated biphenyl (PCB) concentrations (0.33-84.7 microg/g). The work focused on understanding the impact of activated carbon amendment on PCB aqueous partitioning, PCB desorption characteristics, and PCB biouptake in a freshwater oligochaete (Lumbriculus variegatus). The results showed that PCB aqueous equilibrium concentrations, rapid desorption fractions, and biouptake by the oligochaete were reduced after activated carbon amendment. Addition of activated carbon at a dose of 0.5-fold native organic carbon reduced PCB bioaccumulation by 42% for Niagara River sediment, 85% for Grasse River sediment, 74% for Milwaukee River sediment 1, and 70% for Milwaukee River sediment 2. A linear relationship was observed between log biota-sediment accumulation factor and the first 6-h desorption fractions for each PCB homologue for treated and untreated sediments. Water-lipid bioconcentration factors for PCB congeners were largely conserved after amendment with activated carbon. Our present results suggest that at steady state, changes in the aqueous PCB concentrations can be used to predict changes in PCB bioaccumulation in deposit-feeding organisms. Thus, use of advanced pore-water measurement techniques, such as solid-phase extraction passive samplers, may be suitable for long-term monitoring of treatment performance.

Partition functions. I. Improved partition functions and thermodynamic quantities for normal, equilibrium, and ortho and para molecular hydrogen

Science.gov (United States)

Popovas, A.; Jørgensen, U. G.

2016-11-01

Context. Hydrogen is the most abundant molecule in the Universe. Its thermodynamic quantities dominate the physical conditions in molecular clouds, protoplanetary disks, etc. It is also of high interest in plasma physics. Therefore thermodynamic data for molecular hydrogen have to be as accurate as possible in a wide temperature range. Aims: We here rigorously show the shortcomings of various simplifications that are used to calculate the total internal partition function. These shortcomings can lead to errors of up to 40 percent or more in the estimated partition function. These errors carry on to calculations of thermodynamic quantities. Therefore a more complicated approach has to be taken. Methods: Seven possible simplifications of various complexity are described, together with advantages and disadvantages of direct summation of experimental values. These were compared to what we consider the most accurate and most complete treatment (case 8). Dunham coefficients were determined from experimental and theoretical energy levels of a number of electronically excited states of H2. Both equilibrium and normal hydrogen was taken into consideration. Results: Various shortcomings in existing calculations are demonstrated, and the reasons for them are explained. New partition functions for equilibrium, normal, and ortho and para hydrogen are calculated and thermodynamic quantities are reported for the temperature range 1-20 000 K. Our results are compared to previous estimates in the literature. The calculations are not limited to the ground electronic state, but include all bound and quasi-bound levels of excited electronic states. Dunham coefficients of these states of H2 are also reported. Conclusions: For most of the relevant astrophysical cases it is strongly advised to avoid using simplifications, such as a harmonic oscillator and rigid rotor or ad hoc summation limits of the eigenstates to estimate accurate partition functions and to be particularly careful when

Assessing PCB pollution in the Baltic Sea - An equilibrium partitioning based study

DEFF Research Database (Denmark)

Lang, Susann-Cathrin; Mayer, Philipp; Hursthouse, Andrew

2018-01-01

Sediment cores and bottom water samples from across the Baltic Sea region were analyzed for freely dissolved concentrations (Cfree), total sediment concentrations (CT) and the dissolved aqueous fraction in water of seven indicator PCBs. Ex-situ equilibrium sampling of sediment samples was conducted...... with polydimethylsiloxane (PDMS) coated glass fibers that were analyzed by automated thermal desorption GC-MS, which yielded PCB concentrations in the fiber coating (CPDMS). Measurements of CPDMS and CT were then applied to determine (i) spatially resolved freely dissolved PCB concentrations; (ii) baseline toxicity...

Sediment-porewater partition of polycyclic aromatic hydrocarbons (PAHs) from Lanzhou Reach of Yellow River, China

Energy Technology Data Exchange (ETDEWEB)

Yu Yong [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Xu Jian, E-mail: xujian@nankai.edu.cn [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China); Wang Ping; Sun Hongwen; Dai Shugui [Key Laboratory of Pollution Processes and Environmental Criteria, Ministry of Education, College of Environmental Science and Engineering, Nankai University, Tianjin 300071 (China)

2009-06-15

Pollution of polycyclic aromatic hydrocarbons (PAHs) in the aquatic environment has drawn much attention around the world. The occurrence of 16 priority PAHs in the sediments and corresponding porewaters in Lanzhou Reach of Yellow River, China, and their partitioning behavior between the two phases were investigated. The results demonstrated that the total PAH levels in the sediments were positively correlated with the sediment clay contents (R{sup 2} = 0.756). Concentrations of total PAHs in porewaters ranged from 48.2 to 206 {mu}g/L, and indeno[1,2,3-cd]pyrene (InP) was the most abundant compound measured in the porewater samples with a mean value of 42.9 {mu}g/L. The compositions of PAHs in porewaters were dominated by their compositions in the sediment samples. The in situ organic carbon normalized partition coefficients (logK{sub oc}{sup '}) of the PAHs between sediments and porewaters were significantly correlated with their octanol-water partition coefficients (log K{sub ow}) when log K{sub ow} values were less than 5.5 (naphthalene (Nap) excluded). logK{sub oc}{sup '} values of 14 PAHs were lower than those predicted by the Karickhoff relationship. This discrepancy was largest for InP, dibenzo[a,h]anthracene (DBA), and benzo[ghi]perylene (BgP). The results in present study showed the tendency of PAHs release from sediment to porewater, indicating that PAHs sequestered in the sediments may be a pollution source to aquatic ecosystem.

Heavy metal partitioning of suspended particulate matter-water and sediment-water in the Yangtze Estuary.

Science.gov (United States)

Feng, Chenghong; Guo, Xiaoyu; Yin, Su; Tian, Chenhao; Li, Yangyang; Shen, Zhenyao

2017-10-01

The partitioning of ten heavy metals (As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, and Zn) between the water, suspended particulate matter (SPM), and sediments in seven channel sections during three hydrologic seasons in the Yangtze Estuary was comprehensively investigated. Special attention was paid to the role of tides, influential factors (concentrations of SPM and dissolved organic carbon, and particle size), and heavy metal speciation. The SPM-water and sediment-water partition coefficients (K p ) of the heavy metals exhibited similar changes along the channel sections, though the former were larger throughout the estuary. Because of the higher salinity, the K p values of most of the metals were higher in the north branch than in the south branch. The K p values of Cd, Co, and As generally decreased from the wet season to the dry season. Both the diagonal line method and paired samples t-test showed that no specific phase transfer of heavy metals existed during the flood and ebb tides, but the sediment-water K p was more concentrated for the diagonal line method, owing to the relatively smaller tidal influences on the sediment. The partition coefficients (especially the K p for SPM-water) had negative correlations with the dissolved organic carbon (DOC) but positive correlations were noted with the particle size for most of the heavy metals in sediment. Two types of significant correlations were observed between K p and metal speciation (i.e., exchangeable, carbonate, reducible, organic, and residual fractions), which can be used to identify the dominant phase-partition mechanisms (e.g., adsorption or desorption) of heavy metals. Copyright © 2017 Elsevier Ltd. All rights reserved.

Non-equilibrium flow and sediment transport distribution over mobile river dunes

Science.gov (United States)

Hoitink, T.; Naqshband, S.; McElroy, B. J.

2017-12-01

Flow and sediment transport are key processes in the morphodynamics of river dunes. During floods in several rivers (e.g., the Elkhorn, Missouri, Niobrara, and Rio Grande), dunes are observed to grow rapidly as flow strength increases, undergoing an unstable transition regime, after which they are washed out in what is called upper stage plane bed. This morphological evolution of dunes to upper stage plane bed is the strongest bed-form adjustment during non-equilibrium flows and is associated with a significant change in hydraulic roughness and water levels. Detailed experimental investigations, however, have mostly focused on fixed dunes limited to equilibrium flow and bed conditions that are rare in natural channels. Our understanding of the underlying sedimentary processes that result into the washing out of dunes is therefore very limited. In the present study, using the Acoustic Concentration and Velocity Profiler (ACVP), we were able to quantify flow structure and sediment transport distribution over mobile non-equilibrium dunes. Under these non-equilibrium flow conditions average dune heights were decreasing while dune lengths were increasing. Preliminary results suggest that this morphological behaviour is due to a positive phase lag between sediment transport maximum and topographic maximum leading to a larger erosion on the dune stoss side compared to deposition on dune lee side.

Preparation and characterization of nickel-spiked freshwater sediments for toxicity tests: toward more environmentally realistic nickel partitioning

Science.gov (United States)

Brumbaugh, William G.; Besser, John M.; Ingersoll, Christopher G.; May, Thomas W.; Ivey, Chris D.; Schlekat, Christian E.; Garman, Emily R.

2013-01-01

Two spiking methods were compared and nickel (Ni) partitioning was evaluated during a series of toxicity tests with 8 different freshwater sediments having a range of physicochemical characteristics. A 2-step spiking approach with immediate pH adjustment by addition of NaOH at a 2:1 molar ratio to the spiked Ni was effective in producing consistent pH and other chemical characteristics across a range of Ni spiking levels. When Ni was spiked into sediment having a high acid-volatile sulfide and organic matter content, a total equilibration period of at least 10 wk was needed to stabilize Ni partitioning. However, highest spiking levels evidently exceeded sediment binding capacities; therefore, a 7-d equilibration in toxicity test chambers and 8 volume-additions/d of aerobic overlying water were used to avoid unrealistic Ni partitioning during toxicity testing. The 7-d pretest equilibration allowed excess spiked Ni and other ions from pH adjustment to diffuse from sediment porewater and promoted development of an environmentally relevant, 0.5- to 1-cm oxic/suboxic sediment layer in the test chambers. Among the 8 different spiked sediments, the logarithm of sediment/porewater distribution coefficient values (log Kd) for Ni during the toxicity tests ranged from 3.5 to 4.5. These Kd values closely match the range of values reported for various field Ni-contaminated sediments, indicating that testing conditions with our spiked sediments were environmentally realistic.

Uncertain Henry's law constants compromise equilibrium partitioning calculations of atmospheric oxidation products

Directory of Open Access Journals (Sweden)

C. Wang

2017-06-01

Full Text Available Gas–particle partitioning governs the distribution, removal, and transport of organic compounds in the atmosphere and the formation of secondary organic aerosol (SOA. The large variety of atmospheric species and their wide range of properties make predicting this partitioning equilibrium challenging. Here we expand on earlier work and predict gas–organic and gas–aqueous phase partitioning coefficients for 3414 atmospherically relevant molecules using COSMOtherm, SPARC Performs Automated Reasoning in Chemistry (SPARC, and poly-parameter linear free-energy relationships. The Master Chemical Mechanism generated the structures by oxidizing primary emitted volatile organic compounds. Predictions for gas–organic phase partitioning coefficients (KWIOM/G by different methods are on average within 1 order of magnitude of each other, irrespective of the numbers of functional groups, except for predictions by COSMOtherm and SPARC for compounds with more than three functional groups, which have a slightly higher discrepancy. Discrepancies between predictions of gas–aqueous partitioning (KW/G are much larger and increase with the number of functional groups in the molecule. In particular, COSMOtherm often predicts much lower KW/G for highly functionalized compounds than the other methods. While the quantum-chemistry-based COSMOtherm accounts for the influence of intra-molecular interactions on conformation, highly functionalized molecules likely fall outside of the applicability domain of the other techniques, which at least in part rely on empirical data for calibration. Further analysis suggests that atmospheric phase distribution calculations are sensitive to the partitioning coefficient estimation method, in particular to the estimated value of KW/G. The large uncertainty in KW/G predictions for highly functionalized organic compounds needs to be resolved to improve the quantitative treatment of SOA formation.

Inside-sediment partitioning of PAH, PCB and organochlorine compounds and inferences on sampling and normalization methods

International Nuclear Information System (INIS)

Opel, Oliver; Palm, Wolf-Ulrich; Steffen, Dieter; Ruck, Wolfgang K.L.

2011-01-01

Comparability of sediment analyses for semivolatile organic substances is still low. Neither screening of the sediments nor organic-carbon based normalization is sufficient to obtain comparable results. We are showing the interdependency of grain-size effects with inside-sediment organic-matter distribution for PAH, PCB and organochlorine compounds. Surface sediment samples collected by Van-Veen grab were sieved and analyzed for 16 PAH, 6 PCB and 18 organochlorine pesticides (OCP) as well as organic-matter content. Since bulk concentrations are influenced by grain-size effects themselves, we used a novel normalization method based on the sum of concentrations in the separate grain-size fractions of the sediments. By calculating relative normalized concentrations, it was possible to clearly show underlying mechanisms throughout a heterogeneous set of samples. Furthermore, we were able to show that, for comparability, screening at <125 μm is best suited and can be further improved by additional organic-carbon normalization. - Research highlights: → New method for the comparison of heterogeneous sets of sediment samples. → Assessment of organic pollutants partitioning mechanisms in sediments. → Proposed method for more comparable sediment sampling. - Inside-sediment partitioning mechanisms are shown using a new mathematical approach and discussed in terms of sediment sampling and normalization.

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space.

Science.gov (United States)

Wong, Fiona; Wania, Frank

2011-06-01

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

Science.gov (United States)

Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

2015-10-06

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

Estuarine Facies Model Revisited: Conceptual Model of Estuarine Sediment Dynamics During Non-Equilibrium Conditions

Science.gov (United States)

Elliott, E. A.; Rodriguez, A. B.; McKee, B. A.

2017-12-01

Traditional models of estuarine systems show deposition occurs primarily within the central basin. There, accommodation space is high within the deep central valley, which is below regional wave base and where current energy is presumed to reach a relative minimum, promoting direct deposition of cohesive sediment and minimizing erosion. However, these models often reflect long-term (decadal-millennial) timescales, where accumulation rates are in relative equilibrium with the rate of relative sea-level rise, and lack the resolution to capture shorter term changes in sediment deposition and erosion within the central estuary. This work presents a conceptual model for estuarine sedimentation during non-equilibrium conditions, where high-energy inputs to the system reach a relative maximum in the central basin, resulting in temporary deposition and/or remobilization over sub-annual to annual timescales. As an example, we present a case study of Core Sound, NC, a lagoonal estuarine system where the regional base-level has been reached, and sediment deposition, resuspension and bypassing is largely a result of non-equilibrium, high-energy events. Utilizing a 465 cm-long sediment core from a mini-basin located between Core Sound and the continental shelf, a 40-year sub-annual chronology was developed for the system, with sediment accumulation rates (SAR) interpolated to a monthly basis over the 40-year record. This study links erosional processes in the estuary directly with sediment flux to the continental shelf, taking advantage of the highly efficient sediment trapping capability of the mini-basin. The SAR record indicates high variation in the estuarine sediment supply, with peaks in the SAR record at a recurrence interval of 1 year (+/- 0.25). This record has been compared to historical storm influence for the area. Through this multi-decadal record, sediment flushing events occur at a much more frequent interval than previously thought (i.e. annual rather than

New polymers for low-gravity purification of cells by phase partitioning

Science.gov (United States)

Harris, J. M.

1983-01-01

A potentially powerful technique for separating different biological cell types is based on the partitioning of these cells between the immiscible aqueous phases formed by solution of certain polymers in water. This process is gravity-limited because cells sediment rather than associate with the phase most favored on the basis of cell-phase interactions. In the present contract we have been involved in the synthesis of new polymers both to aid in understanding the partitioning process and to improve the quality of separations. The prime driving force behind the design of these polymers is to produce materials which will aid in space experiments to separate important cell types and to study the partitioning process in the absence of gravity (i.e., in an equilibrium state).

Variable-Field Analytical Ultracentrifugation: I. Time-Optimized Sedimentation Equilibrium

Science.gov (United States)

Ma, Jia; Metrick, Michael; Ghirlando, Rodolfo; Zhao, Huaying; Schuck, Peter

2015-01-01

Sedimentation equilibrium (SE) analytical ultracentrifugation (AUC) is a gold standard for the rigorous determination of macromolecular buoyant molar masses and the thermodynamic study of reversible interactions in solution. A significant experimental drawback is the long time required to attain SE, which is usually on the order of days. We have developed a method for time-optimized SE (toSE) with defined time-varying centrifugal fields that allow SE to be attained in a significantly (up to 10-fold) shorter time than is usually required. To achieve this, numerical Lamm equation solutions for sedimentation in time-varying fields are computed based on initial estimates of macromolecular transport properties. A parameterized rotor-speed schedule is optimized with the goal of achieving a minimal time to equilibrium while limiting transient sample preconcentration at the base of the solution column. The resulting rotor-speed schedule may include multiple over- and underspeeding phases, balancing the formation of gradients from strong sedimentation fluxes with periods of high diffusional transport. The computation is carried out in a new software program called TOSE, which also facilitates convenient experimental implementation. Further, we extend AUC data analysis to sedimentation processes in such time-varying centrifugal fields. Due to the initially high centrifugal fields in toSE and the resulting strong migration, it is possible to extract sedimentation coefficient distributions from the early data. This can provide better estimates of the size of macromolecular complexes and report on sample homogeneity early on, which may be used to further refine the prediction of the rotor-speed schedule. In this manner, the toSE experiment can be adapted in real time to the system under study, maximizing both the information content and the time efficiency of SE experiments. PMID:26287634

Experimental determination and thermodynamic modeling of phase equilibrium and protein partitioning in aqueous two-phase systems containing biodegradable salts

International Nuclear Information System (INIS)

Perez, Brenda; Malpiedi, Luciana Pellegrini; Tubío, Gisela; Nerli, Bibiana; Alcântara Pessôa Filho, Pedro de

2013-01-01

Highlights: ► Binodal data of systems (water + polyethyleneglycol + sodium) succinate are reported. ► Pitzer model describes the phase equilibrium of systems formed by polyethyleneglycol and biodegradable salts satisfactorily. ► This simple thermodynamic framework was able to predict the partitioning behaviour of model proteins acceptably well. - Abstract: Phase diagrams of sustainable aqueous two-phase systems (ATPSs) formed by polyethyleneglycols (PEGs) of different average molar masses (4000, 6000, and 8000) and sodium succinate are reported in this work. Partition coefficients (Kps) of seven model proteins: bovine serum albumin, catalase, beta-lactoglobulin, alpha-amylase, lysozyme, pepsin, urease and trypsin were experimentally determined in these systems and in ATPSs formed by the former PEGs and other biodegradable sodium salts: citrate and tartrate. An extension of Pitzer model comprising long and short-range term contributions to the excess Gibbs free energy was used to describe the (liquid + liquid) equilibrium. Comparison between experimental and calculated tie line data showed mean deviations always lower than 3%, thus indicating a good correlation. The partition coefficients were modeled by using the same thermodynamic approach. Predicted and experimental partition coefficients correlated quite successfully. Mean deviations were found to be lower than the experimental uncertainty for most of the assayed proteins.

Impacts of Sediments on Coral Energetics: Partitioning the Effects of Turbidity and Settling Particles

Science.gov (United States)

Junjie, Reef K.; Browne, Nicola K.; Erftemeijer, Paul L. A.; Todd, Peter A.

2014-01-01

Sediment loads have long been known to be deleterious to corals, but the effects of turbidity and settling particles have not previously been partitioned. This study provides a novel approach using inert silicon carbide powder to partition and quantify the mechanical effects of sediment settling versus reduced light under a chronically high sedimentary regime on two turbid water corals commonly found in Singapore (Galaxea fascicularis and Goniopora somaliensis). Coral fragments were evenly distributed among three treatments: an open control (30% ambient PAR), a shaded control (15% ambient PAR) and sediment treatment (15% ambient PAR; 26.4 mg cm−2 day−1). The rate of photosynthesis and respiration, and the dark-adapted quantum yield were measured once a week for four weeks. By week four, the photosynthesis to respiration ratio (P/R ratio) and the photosynthetic yield (Fv/Fm) had fallen by 14% and 3–17% respectively in the shaded control, contrasting with corals exposed to sediments whose P/R ratio and yield had declined by 21% and 18–34% respectively. The differences in rates between the shaded control and the sediment treatment were attributed to the mechanical effects of sediment deposition. The physiological response to sediment stress differed between species with G. fascicularis experiencing a greater decline in the net photosynthetic yield (13%) than G. somaliensis (9.5%), but a smaller increase in the respiration rates (G. fascicularis = 9.9%, G. somaliensis = 14.2%). These different physiological responses were attributed, in part, to coral morphology and highlighted key physiological processes that drive species distribution along high to low turbidity and depositional gradients. PMID:25197883

Impacts of sediments on coral energetics: partitioning the effects of turbidity and settling particles.

Directory of Open Access Journals (Sweden)

Reef K Junjie

Full Text Available Sediment loads have long been known to be deleterious to corals, but the effects of turbidity and settling particles have not previously been partitioned. This study provides a novel approach using inert silicon carbide powder to partition and quantify the mechanical effects of sediment settling versus reduced light under a chronically high sedimentary regime on two turbid water corals commonly found in Singapore (Galaxea fascicularis and Goniopora somaliensis. Coral fragments were evenly distributed among three treatments: an open control (30% ambient PAR, a shaded control (15% ambient PAR and sediment treatment (15% ambient PAR; 26.4 mg cm(-2 day(-1. The rate of photosynthesis and respiration, and the dark-adapted quantum yield were measured once a week for four weeks. By week four, the photosynthesis to respiration ratio (P/R ratio and the photosynthetic yield (Fv/Fm had fallen by 14% and 3-17% respectively in the shaded control, contrasting with corals exposed to sediments whose P/R ratio and yield had declined by 21% and 18-34% respectively. The differences in rates between the shaded control and the sediment treatment were attributed to the mechanical effects of sediment deposition. The physiological response to sediment stress differed between species with G. fascicularis experiencing a greater decline in the net photosynthetic yield (13% than G. somaliensis (9.5%, but a smaller increase in the respiration rates (G. fascicularis = 9.9%, G. somaliensis  = 14.2%. These different physiological responses were attributed, in part, to coral morphology and highlighted key physiological processes that drive species distribution along high to low turbidity and depositional gradients.

Comparison of modeling approaches for carbon partitioning: Impact on estimates of global net primary production and equilibrium biomass of woody vegetation from MODIS GPP

Science.gov (United States)

Ise, Takeshi; Litton, Creighton M.; Giardina, Christian P.; Ito, Akihiko

2010-12-01

Partitioning of gross primary production (GPP) to aboveground versus belowground, to growth versus respiration, and to short versus long-lived tissues exerts a strong influence on ecosystem structure and function, with potentially large implications for the global carbon budget. A recent meta-analysis of forest ecosystems suggests that carbon partitioning to leaves, stems, and roots varies consistently with GPP and that the ratio of net primary production (NPP) to GPP is conservative across environmental gradients. To examine influences of carbon partitioning schemes employed by global ecosystem models, we used this meta-analysis-based model and a satellite-based (MODIS) terrestrial GPP data set to estimate global woody NPP and equilibrium biomass, and then compared it to two process-based ecosystem models (Biome-BGC and VISIT) using the same GPP data set. We hypothesized that different carbon partitioning schemes would result in large differences in global estimates of woody NPP and equilibrium biomass. Woody NPP estimated by Biome-BGC and VISIT was 25% and 29% higher than the meta-analysis-based model for boreal forests, with smaller differences in temperate and tropics. Global equilibrium woody biomass, calculated from model-specific NPP estimates and a single set of tissue turnover rates, was 48 and 226 Pg C higher for Biome-BGC and VISIT compared to the meta-analysis-based model, reflecting differences in carbon partitioning to structural versus metabolically active tissues. In summary, we found that different carbon partitioning schemes resulted in large variations in estimates of global woody carbon flux and storage, indicating that stand-level controls on carbon partitioning are not yet accurately represented in ecosystem models.

Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

Science.gov (United States)

Kim, Du Yung; Kwon, Jung-Hwan

2018-05-04

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Silicone passive equilibrium samplers as ‘chemometers’ in eels and sediments of a Swedish lake

DEFF Research Database (Denmark)

Jahnke, Annika; Mayer, Philipp; McLachlan, Michael S.

2014-01-01

Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as ‘chemometers’ that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemica...... diagenesis and sorption to phytoplankton. The ‘chemometer’ approach has the potential to become a powerful tool to study the thermodynamic controls on persistent organic chemicals in the environment and should be extended to other environmental compartments.......Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as ‘chemometers’ that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemical...... activities of seven ‘indicator’ polychlorinated biphenyls (PCBs) and hexachlorobenzene in eels and sediments from a Swedish lake. Chemical concentrations in eels and sediments were also measured using exhaustive extraction methods. Lipid-normalized concentrations in eels were higher than organic carbon...

Sediment Equilibrium and Diffusive Fluxes in Relation to Phosphorus Dynamics in the Turbid Minnesota River

National Research Council Canada - National Science Library

James, William F

2009-01-01

...) concentration in large river systems. However, in-stream processes such as equilibrium P flux from suspended sediment and diffusive P flux from deposited sediment stored in river channels may also play a role in soluble P control...

Interpreting time trends and biomagnification of PCBs in the Baltic region using the equilibrium lipid partitioning approach

International Nuclear Information System (INIS)

Nfon, Erick; Cousins, Ian T.

2006-01-01

Multi-year monitoring data for PCBs in abiotic media and biota collected from the Baltic region were compiled into a database and analyzed using the equilibrium lipid partitioning (ELP) approach to study temporal trends as well as to investigate food web biomagnification. Statistically significant reductions in ELP concentrations between 1987 and 2001 were observed in guillemots, air, and some fish species and a general, but not always statistically significant decline in concentrations was observed throughout the Baltic ecosystem. Estimated clearance half-lives ranged from 2.7-10.7 years. The database contained concentrations for a range of different Baltic species, which comprise a well-known Baltic food web. It was possible to derive the trophic position of the species in this food web and relate them to ELP concentrations. A significant positive correlation between ELP concentrations and trophic position was obtained. Estimated food web magnification factors ranged between 1.9 and 5.1 for selected congeners. - The equilibrium lipid partitioning approach is applied to a large Baltic database of PCB concentrations in abiotic and biota media to investigate time trends and biomagnification

Interactions between eutrophication and contaminants - partitioning, bioaccumulation and effects on sediment-dwelling organisms

Energy Technology Data Exchange (ETDEWEB)

Hylland, Ketil; Schaanning, Morten; Skei, Jens; Berge, John Arthur; Eriksen, Dag Oe.; Skoeld, Mattias; Gunnarsson, Jonas

1997-12-31

This report describes an experiment on the interactions between eutrophication and contaminants in marine sediments. The experiment was performed in 24 continuously flushed glass aquaria within which three sediment-dwelling species were kept in a marine sediment. A filter-feeder, blue mussel, was kept in downstream aquaria. The experiment combined three environmental factors: oxygen availability, the presence or absence of contaminants, the addition of organic matter. The objectives were: (1) to quantify differences in the partitioning of contaminants between sediment, pore water and biota as a result of the treatment, (2) to quantify effects of treatments and interactions between treatments on sediment-dwelling organisms, (3) to identify differences, if any, in the release of contaminants from the sediment as the result of treatments. All three contaminants bio accumulated to higher levels in sediments with increased levels of organic material. Feeding directly or indirectly appeared to be the major route for bioaccumulation of benzo(a)pyrene and mercury. Cadmium was also controlled by the concentration in pore water. Sediment in enriched aquaria released more contaminants than sediment with low organic content. Organic enrichment strongly affected growth in the three sediment-dwelling organisms. Growth was less affected by decreased oxygen availability. The presence of contaminants had little effect on the three sediment-dwelling species at the concentrations used in the experiment. 103 refs., 14 figs., 12 tabs.

Allowance for effects of thermodynamic nonideality in sedimentation equilibrium distributions reflecting protein dimerization.

Science.gov (United States)

Wills, Peter R; Scott, David J; Winzor, Donald J

2012-03-01

This reexamination of a high-speed sedimentation equilibrium distribution for α-chymotrypsin under slightly acidic conditions (pH 4.1, I(M) 0.05) has provided experimental support for the adequacy of nearest-neighbor considerations in the allowance for effects of thermodynamic nonideality in the characterization of protein self-association over a moderate concentration range (up to 8 mg/mL). A widely held but previously untested notion about allowance for thermodynamic nonideality effects is thereby verified experimentally. However, it has also been shown that a greater obstacle to better characterization of protein self-association is likely to be the lack of a reliable estimate of monomer net charge, a parameter that has a far more profound effect on the magnitude of the measured equilibrium constant than any deficiency in current procedures for incorporating the effects of thermodynamic nonideality into the analysis of sedimentation equilibrium distributions reflecting reversible protein self-association. Copyright © 2011 Elsevier Inc. All rights reserved.

Sediment-to-Water Partition Coefficients: the Influence of Physicochemical and Seasonal Factors in Eastern Ontario

Energy Technology Data Exchange (ETDEWEB)

Yankovich, Tamara L. [International Atomic Energy Agency, P.O. Box 100, 1400 Vienna (Austria); Shultz, Carmen; Hartwig, Dale; Wills, C. Anne [Atomic Energy of Canada Limited, Chalk River Laboratories, Chalk River, Ontario, K0J 1J0 (Canada); Beresford, Nicholas A. [NERC Centre for Ecology and Hydrology, Lancaster Environment Center, Library Av., Bailrigg, Lancaster, LA1 4AP (United Kingdom); School of Environment and Life Sciences, University of Salford, Manchester, M4 4WT (United Kingdom); Wood, Michael D. [School of Environment and Life Sciences, University of Salford, Manchester, M4 4WT (United Kingdom)

2014-07-01

Sediments often represent an important reservoir for contaminants, such as radionuclides and metals, in aquatic ecosystems. Consequently, lake, stream, and river sediments can potentially act as significant contributors to the total contaminant exposure and radiological doses received by wildlife. Exposure to contaminated sediments is dependent upon several factors. These include net contaminant inputs to a system through time, the physicochemical attributes of the system, the tendency of each contaminant to partition into the sediments relative to water, the spatial distribution of contaminants in the sediments, and the behaviour or life-style of the biota inhabiting a water body. Increased understanding of such factors and their interactions will lead to improved predictions of the radionuclide exposure received by aquatic biota, particularly benthic organisms. Despite the complexity and the dynamic nature of sediments in general, for practical purposes, in environmental impact assessments (EIAs), it is often assumed that radionuclide activity concentrations in various compartments are at steady state with respect to one another. Therefore, ratios can be used to estimate concentrations in one compartment given a known concentration in another. In the case of sediments, sediment-to-water partition coefficients (K{sub d}) are often applied to estimate the contaminant concentration sorbed to particulate matter relative to the concentration measured in the surface water. However, K{sub d} values often range by several orders of magnitude between sampling locations due to site-specific differences in physicochemical conditions in surface waters, seasonal factors, as well as differences in sediment attributes that can affect contaminant partitioning between the dissolved and particulate phases. Consequently, in conducting EIAs, it becomes necessary to either apply generic K{sub d} values that ensure contaminant concentrations in sediments to which biota are exposed are

An assessment of post-remediation changes in sediment chemistry partitioning in an S/S treated soil.

Science.gov (United States)

Cutter, S.; MacLeod, C. L.; Canning, K.; Carey, P. J.; Hills, C. D.

2003-04-01

The Astra Pyrotechnics plant located in the Dartford Marshes, Kent, UK was the site of a field trial utilizing cement stabilization/solidification (S/S) in September 2000. A hotspot containing 35% copper and several thousand part per million lead and zinc was treated in order to trial an new form of cement stabilization (accelerated carbonation technology or ACT) developed by the Centre for Contaminated Land Remediation. A 10 by 20 meter plot was divided into 4 cells into which untreated, OPC (ordinary Portland cement) treated, Envirocem (a Lafarge special cement) treated and ACT treated soil was placed. Each cell has a leachate collection system and the leachate is monitored monthly. In August 2003, 24 cm cores were collected from each cell. These cores were analysed to determine changes in sediment chemistry and metal partitioning characteristics. Sediment chemistry was determined using an aqua regia digestion followed by ICP OES analysis. The CISMED extraction procedure was used to examine partitioning changes. The contaminant concentrations in the leachates remain below UK drinking water standards. However, seasonal cyclicity is observed with an increase of metals in the leachates during winter months. The sediment cores were analysed for Ca, Cr, Cu, Fe, K, Mn, Mg, Na, Ni, Pb and Zn. Only the untreated cell showed any discernable changes in metal concentration with depth. The S/S treated cells show no trends although differences in partitioning between the cells is observed.

Partition of iodine (129I and 127I) isotopes in soils and marine sediments

DEFF Research Database (Denmark)

Hansen, Violeta; Roos, Per; Aldahan, Ala

2011-01-01

Natural organic matter, such as humic and fulvic acids and humin, plays a key role in determining the fate and mobility of radioiodine in soil and sediments. The radioisotope 129I is continuously produced and released from nuclear fuel reprocessing plants, and as a biophilic element, its......–60% of the total 129I are associated with organic matter in soil and sediment samples. At a soil/sediment pH below 5.0–5.5, 127I and 129I in the organic fraction associate primarily with the humic acid while at soil/sediment pH > 6 129I was mostly found to be bound to fulvic acid. Anoxic conditions seem...... environmental mobility is strongly linked to organic matter. Due to its long half-life (15.7 million years), 129I builds up in the environment and can be traced since the beginning of the nuclear era in reservoirs such as soils and marine sediments. Nevertheless, partition of the isotope between the different...

Calculation of the equilibrium pH in a multiple-buffered aqueous solution based on partitioning of proton buffering: a new predictive formula.

Science.gov (United States)

Nguyen, Minhtri K; Kao, Liyo; Kurtz, Ira

2009-06-01

Upon the addition of protons to an aqueous solution containing multiple buffers, the final H+ concentration ([H+]) at equilibrium is determined by the partitioning of added H+ among the various buffer components. In the analysis of acid-base chemistry, the Henderson-Hasselbalch equation and the Stewart strong ion formulation can only describe (rather than predict) the equilibrium pH following a proton load since these formulas calculate the equilibrium pH only when the reactant concentrations at equilibrium(1) 1The term "equilibrium" refers to the steady state proton and reactant concentrations when the buffering of excess protons by the various buffers is complete. are already known. In this regard, it is simpler to directly measure the equilibrium pH rather than measure the equilibrium reactant concentrations to calculate the equilibrium pH. As these formulas cannot predict the final equilibrium [H+] following a proton load to a multiple-buffered aqueous solution, we developed a new quantitative approach for predicting the equilibrium [H+] that is based on the preequilibrium(2)2 The term "preequilibrium" refers to the initial proton and reactant concentrations immediately upon addition of protons and before the buffering of excess protons by the various buffers. concentrations of all buffers in an aqueous solution. The mathematical model used to derive our equation is based on proton transfer buffer equilibria without requiring the incorporation of electroneutrality considerations. The model consists of a quartic polynomial equation that is derived based solely on the partitioning of H+ among the various buffer components. We tested the accuracy of the model using aqueous solutions with various buffers and measured the equilibrium pH values following the addition of HCl. Our results confirmed the accuracy of our new equation (r2 = 1; measured pH vs. predicted pH), indicating that it quantitatively accounts for the underlying acid-base phenomenology.

Calculation of the equilibrium pH in a multiple-buffered aqueous solution based on partitioning of proton buffering: a new predictive formula

Science.gov (United States)

Nguyen, Minhtri K.; Kao, Liyo; Kurtz, Ira

2009-01-01

Upon the addition of protons to an aqueous solution containing multiple buffers, the final H+ concentration ([H+]) at equilibrium is determined by the partitioning of added H+ among the various buffer components. In the analysis of acid-base chemistry, the Henderson-Hasselbalch equation and the Stewart strong ion formulation can only describe (rather than predict) the equilibrium pH following a proton load since these formulas calculate the equilibrium pH only when the reactant concentrations at equilibrium1 1The term “equilibrium” refers to the steady state proton and reactant concentrations when the buffering of excess protons by the various buffers is complete. are already known. In this regard, it is simpler to directly measure the equilibrium pH rather than measure the equilibrium reactant concentrations to calculate the equilibrium pH. As these formulas cannot predict the final equilibrium [H+] following a proton load to a multiple-buffered aqueous solution, we developed a new quantitative approach for predicting the equilibrium [H+] that is based on the preequilibrium22The term “preequilibrium” refers to the initial proton and reactant concentrations immediately upon addition of protons and before the buffering of excess protons by the various buffers. concentrations of all buffers in an aqueous solution. The mathematical model used to derive our equation is based on proton transfer buffer equilibria without requiring the incorporation of electroneutrality considerations. The model consists of a quartic polynomial equation that is derived based solely on the partitioning of H+ among the various buffer components. We tested the accuracy of the model using aqueous solutions with various buffers and measured the equilibrium pH values following the addition of HCl. Our results confirmed the accuracy of our new equation (r2 = 1; measured pH vs. predicted pH), indicating that it quantitatively accounts for the underlying acid-base phenomenology. PMID

Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

International Nuclear Information System (INIS)

Zhao, Shengnan; Liu, Xinhui; Cheng, Dengmiao; Liu, Guannan; Liang, Baocui; Cui, Baoshan; Bai, Junhong

2016-01-01

As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L"− "1 and 40.97–207.44 ng·g"− "1, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using the physicochemical

Ammonia gas transport and reactions in unsaturated sediments: Implications for use as an amendment to immobilize inorganic contaminants

International Nuclear Information System (INIS)

Zhong, L.; Szecsody, J.E.; Truex, M.J.; Williams, M.D.; Liu, Y.

2015-01-01

Highlights: • Ammonia transport can be predicted from gas movement and equilibrium partitioning. • Ammonia diffusion rate in unsaturated sediment is a function of water contents. • High pH induced by ammonia causes mineral dissolution and sequential precipitation. • Ammonia treatment effectively immobilized uranium from contaminated sediments. - Abstract: Use of gas-phase amendments for in situ remediation of inorganic contaminants in unsaturated sediments of the vadose zone may be advantageous, but there has been limited development and testing of gas remediation technologies. Treatment with ammonia gas has a potential for use in treating inorganic contaminants (such as uranium) because it induces a high pore-water pH, causing mineral dissolution and subsequent formation of stable precipitates that decrease the mobility of some contaminants. For field application of this treatment, further knowledge of ammonia transport in porous media and the geochemical reactions induced by ammonia treatment is needed. Laboratory studies were conducted to support calculations needed for field treatment design, to quantify advective and diffusive ammonia transport in unsaturated sediments, to evaluate inter-phase (gas/sediment/pore water) reactions, and to study reaction-induced pore-water chemistry changes as a function of ammonia delivery conditions, such as flow rate, gas concentration, and water content. Uranium-contaminated sediment was treated with ammonia gas to demonstrate U immobilization. Ammonia gas quickly partitions into sediment pore water and increases the pH up to 13.2. Injected ammonia gas advection front movement can be reasonably predicted by gas flow rate and equilibrium partitioning. The ammonia gas diffusion rate is a function of the water content in the sediment. Sodium, aluminum, and silica pore-water concentrations increase upon exposure to ammonia and then decline as aluminosilicates precipitate when the pH declines due to buffering. Up to 85% of

Variable partitioning of flow and sediment transfer through a large river diffluence-confluence unit across a monsoonal flood pulse

Science.gov (United States)

Hackney, C. R.; Aalto, R. E.; Darby, S. E.; Parsons, D. R.; Leyland, J.; Nicholas, A. P.; Best, J.

2016-12-01

Bifurcations represent key morphological nodes within the channel networks of anabranching and braided fluvial channels, playing an important role in controlling local bed morphology, the routing of sediment and water, and defining the stability of the downstream reaches. Herein, we detail field observations of the three-dimensional flow structure, bed morphological changes and partitioning of both flow discharge and suspended sediment through a large diffluence-confluence unit on the Mekong River, Cambodia, across a range of flow stages (from 13,500 m3 s-1 to 27,000 m3 s-1) over the monsoonal flood-pulse cycle. We show that the discharge asymmetry (a measure of the disparity between discharges distributed down the left and right branches of the bifurcation) varies with flow discharge and that the influence of upstream curvature-induced cross-stream water surface slope and bed morphological changes are first-order controls in modulating the asymmetry in bifurcation discharge. Flow discharge is shown to play a key role in defining the morphodynamics of the diffluence-confluence unit downstream of the bifurcation. Our data show that during peak flows (Q 27,000 m3 s-1), the downstream island complex acts as a net sink of suspended sediment (with 2600 kg s-1 being deposited between the diffluence and confluence), whereas during lower flows, on both the rising and falling limbs of the flood wave, the sediment balance is in quasi-equilibrium. We propose a new conceptual model of bifurcation stability that incorporates varying flood discharge and in which the long term stability of the bifurcation, as well as the larger channel planform and morphology of the diffluence-confluence unit, are controlled by the variations in flood discharge.

Quantifying differences in the impact of variable chemistry on equilibrium Uranium(VI) adsorption properties of aquifer sediments.

Science.gov (United States)

Stoliker, Deborah L; Kent, Douglas B; Zachara, John M

2011-10-15

Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO₂²⁺ + 2CO₃²⁻ = >SOUO₂(CO₃HCO₃)²⁻, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logK(c)) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logK(c) values. Using this approach, logK(c) values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (< 0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logK(c) uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

Temporal–spatial variation and partitioning prediction of antibiotics in surface water and sediments from the intertidal zones of the Yellow River Delta, China

Energy Technology Data Exchange (ETDEWEB)

Zhao, Shengnan [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Liu, Xinhui, E-mail: xhliu@bnu.edu.cn [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China); Cheng, Dengmiao [Institute of Agricultural Resources and Regional Planning, Chinese Academy of Agricultural Sciences, Key Laboratory of Plant Nutrition and Fertilizer, Ministry of Agriculture, Beijing 100081 (China); Liu, Guannan [MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, CAGS, Beijing 100037 (China); Liang, Baocui; Cui, Baoshan; Bai, Junhong [State Key Laboratory of Water Environment Simulation, School of Environment, Beijing Normal University, Beijing 100875 (China)

2016-11-01

As special zones, the intertidal zones of the Yellow River Delta (YRD) are highly variable along with time and space. Fluvial–marine and land–ocean interactions which frequently occur in these areas have a great impact on the fate of pollutants. Antibiotics, which contribute to antibiotic-resistant genes (ARGs), are widely detected in wastewater, natural water, soil, sediments, and even drinking water. Therefore, it is meaningful to investigate the occurrence and fate of antibiotics in these special zones. In this study, eight antibiotics belonging to tetracyclines (TCs), fluoroquinolones (FQs), and macrolides (MLs) were detected in the surface water and sediments from the intertidal zones of YRD during two seasons. Two models were established to predict the partitioning coefficients of norfloxacin (NOR) and erythromycin (ETM) using physicochemical properties of sediments, respectively. The total concentrations of these antibiotics were 82.94–230.96 ng·L{sup −} {sup 1} and 40.97–207.44 ng·g{sup −} {sup 1}, respectively, in the surface water and sediments. Seasonal variation was mainly influenced by the frequency of antibiotics use and environment factors. The regions with river supply exhibited the highest concentrations of antibiotics in surface water and sediments. Meanwhile, particle-size fractions, cation exchange capability (CEC), and metal ions content played dominant roles in the partitioning behaviors of NOR and ETM between the surface water and sediments. Both models established in this study featured accuracy and feasibility, which provided the methods for predicting the partitioning coefficients of emerging contaminants similar in structures to NOR and ETM in the intertidal zones. - Highlights: • The intertidal zones of YRD were polluted by antibiotics to some extent. • The river supply was a major pathway for the antibiotic pollution of the intertidal zones of YRD. • The partitioning coefficients of NOR and ETM can be predicted using

VARIATIONS IN THE SPECTRAL PROPERTIES OF FRESHWATER AND ESTUARINE CDOM CAUSED BY PARTITIONING ONTO RIVER AND ESTUARINE SEDIMENTS

Science.gov (United States)

The optical properties and geochemical cycling of chromophoric dissolved organic matter (CDOM) are altered by its sorption to freshwater and estuarine sediments. Measured partition coefficients (Kp) of Satilla River (Georgia) and Cape Fear River estuary (North Carolina) CDOM ran...

Partitioning behaviour of perfluorinated alkyl contaminants between water, sediment and fish in the Orge River (nearby Paris, France)

International Nuclear Information System (INIS)

Labadie, Pierre; Chevreuil, Marc

2011-01-01

This paper reports on the partitioning behaviour of 15 perfluorinated compounds (PFCs), including C 4 -C 10 sulfonates and C 5 -C 14 carboxylic acids, between water, sediment and fish (European chub, Leuciscus cephalus) in the Orge River (nearby Paris). Total PFC levels were 73.0 ± 3.0 ng L -1 in water and 8.4 ± 0.5 ng g -1 in sediment. They were in the range 43.1-4997.2 ng g -1 in fish, in which PFC tissue distribution followed the order plasma > liver > gills > gonads > muscle. Sediment-water distribution coefficients (log K d ) and bioaccumulation factors (log BAF) were in the range 0.8-4.3 and 0.9-6.7, respectively. Both distribution coefficients positively correlated with perfluoroalkyl chain length. Field-based biota-sediment accumulation factors (BSAFs) are also reported, for the first time for PFCs other than perfluorooctane sulfonate. log BSAF ranged between -1.3 and 1.5 and was negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids. - Research highlights: → PFC tissue distribution in European chub followed the order plasma > liver > gills > gonads > muscle. → K d and BAF correlated with PFC alkyl chain length. → BSAF negatively correlated with the perfluoroalkyl chain length in the case of carboxylic acids. → BSAF did not correlate with alkyl chain length of sulfonates. - Sediment-water, biota-water and biota-sediment partitioning coefficients were determined for perfluorinated acids and sulfonates and were generally correlated with alkyl chain length.

Field determination and QSPR prediction of equilibrium-status soil/vegetation partition coefficient of PCDD/Fs.

Science.gov (United States)

Li, Li; Wang, Qiang; Qiu, Xinghua; Dong, Yian; Jia, Shenglan; Hu, Jianxin

2014-07-15

Characterizing pseudo equilibrium-status soil/vegetation partition coefficient KSV, the quotient of respective concentrations in soil and vegetation of a certain substance at remote background areas, is essential in ecological risk assessment, however few previous attempts have been made for field determination and developing validated and reproducible structure-based estimates. In this study, KSV was calculated based on measurements of seventeen 2,3,7,8-substituted PCDD/F congeners in soil and moss (Dicranum angustum), and rouzi grass (Thylacospermum caespitosum) of two background sites, Ny-Ålesund of the Arctic and Zhangmu-Nyalam region of the Tibet Plateau, respectively. By both fugacity modeling and stepwise regression of field data, the air-water partition coefficient (KAW) and aqueous solubility (SW) were identified as the influential physicochemical properties. Furthermore, validated quantitative structure-property relationship (QSPR) model was developed to extrapolate the KSV prediction to all 210 PCDD/F congeners. Molecular polarizability, molecular size and molecular energy demonstrated leading effects on KSV. Copyright © 2014 Elsevier B.V. All rights reserved.

An Analytic Equation Partitioning Climate Variation and Human Impacts on River Sediment Load

Science.gov (United States)

Zhang, J.; Gao, G.; Fu, B.

2017-12-01

Spatial or temporal patterns and process-based equations could co-exist in hydrologic model. Yet, existing approaches quantifying the impacts of those variables on river sediment load (RSL) changes are found to be severely limited, and new ways to evaluate the contribution of these variables are thus needed. Actually, the Newtonian modeling is hardly achievable for this process due to the limitation of both observations and knowledge of mechanisms, whereas laws based on the Darwinian approach could provide one component of a developed hydrologic model. Since that streamflow is the carrier of suspended sediment, sediment load changes are documented in changes of streamflow and suspended sediment concentration (SSC) - water discharge relationships. Consequently, an analytic equation for river sediment load changes are proposed to explicitly quantify the relative contributions of climate variation and direct human impacts on river sediment load changes. Initially, the sediment rating curve, which is of great significance in RSL changes analysis, was decomposed as probability distribution of streamflow and the corresponding SSC - water discharge relationships at equally spaced discharge classes. Furthermore, a proposed segmentation algorithm based on the fractal theory was used to decompose RSL changes attributed to these two portions. Additionally, the water balance framework was utilized and the corresponding elastic parameters were calculated. Finally, changes in climate variables (i.e. precipitation and potential evapotranspiration) and direct human impacts on river sediment load could be figured out. By data simulation, the efficiency of the segmentation algorithm was verified. The analytic equation provides a superior Darwinian approach partitioning climate and human impacts on RSL changes, as only data series of precipitation, potential evapotranspiration and SSC - water discharge are demanded.

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides

Energy Technology Data Exchange (ETDEWEB)

Nowell, Lisa H., E-mail: lhnowell@usgs.gov [U.S. Geological Survey, California Water Science Center, Placer Hall, 6000 J Street, Sacramento, CA 95819 (United States); Norman, Julia E., E-mail: jnorman@usgs.gov [U.S. Geological Survey, Oregon Water Science Center, 2130 SW 5" t" h Avenue, Portland, OR 97201 (United States); Ingersoll, Christopher G., E-mail: cingersoll@usgs.gov [U.S. Geological Survey, Columbia Environmental Research Center, 4200 New Haven Road, Columbia, MO 65021 (United States); Moran, Patrick W., E-mail: pwmoran@usgs.gov [U.S. Geological Survey, Washington Water Science Center, 934 Broadway, Suite 300, Tacoma, WA 98402 (United States)

2016-04-15

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n = 3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical/chemical characteristics

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides

International Nuclear Information System (INIS)

Nowell, Lisa H.; Norman, Julia E.; Ingersoll, Christopher G.; Moran, Patrick W.

2016-01-01

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n = 3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical/chemical characteristics

Geochemical partitioning of lead in biogenic carbonate sediments in a coral reef depositional environment

International Nuclear Information System (INIS)

Horta-Puga, Guillermo

2017-01-01

The fate of trace elements in reef depositional environments has not been extensively investigated. The aim of this study was to determine the partitioning of Pb in sediments of the Veracruz Reef System, and its relation to local environmental sources. Lead was determined in four geochemical fractions: exchangeable (3.8 ± 0.4 μg g −1 ), carbonate (57.0 ± 13.6 μg g −1 ), organic matter (2.0 ± 0.9 μg g −1 ), and mineral (17.5 ± 5.4 μg g −1 ). For the mineral fraction, lead concentrations were higher in those reefs influenced by river discharge or by long-distance transport of terrigenous sediments. The bioavailable concentration of lead (range: 21.9–85.6 μg g −1 ) indicates that the Veracruz Reef System is a moderately polluted area. As expected, the carbonate fraction contained the highest proportion of Pb (70%), and because the reef framework is largely made up of by biogenic carbonate sediments, hence, it is therefore the most important repository of Pb in coral reef depositional environments. - Highlights: • Lead concentrations were determined in four geochemical fractions of reef sediments. • The carbonate fraction accounted for > 70% of the content of Pb in reef sediments. • Terrigenous sediments are the main source of Pb associated to the mineral fraction. • The Veracruz Reef System is considered a moderately polluted area. • Sediments are the main repositories of lead in coral reef depositional environments.

Aqueous two-phase (polyethylene glycol + sodium sulfate) system for caffeine extraction: Equilibrium diagrams and partitioning study

International Nuclear Information System (INIS)

Araujo Sampaio, Daniela de; Mafra, Luciana Igarashi; Yamamoto, Carlos Itsuo; Forville de Andrade, Eriel; Oberson de Souza, Michèle; Mafra, Marcos Rogério; Castilhos, Fernanda de

2016-01-01

Highlights: • Binodal curves of PEG (400, 4000 and 6000) + Na_2SO_4 ATPS were determined. • Tie-lines were experimentally determined for aqueous (PEG 400 + Na_2SO_4) system. • Influence of caffeine on LLE of aqueous (PEG 400 + Na_2SO_4) system was investigated. • Partitioning of caffeine in aqueous (PEG 400 + Na_2SO_4) system was investigated. • Caffeine partition showed to be dependent on temperature and TLL. - Abstract: Environmental friendly methods for liquid–liquid extraction have been taken into account due to critical conditions and ecotoxicological effects potentially produced by organic solvents applied in traditional methods. Liquid–liquid extraction using aqueous two phase systems (ATPSs) presents advantages when compared to traditional liquid–liquid extraction. (Polyethylene glycol (PEG) + sodium sulfate + water) ATPS was applied to study partition of caffeine. Binodal curves for ATPSs composed of PEG of different molecular weights (400 g · mol"−"1, 4000 g · mol"−"1 and 6000 g · mol"−"1) sodium sulfate + water were determined by cloud point method at three different temperatures (293.15, 313.15 and 333.15) K. Liquid–liquid equilibrium (LLE) data (tie-lines, slope of the tie-line and tie-lines length) were obtained applying a gravimetric method proposed by Merchuck and co-workers at the same temperatures for aqueous (PEG 400 + sodium sulfate) and aqueous (PEG 400 + sodium sulfate + caffeine) systems. Reliability of the experimental tie-line (TL) data was evaluated using the equations reported by Othmer–Tobias and satisfactory linearity was obtained. Concerning to aqueous (PEG + sodium sulfate) system, the results pointed out that the higher PEG molecular weight the largest is the heterogeneous region. Moreover, temperature showed not to be relevant on binodal curves behavior, but it influenced on tie-line slopes. Partitioning of caffeine in aqueous (PEG 400 + sodium sulfate) system was investigated at different temperatures

The adsorption/desorption of phosphorus in freshwater sediments from buffer zones: the effects of sediment concentration and pH.

Science.gov (United States)

Zhang, Liang; Du, Yun; Du, Chao; Xu, Meng; Loáiciga, Hugo A

2016-01-01

Riparian buffer zones adjacent to reservoirs and lakes protect aquatic ecosystems from polluted surface runoff. Sediments, collected from the buffer zones of Danjiangkou Reservoir (SR) and Honghu Lake (SL) in an ecologically fragile region in central China, were evaluated to reveal their phosphorus-adsorbing/desorbing properties and storage capacities. A nonlinear regression method was used to fit the pseudo-second-order kinetic and the modified crossover-type Langmuir isotherm models to the experimental data. It is shown that the adsorption of phosphorus onto the studied sediments followed the pseudo-second-order kinetic expression. The modified crossover-type Langmuir isotherm model was found to be a suitable method for describing adsorption/desorption processes in the experimental sediments. The maximum adsorption capacities (Q m), partitioning coefficients (K p), native adsorbed exchangeable phosphorus (NAP), and equilibrium phosphorus concentration (EPC0) were subsequently obtained for the experimental sediments. The effects of sediment concentration and pH were also investigated by batch experiments and Fourier transformation infrared and scanning electron microscopy analyses. The adsorption/desorption characteristics of different phosphate species on the sediments from reservoir and lake buffer zones were identified.

Passive sampling methods for contaminated sediments: State of the science for organic contaminants

Science.gov (United States)

Lydy, Michael J; Landrum, Peter F; Oen, Amy MP; Allinson, Mayumi; Smedes, Foppe; Harwood, Amanda D; Li, Huizhen; Maruya, Keith A; Liu, Jingfu

2014-01-01

This manuscript surveys the literature on passive sampler methods (PSMs) used in contaminated sediments to assess the chemical activity of organic contaminants. The chemical activity in turn dictates the reactivity and bioavailability of contaminants in sediment. Approaches to measure specific binding of compounds to sediment components, for example, amorphous carbon or specific types of reduced carbon, and the associated partition coefficients are difficult to determine, particularly for native sediment. Thus, the development of PSMs that represent the chemical activity of complex compound–sediment interactions, expressed as the freely dissolved contaminant concentration in porewater (Cfree), offer a better proxy for endpoints of concern, such as reactivity, bioaccumulation, and toxicity. Passive sampling methods have estimated Cfree using both kinetic and equilibrium operating modes and used various polymers as the sorbing phase, for example, polydimethylsiloxane, polyethylene, and polyoxymethylene in various configurations, such as sheets, coated fibers, or vials containing thin films. These PSMs have been applied in laboratory exposures and field deployments covering a variety of spatial and temporal scales. A wide range of calibration conditions exist in the literature to estimate Cfree, but consensus values have not been established. The most critical criteria are the partition coefficient between water and the polymer phase and the equilibrium status of the sampler. In addition, the PSM must not appreciably deplete Cfree in the porewater. Some of the future challenges include establishing a standard approach for PSM measurements, correcting for nonequilibrium conditions, establishing guidance for selection and implementation of PSMs, and translating and applying data collected by PSMs. Integr Environ Assess Manag 2014;10:167–178. © 2014 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals, Inc. on behalf of

Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field

NARCIS (Netherlands)

Rakowska, M.I.; Kupryianchyk, D.; Koelmans, A.A.; Grotenhuis, J.T.C.; Rijnaarts, H.H.M.

2014-01-01

Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of

Prediction of gas/particle partitioning of polybrominated diphenyl ethers (PBDEs) in global air: A theoretical study

Science.gov (United States)

Li, Y.-F.; Ma, W.-L.; Yang, M.

2015-02-01

Gas/particle (G/P) partitioning of semi-volatile organic compounds (SVOCs) is an important process that primarily governs their atmospheric fate, long-range atmospheric transport, and their routes of entering the human body. All previous studies on this issue are hypothetically based on equilibrium conditions, the results of which do not predict results from monitoring studies well in most cases. In this study, a steady-state model instead of an equilibrium-state model for the investigation of the G/P partitioning behavior of polybrominated diphenyl ethers (PBDEs) was established, and an equation for calculating the partition coefficients under steady state (KPS) of PBDEs (log KPS = log KPE + logα) was developed in which an equilibrium term (log KPE = log KOA + logfOM -11.91 where fOM is organic matter content of the particles) and a non-equilibrium term (log α, caused by dry and wet depositions of particles), both being functions of log KOA (octanol-air partition coefficient), are included. It was found that the equilibrium is a special case of steady state when the non-equilibrium term equals zero. A criterion to classify the equilibrium and non-equilibrium status of PBDEs was also established using two threshold values of log KOA, log KOA1, and log KOA2, which divide the range of log KOA into three domains: equilibrium, non-equilibrium, and maximum partition domain. Accordingly, two threshold values of temperature t, tTH1 when log KOA = log KOA1 and tTH2 when log KOA = log KOA2, were identified, which divide the range of temperature also into the same three domains for each PBDE congener. We predicted the existence of the maximum partition domain (the values of log KPS reach a maximum constant of -1.53) that every PBDE congener can reach when log KOA ≥ log KOA2, or t ≤ tTH2. The novel equation developed in this study was applied to predict the G/P partition coefficients of PBDEs for our Chinese persistent organic pollutants (POPs) Soil and Air Monitoring

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments

International Nuclear Information System (INIS)

Ahmadi, Fardin; Sparham, Chris; Pawliszyn, Janusz

2017-01-01

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log K DOC ) ranged from 20 to 98% and 3.71–6.72, respectively. Furthermore, sediment-water partition coefficients (K d ), organic-carbon normalized partition coefficients (Log K OC ), and DOC distribution coefficients (Log K DOC ) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31–5.24 and 4.52–5.75 Lkg -1 , respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable

Research on the neutron flux, secular equilibrium of chlorine-36 and groundwater age of the deep quaternary sediments, Hebei plain

International Nuclear Information System (INIS)

Dong Yuean; He Ming; Jiang Songsheng; Wu Shaoyong; Jiang Shan

2001-01-01

For the study of the neutron flux, secular equilibrium of chlorine-36 in the deep quaternary sediments of Hebei plain, the main chemical composition of water sand and confining bed was determined by neutron activation analysis. The mean neutron flux is 2.79 x 10 -5 cm -2 s -1 which was calculated by the chemical composition of the strata. The mean 36 Cl/Cl ratio in secular equilibrium is 1.27 x 10 -14 in the deep quaternary sediments, Hebei Plain. For the study of the groundwater age of the deep Quaternary sediments of Hebei Plain, the 36 Cl/Cl ratio of groundwater samples were determined by tandem accelerator mass spectrometry. The mixed groundwater 36 Cl/Cl ratio of the second and the third aquifer of Quaternary sediments in Baoding district is 247 x 10 -15 , that of the fourth aquifer in Baoding city is 224 x 10 -15 and the third aquifer in Cangzhou district is 40.5 x 10 -15 . The groundwater age of Baoding district was young and that of the third aquifer in Cangzhou was 229.2 ka

Morphodynamic Modeling of the Lower Yellow River, China: Flux (Equilibrium) Form or Entrainment (Nonequilibrium) Form of Sediment Mass Conservation?

Science.gov (United States)

An, C.; Parker, G.; Ma, H.; Naito, K.; Moodie, A. J.; Fu, X.

2017-12-01

Models of river morphodynamics consist of three elements: (1) a treatment of flow hydraulics, (2) a formulation relating some aspect of sediment transport to flow hydraulics, and (3) a description of sediment conservation. In the case of unidirectional river flow, the Exner equation of sediment conservation is commonly described in terms of a flux-based formulation, in which bed elevation variation is related to the streamwise gradient of sediment transport rate. An alternate formulation of the Exner equation, however, is the entrainment-based formulation in which bed elevation variation is related to the difference between the entrainment rate of bed sediment into suspension and the deposition rate of suspended sediment onto the bed. In the flux-based formulation, sediment transport is regarded to be in a local equilibrium state (i.e., sediment transport rate locally equals sediment transport capacity). However, the entrainment-based formulation does not require this constraint; the sediment transport rate may lag in space and time behind the changing flow conditions. In modeling the fine-grained Lower Yellow River, it is usual to treat sediment conservation in terms of an entrainment-based (nonequilibrium) rather than a flux-based (equilibrium) formulation with the consideration that fine-grained sediment may be entrained at one place but deposited only at some distant location downstream. However, the differences in prediction between the two formulations are still not well known, and the entrainment formulation may not always be necessary for the Lower Yellow River. Here we study this problem by comparing the results of flux-based and entrainment-based morphodynamics under conditions typical of the Yellow River, using sediment transport equations specifically designed for the Lower Yellow River. We find, somewhat unexpectedly, that in a treatment of a 200-km reach using uniform sediment, there is little difference between the two formulations unless the

Partitioning of trace metals in the chemical fractions of bed-load sediments of Nahr-Ibrahim river, Lebanon

International Nuclear Information System (INIS)

Korfali, Samira I.; Davies, Brian E.

1999-01-01

Full text.Sediments are the ultimate sink of trace elements. The total metal analysis may only give information concerning possible enrichment of metals. The analysis of metal partitioning in the different chemical components of sediments (exchangeable, carbonate, easily reducible, moderately reducible, organic and residual); give a detailed information on the way in which these metals are bound to sediments, their mobilization capacity and their ability to affect water quality under different environmental conditions. The studied river basin is dominated by limestone formation, the enrichment of metals in the carbonate sediment fraction is a high probability. The objective of the study was to determine the percentage of the total metal content (Fe, Mn, Zn, Cu and Pb) in the six chemical fractions of the bed load sediments of Nahr-Ibrahim river during the dry season and verify the role of carbonate for metal sediment deposition. Bed load sediments were sampled at five locations 13Km stretch, upstream from river mouth at two dates, August and October 1996. the dried samples were sieved into three mechanical fractions (1180-250 μm, 250-75 μm and <75 μm). A sequential chemical extraction was carried on each sized sample sediment, Fe, Mn, Zn, Cu and Pb were determined on the extracts by AAS. The reported data showed that Fe in mainly in the residual fraction, Mn in the residual and carbonate fraction, Zn in the residual, carbonate and Fe oxide fraction, Cu in the residual, carbonate and organic fraction, Pb in the carbonate fraction. The carbonate fraction in sediments played the major common role for metal sediment deposition

Solid/liquid partition coefficients (Kd) for selected soils and sediments at Forsmark and Laxemar-Simpevarp

Energy Technology Data Exchange (ETDEWEB)

Sheppard, Steve; Long, Jeff; Sanipelli, Barb [ECOMatters Inc., Pinawa (Canada); Sohlenius, Gustav [Geological Survey of Sweden (SGU), Uppsala (Sweden)

2009-03-15

Soil and sediment solid/liquid partition coefficients (Kd) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. The Kd data are inherently extremely variable, but also vary systematically with key environmental attributes. For soil Kd, the key variables are pH, clay content and organic carbon content. For sediment Kd, water type (freshwater versus marine) and sediment type (benthic versus suspended) are important. This report summarized Kd data for soils and sediments computed from indigenous stable element concentrations measured at the Forsmark and Laxemar-Simpevarp sites. These were then compared to several literature sources of Kd data for Ce, Cl, Co, Cr, Cs, Fe, Ho, I, La, Mn, Mo, Nb, Nd, Ni, Np, Pa, Pb, Pu, Ra, Sb, Se, Sm, Sn, Sr, Tc, Th, Tm, U and Yb. The Kd data computed from indigenous stable element concentrations may be especially relevant for assessment of long-lived radionuclides from deep disposal of waste, because the long time frame for the potential releases is more consistent with the steady state measured using indigenous stable elements. For almost every one of these elements in soils, a statistically meaningful regression equation was developed to allow estimation of Kd for any soil given a modest amount of information about the soil. Nonetheless, the median residual geometric standard deviation (GSD) was 4.3-fold, implying confidence bounds of about 18-fold above and below the best estimate Kd. For sediment, the values are categorised simply by water type and sediment type. The median GSD for sediment Kd as measured at the Forsmark and Laxemar-Simpevarp sites was 2.5-fold, but the median GSD among literature values was as high as 8.6-fold. Clearly, there remains considerable uncertainty in Kd values, and it is important to account for this in assessment applications

Solid/liquid partition coefficients (Kd) for selected soils and sediments at Forsmark and Laxemar-Simpevarp

International Nuclear Information System (INIS)

Sheppard, Steve; Long, Jeff; Sanipelli, Barb; Sohlenius, Gustav

2009-03-01

Soil and sediment solid/liquid partition coefficients (Kd) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. The Kd data are inherently extremely variable, but also vary systematically with key environmental attributes. For soil Kd, the key variables are pH, clay content and organic carbon content. For sediment Kd, water type (freshwater versus marine) and sediment type (benthic versus suspended) are important. This report summarized Kd data for soils and sediments computed from indigenous stable element concentrations measured at the Forsmark and Laxemar-Simpevarp sites. These were then compared to several literature sources of Kd data for Ce, Cl, Co, Cr, Cs, Fe, Ho, I, La, Mn, Mo, Nb, Nd, Ni, Np, Pa, Pb, Pu, Ra, Sb, Se, Sm, Sn, Sr, Tc, Th, Tm, U and Yb. The Kd data computed from indigenous stable element concentrations may be especially relevant for assessment of long-lived radionuclides from deep disposal of waste, because the long time frame for the potential releases is more consistent with the steady state measured using indigenous stable elements. For almost every one of these elements in soils, a statistically meaningful regression equation was developed to allow estimation of Kd for any soil given a modest amount of information about the soil. Nonetheless, the median residual geometric standard deviation (GSD) was 4.3-fold, implying confidence bounds of about 18-fold above and below the best estimate Kd. For sediment, the values are categorised simply by water type and sediment type. The median GSD for sediment Kd as measured at the Forsmark and Laxemar-Simpevarp sites was 2.5-fold, but the median GSD among literature values was as high as 8.6-fold. Clearly, there remains considerable uncertainty in Kd values, and it is important to account for this in assessment applications

Equilibrium Partitioning Sediment Guidelines (ESGs) for the ...

Science.gov (United States)

... PLC = partial life-cycle ... 5 ii mini iiiiiiiii iiiiiii mi 1 1 iii mini ii i B : - Benthic vs WQC i— w ~_ ~ _ o° _ -0 ° - - - ii mini iiiiiiiii iiiiiii iiiiiiiii mini ii 0.1 ... PhD thesis. ...

Equilibrium passive sampling as a tool to study polycyclic aromatic hydrocarbons in Baltic Sea sediment pore-water systems

DEFF Research Database (Denmark)

Lang, Susann-Cathrin; Hursthouse, Andrew; Mayer, Philipp

2015-01-01

Solid Phase Microextraction (SPME) was applied to provide the first large scale dataset of freely dissolved concentrations for 9 polycyclic aromatic hydrocarbons (PAHs) in Baltic Sea sediment cores. Polydimethylsiloxane (PDMS) coated glass fibers were used for ex-situ equilibrium sampling followed...

A Strategic-Equilibrium Based

Directory of Open Access Journals (Sweden)

Gabriel J. Turbay

2011-03-01

Full Text Available The strategic equilibrium of an N-person cooperative game with transferable utility is a system composed of a cover collection of subsets of N and a set of extended imputations attainable through such equilibrium cover. The system describes a state of coalitional bargaining stability where every player has a bargaining alternative against any other player to support his corresponding equilibrium claim. Any coalition in the sable system may form and divide the characteristic value function of the coalition as prescribed by the equilibrium payoffs. If syndicates are allowed to form, a formed coalition may become a syndicate using the equilibrium payoffs as disagreement values in bargaining for a part of the complementary coalition incremental value to the grand coalition when formed. The emergent well known-constant sum derived game in partition function is described in terms of parameters that result from incumbent binding agreements. The strategic-equilibrium corresponding to the derived game gives an equal value claim to all players.  This surprising result is alternatively explained in terms of strategic-equilibrium based possible outcomes by a sequence of bargaining stages that when the binding agreements are in the right sequential order, von Neumann and Morgenstern (vN-M non-discriminatory solutions emerge. In these solutions a preferred branch by a sufficient number of players is identified: the weaker players syndicate against the stronger player. This condition is referred to as the stronger player paradox.  A strategic alternative available to the stronger players to overcome the anticipated not desirable results is to voluntarily lower his bargaining equilibrium claim. In doing the original strategic equilibrium is modified and vN-M discriminatory solutions may occur, but also a different stronger player may emerge that has eventually will have to lower his equilibrium claim. A sequence of such measures converges to the equal

Partitioning and desorption behavior of polycyclic aromatic hydrocarbons from disparate sources

International Nuclear Information System (INIS)

Reeves, W.R.; McDonald, T.J.; Cizmas, L.; Donnelly, K.C.

2004-01-01

Contaminated sediments pose a unique challenge for risk assessment or remediation because the overlying water column may transport contaminants offsite or to ecological receptors. This research compares the behavior of polycyclic aromatic hydrocarbons (PAHs) on marine sediments from two sites. The first site was affected by shipping activities and the second was impacted by a creosote seep. Organic carbon:water partitioning coefficients (K oc values) were measured with three solutions. Desorption was measured using Tenax beads. PAHs from the ship channel had lower K oc values than those from the creosote facility. For example, the average log K oc value of ship channel pyrene was significantly lower than that of creosote facility pyrene (4.39±0.35 and 5.29±0.09, respectively, when tested in 5 mM calcium chloride). These results were consistent with the greater desorption of pyrene, phenanthrene and benzo(a)pyrene from the ship channel than from the creosote facility sediments. Organic compound desorption from sediments can be considered to be a two-stage process, with a labile fraction that desorbs quickly and a refractory fraction that desorbs much more slowly. In both sediments, more than 75% of the benzo(a)pyrene was found to have partitioned into the refractory phase. The amounts of phenanthrene and pyrene that partitioned into the refractory phase were lower. Linear correlations of log K oc with log (C R /C L ) (where C R and C L are the fractions of the compound in the refractory and labile phases, respectively, at time zero) showed that partitioning measurements made with the US EPA's Toxicity Characteristic Leaching Procedure fluid (US EPA, 1996) most closely matched predictions of desorption behavior. The data imply that with a larger data set, it may be possible to relate simple partitioning measurements to desorption behavior. Partitioning measurements were used to predict water concentrations. Despite having higher concentrations of carcinogenic PAHs

Occurrence and partitioning of antibiotic compounds found in the water column and bottom sediments from a stream receiving two wastewater treatment plant effluents in Northern New Jersey, 2008

Energy Technology Data Exchange (ETDEWEB)

Gibs, Jacob, E-mail: jgibs@usgs.gov [U.S. Geological Survey, 810 Bear Tavern Road, West Trenton, NJ 08628 (United States); Heckathorn, Heather A. [U.S. Geological Survey, 810 Bear Tavern Road, West Trenton, NJ 08628 (United States); Meyer, Michael T. [U.S. Geological Survey, 4821 Quail Crest Place, Lawrence, KS 66049 (United States); Klapinski, Frank R.; Alebus, Marzooq; Lippincott, Robert L. [New Jersey Department of Environmental Protection, PO Box 413, Trenton, NJ 08625 (United States)

2013-08-01

An urban watershed in northern New Jersey was studied to determine the presence of four classes of antibiotic compounds (macrolides, fluoroquinolones, sulfonamides, and tetracyclines) and six degradates in the water column and bottom sediments upstream and downstream from the discharges of two wastewater treatment plants (WWTPs) and a drinking-water intake (DWI). Many antibiotic compounds in the four classes not removed by conventional WWTPs enter receiving waters and partition to stream sediments. Samples were collected at nine sampling locations on 2 days in September 2008. Two of the nine sampling locations were background sites upstream from two WWTP discharges on Hohokus Brook. Another background site was located upstream from a DWI on the Saddle River above the confluence with Hohokus Brook. Because there is a weir downstream of the confluence of Hohokus Brook and Saddle River, the DWI receives water from Hohokus Brook at low stream flows. Eight antibiotic compounds (azithromycin (maximum concentration 0.24 μg/L), ciprofloxacin (0.08 μg/L), enrofloxacin (0.015 μg/L), erythromycin (0.024 μg/L), ofloxacin (0.92 μg/L), sulfamethazine (0.018 μg/L), sulfamethoxazole (0.25 μg/L), and trimethoprim (0.14 μg/L)) and a degradate (erythromycin–H{sub 2}O (0.84 μg/L)) were detected in the water samples from the sites downstream from the WWTP discharges. The concentrations of six of the eight detected compounds and the detected degradate compound decreased with increasing distance downstream from the WWTP discharges. Azithromycin, ciprofloxacin, ofloxacin, and trimethoprim were detected in stream-bottom sediments. The concentrations of three of the four compounds detected in sediments were highest at a sampling site located downstream from the WWTP discharges. Trimethoprim was detected in the sediments from a background site. Pseudo-partition coefficients normalized for streambed sediment organic carbon concentration were calculated for azithromycin

Occurrence and partitioning of antibiotic compounds found in the water column and bottom sediments from a stream receiving two wastewater treatment plant effluents in Northern New Jersey, 2008

International Nuclear Information System (INIS)

Gibs, Jacob; Heckathorn, Heather A.; Meyer, Michael T.; Klapinski, Frank R.; Alebus, Marzooq; Lippincott, Robert L.

2013-01-01

An urban watershed in northern New Jersey was studied to determine the presence of four classes of antibiotic compounds (macrolides, fluoroquinolones, sulfonamides, and tetracyclines) and six degradates in the water column and bottom sediments upstream and downstream from the discharges of two wastewater treatment plants (WWTPs) and a drinking-water intake (DWI). Many antibiotic compounds in the four classes not removed by conventional WWTPs enter receiving waters and partition to stream sediments. Samples were collected at nine sampling locations on 2 days in September 2008. Two of the nine sampling locations were background sites upstream from two WWTP discharges on Hohokus Brook. Another background site was located upstream from a DWI on the Saddle River above the confluence with Hohokus Brook. Because there is a weir downstream of the confluence of Hohokus Brook and Saddle River, the DWI receives water from Hohokus Brook at low stream flows. Eight antibiotic compounds (azithromycin (maximum concentration 0.24 μg/L), ciprofloxacin (0.08 μg/L), enrofloxacin (0.015 μg/L), erythromycin (0.024 μg/L), ofloxacin (0.92 μg/L), sulfamethazine (0.018 μg/L), sulfamethoxazole (0.25 μg/L), and trimethoprim (0.14 μg/L)) and a degradate (erythromycin–H 2 O (0.84 μg/L)) were detected in the water samples from the sites downstream from the WWTP discharges. The concentrations of six of the eight detected compounds and the detected degradate compound decreased with increasing distance downstream from the WWTP discharges. Azithromycin, ciprofloxacin, ofloxacin, and trimethoprim were detected in stream-bottom sediments. The concentrations of three of the four compounds detected in sediments were highest at a sampling site located downstream from the WWTP discharges. Trimethoprim was detected in the sediments from a background site. Pseudo-partition coefficients normalized for streambed sediment organic carbon concentration were calculated for azithromycin, ciprofloxacin

Assessing bioavailability of DDT and metabolites in marine sediments using solid-phase microextraction with performance reference compounds.

Science.gov (United States)

Bao, Lian-Jun; Jia, Fang; Crago, J; Zeng, Eddy Y; Schlenk, D; Gan, Jay

2013-09-01

Solid-phase microextraction (SPME) has often been used to estimate the freely dissolved concentration (Cfree ) of organic contaminants in sediments. A significant limitation in the application of SPME for Cfree measurement is the requirement for attaining equilibrium partition, which is often difficult for strongly hydrophobic compounds such as DDT. A method was developed using SPME with stable isotope-labeled analogues as performance reference compounds (PRCs) to measure Cfree of DDT and metabolites (DDTs) in marine sediments. Six (13) C-labeled or deuterated PRCs were impregnated into polydimethylsiloxane (PDMS) fiber before use. Desorption of PRCs from PDMS fibers and absorption of DDTs from sediment were isotropic in a range of sediments evaluated ex situ under well-mixed conditions. When applied to a historically contaminated marine sediment from a Superfund site, the PRC-SPME method yielded Cfree values identical to those found by using a conventional equilibrium SPME approach (Eq-SPME), whereas the time for mixing was reduced from 9 d to only 9 h. The PRC-SPME method was further evaluated against bioaccumulation of DDTs by Neanthes arenaceodentata in the contaminated sediment with or without amendment of activated carbon or sand. Strong correlations were consistently found between the derived equilibrium concentrations on the fiber and lipid-normalized tissue residues for DDTs in the worms. Results from the present study clearly demonstrated the feasibility of coupling PRCs with SPME sampling to greatly shorten sampling time, thus affording much improved flexibility in the use of SPME for bioavailability evaluation. Copyright © 2013 SETAC.

Superfluid Kubo formulas from partition function

International Nuclear Information System (INIS)

Chapman, Shira; Hoyos, Carlos; Oz, Yaron

2014-01-01

Linear response theory relates hydrodynamic transport coefficients to equilibrium retarded correlation functions of the stress-energy tensor and global symmetry currents in terms of Kubo formulas. Some of these transport coefficients are non-dissipative and affect the fluid dynamics at equilibrium. We present an algebraic framework for deriving Kubo formulas for such thermal transport coefficients by using the equilibrium partition function. We use the framework to derive Kubo formulas for all such transport coefficients of superfluids, as well as to rederive Kubo formulas for various normal fluid systems

Foundational aspects of the concept of chemical activity

DEFF Research Database (Denmark)

Mayer, Philipp

2015-01-01

The chemical activity of an organic chemical quantifies its potential for spontaneous physicochemical processes, such as diffusion, sorption, and partitioning. For instance, the chemical activity of a sediment contaminant determines its equilibrium partitioning concentration in sediment-dwelling ...

Factors affecting the partitioning of Cu, Zn and Pb in boulder coatings and stream sediments in the vicinity of a polymetallic sulfide deposit

Science.gov (United States)

Filipek, L.H.; Chao, T.T.; Carpenter, R.H.

1981-01-01

A sequential extraction scheme is utilized to determine the geochemical partitioning of Cu, Zn and Pb among hydrous Mn- and Fe-oxides, organics and residual crystalline silicates and oxides in the minus-80-mesh ( Fe-oxides > Mn-oxides; Zn, Mn-oxides {reversed tilde equals} organics > Fe-oxides; Pb, Fe-oxides > organics > Mn-oxides. In the sediments, organics are the most efficient scavengers of all three ore metals. These results emphasize the importance of organics as sinks for the ore metals, even in environments with high concentrations of Mn- and Fe-oxides. Of the ore metals, Zn appears to be the most mobile, and is partitioned most strongly into the coatings. However, anomaly contrast for hydromorphic Zn, normalized to the MnFe-oxide or organic content, is similar in sediments and coatings. Cu shows the highest anomaly on the boulder coatings, probably due to precipitation of a secondary Cu mineral. In contrast, detrital Pb in the pan concentrates shows a better anomaly than any hydromorphic Pb component. ?? 1981.

Predicting the bioaccumulation of polyaromatic hydrocarbons and polychlorinated biphenyls in benthic animals in sediments

Energy Technology Data Exchange (ETDEWEB)

Tuikka, A.I., E-mail: anitat@student.uef.fi [University of Eastern Finland, Department of Environmental and Biological Sciences, P.O. Box 111, FI-80101 Joensuu (Finland); Leppänen, M.T., E-mail: Matti.T.Leppanen@ymparisto.fi [Finnish Environment Institute, Laboratories/Research and Innovation Laboratory, P.O. Box 35, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Akkanen, J., E-mail: jarkko.akkanen@uef.fi [University of Eastern Finland, Department of Environmental and Biological Sciences, P.O. Box 111, FI-80101 Joensuu (Finland); Sormunen, A.J., E-mail: Arto.Sormunen@mamk.fi [University of Eastern Finland, Department of Environmental and Biological Sciences, P.O. Box 111, FI-80101 Joensuu (Finland); Leonards, P.E.G., E-mail: pim.leonards@vu.nl [Institute for Environmental Studies, Vrije Universiteit Amsterdam, De Boelelaan 1087, 1081 HV Amsterdam (Netherlands); Hattum, B. van, E-mail: bert.vanhattum@deltares.nl [Institute for Environmental Studies, Vrije Universiteit Amsterdam, De Boelelaan 1087, 1081 HV Amsterdam (Netherlands); Vliet, L.A. van, E-mail: lavanvliet@hotmail.com [Ministry of Transport, Public Works and Water Management, National Institute for Coastal and Marine Management/RIKZ, P.O. Box 207, 9750 AE Haren (Netherlands); Brack, W., E-mail: werner.brack@ufz.de [Helmholtz Centre for Environmental Research - UFZ, Department of Effect-Directed Analysis, Permoserstraße 15, 04318 Leipzig (Germany); Smedes, F., E-mail: smedes@recetox.muni.cz [Ministry of Transport, Public Works and Water Management, National Institute for Coastal and Marine Management/RIKZ, P.O. Box 207, 9750 AE Haren (Netherlands); and others

2016-09-01

There were two main objectives in this study. The first was to compare the accuracy of different prediction methods for the chemical concentrations of polyaromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the organism, based on the measured chemical concentrations existing in sediment dry matter or pore water. The predicted tissue concentrations were compared to the measured ones after 28-day laboratory test using oligochaeta worms (Lumbriculus variegatus). The second objective was to compare the bioaccumulation of PAHs and PCBs in the laboratory test with the in situ bioaccumulation of these compounds. Using the traditional organic carbon-water partitioning model, tissue concentrations were greatly overestimated, based on the concentrations in the sediment dry matter. Use of an additional correction factor for black carbon with a two-carbon model, significantly improved the bioaccumulation predictions, thus confirming that black carbon was important in binding the chemicals and reducing their accumulation. The predicted PAH tissue concentrations were, however, high compared to the observed values. The chemical concentrations were most accurately predicted from their freely dissolved pore water concentrations, determined using equilibrium passive sampling. The patterns of PCB and PAH accumulation in sediments for laboratory-exposed L. variegatus were similar to those in field-collected Lumbriculidae worms. Field-collected benthic invertebrates and L. variegatus accumulated less PAHs than PCBs with similar lipophilicity. The biota to sediment accumulation factors of PAHs tended to decrease with increasing sediment organic carbon normalized concentrations. The presented data yields bioconcentration factors (BCF) describing the chemical water-lipid partition, which were found to be higher than the octanol-water partition coefficients, but on a similar level with BCFs drawn from relevant literature. In conclusion, using the two-carbon model method

Equilibrium shoreface profiles

DEFF Research Database (Denmark)

Aagaard, Troels; Hughes, Michael G

2017-01-01

Large-scale coastal behaviour models use the shoreface profile of equilibrium as a fundamental morphological unit that is translated in space to simulate coastal response to, for example, sea level oscillations and variability in sediment supply. Despite a longstanding focus on the shoreface...... profile and its relevance to predicting coastal response to changing environmental conditions, the processes and dynamics involved in shoreface equilibrium are still not fully understood. Here, we apply a process-based empirical sediment transport model, combined with morphodynamic principles to provide......; there is no tuning or calibration and computation times are short. It is therefore easily implemented with repeated iterations to manage uncertainty....

Kinetics of Solute Partitioning During Intercritical Annealing of a Medium-Mn Steel

Science.gov (United States)

Kamoutsi, H.; Gioti, E.; Haidemenopoulos, Gregory N.; Cai, Z.; Ding, H.

2015-11-01

The evolution of austenite fraction and solute partitioning (Mn, Al, and C) during intercritical annealing was calculated for a medium-Mn steel containing 11 pct Mn. Austenite growth takes place in three stages. The first stage is growth under non-partitioning local equilibrium (NPLE) controlled by carbon diffusion in ferrite. The second stage is growth under partitioning local equilibrium (PLE) controlled by diffusion of Mn in ferrite. The third stage is shrinkage of austenite under PLE controlled by diffusion of Mn in austenite. During PLE growth, the austenite is progressively enriched in Mn. Compositional spikes evolve early during NPLE growth and broaden with annealing temperature and time.

Metal/silicate partitioning of Pt and the origin of the "late veneer"

Science.gov (United States)

Ertel, W.; Walter, M. J.; Drake, M. J.; Sylvester, P. J.

2002-12-01

Highly siderophile elements (HSEs) are perfect tools for investigating core forming processes in planetary bodies due to their Fe-loving (siderophile) geochemical behavior. Tremendous scientific effort was invested into this field during the past 10 years - mostly in 1 atm experiments. However, little is known about their high-pressure geochemistry and partitioning behavior between core and mantle forming phases. This knowledge is essential to distinguish between equilibrium (Magma Ocean) and non-equilibrium (heterogeneous accretion, late veneer) models for the accretion history for the early Earth. We therefore chose to investigate the partitioning behavior of Pt up to pressures of 140 kbar (14 GPa) and temperatures of 1950°C. The used melt composition - identical to melt systems used in 1 atm experiments - is the eutectic composition of Anorthite-Diopside (AnDi), a pseudo-basalt. A series of runs were performed which were internaly buffered by the piston cylinder apparatus, and were followed by duplicate experiments buffered in the AnDi-C-CO2 system. These experiments constitute reversals since they approach equilibrium from an initially higher and lower Pt solubility (8 ppm in the non-buffered runs, and essentially Pt free in the buffered runs). Experimental charges were encapsulated in Pt capsules which served as source for Pt. Experiments up to 20 kbar were performed in a Quickpress piston cylinder apparatus, while experiments at higher pressures were performed in a Walker-type (Tucson, AZ) and a Kawai-type (Misasa, Japan) multi anvil apparatus. Time series experiments were performed in piston-cylinder runs to determine minimum run durations for the achievement of equilibrium, and to guarantee high-quality partitioning data. 6 hours was found to be sufficient to obtain equilibrium. In practice, all experiments exceeded 12 hours to assure equilibrium. In a second set of runs the temperature dependence of the partitioning behavior of Pt was investigated between

A gel probe equilibrium sampler for measuring arsenic porewater profiles and sorption gradients in sediments: II. Field application to Haiwee reservoir sediment

Science.gov (United States)

Campbell, K.M.; Root, R.; O'Day, P. A.; Hering, J.G.

2008-01-01

Arsenic (As) geochemistry and sorption behavior were measured in As- and iron (Fe)-rich sediments of Haiwee Reservoir by deploying undoped (clear) polyacrylamide gels and hydrous ferric oxide (HFO)-doped gels in a gel probe equilibrium sampler, which is a novel technique for directly measuring the effects of porewater composition on As adsorption to Fe oxides phases in situ. Arsenic is deposited at the sediment surface as As(V) and is reduced to As(III) in the upper layers of the sediment (0-8 cm), but the reduction of As(V) does not cause mobilization into the porewater. Dissolved As and Fe concentrations increased at depth in the sediment column driven by the reductive dissolution of amorphous Fe(III) oxyhydroxides and conversion to a mixed Fe(II, III) green rust-type phase. Adsorption of As and phosphorous (P) onto HFO-doped gels was inhibited at intermediate depths (10-20 cm), possibly due to dissolved organic or inorganic carbon, indicating that dissolved As concentrations were at least partially controlled by porewater composition rather than surface site availability. In sediments that had been recently exposed to air, the region of sorption inhibition was not observed, suggesting that prior exposure to air affected the extent of reductive dissolution, porewater chemistry, and As adsorption behavior. Arsenic adsorption onto the HFO-doped gels increased at depths >20 cm, and the extent of adsorption was most likely controlled by the competitive effects of dissolved phosphate. Sediment As adsorption capacity appeared to be controlled by changes in porewater composition and competitive effects at shallower depths, and by reductive dissolution and availability of sorption sites at greater burial depths. ?? 2008 American Chemical Society.

The distribution and partitioning of common antibiotics in water and sediment of the Pearl River Estuary, South China.

Science.gov (United States)

Liang, Ximei; Chen, Baowei; Nie, Xiangping; Shi, Zhen; Huang, Xiaoping; Li, Xiangdong

2013-09-01

Antibiotics released into the aquatic environment play an important role in the spread of antibiotic resistance. In the Pearl River Estuary (PRE) and the coastal zone, the concentrations of antibiotics decreased from the Pearl River to the estuary, suggesting that antibiotics primarily originated from river tributaries and terrigenous sources. Within the PRE area, the concentrations of antibiotics in water were higher in the west coast than the east side, reflecting the high density of anthropogenic activities and hydraulic conditions along the west riverbank. Seasonal variations were also observed for most of detected antibiotics in water. The pseudo-partitioning coefficient of norfloxacin had a good correlation with the TOC content of sediments, as did erythromycin-H2O with the pH of water. The results suggest that environmental conditions can significantly affect the distribution of antibiotics between water and sediment. Copyright © 2013 Elsevier Ltd. All rights reserved.

A partition function approximation using elementary symmetric functions.

Directory of Open Access Journals (Sweden)

Ramu Anandakrishnan

Full Text Available In statistical mechanics, the canonical partition function [Formula: see text] can be used to compute equilibrium properties of a physical system. Calculating [Formula: see text] however, is in general computationally intractable, since the computation scales exponentially with the number of particles [Formula: see text] in the system. A commonly used method for approximating equilibrium properties, is the Monte Carlo (MC method. For some problems the MC method converges slowly, requiring a very large number of MC steps. For such problems the computational cost of the Monte Carlo method can be prohibitive. Presented here is a deterministic algorithm - the direct interaction algorithm (DIA - for approximating the canonical partition function [Formula: see text] in [Formula: see text] operations. The DIA approximates the partition function as a combinatorial sum of products known as elementary symmetric functions (ESFs, which can be computed in [Formula: see text] operations. The DIA was used to compute equilibrium properties for the isotropic 2D Ising model, and the accuracy of the DIA was compared to that of the basic Metropolis Monte Carlo method. Our results show that the DIA may be a practical alternative for some problems where the Monte Carlo method converge slowly, and computational speed is a critical constraint, such as for very large systems or web-based applications.

Distribution, partitioning and sources of polycyclic aromatic hydrocarbons in the water–SPM–sediment system of Lake Chaohu, China

Energy Technology Data Exchange (ETDEWEB)

Qin, Ning [MOE Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Peking University, Beijing 100871 (China); State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Wei; Kong, Xiang-Zhen; Liu, Wen-Xiu; He, Qi-Shuang; Yang, Bin; Wang, Qing-Mei; Yang, Chen; Jiang, Yu-Jiao [MOE Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Peking University, Beijing 100871 (China); Jorgensen, Sven Erik [Section of Toxicology and Environmental Chemistry, Institute A, University of Copenhagen, University Park 2, DK 2100, Copenhagen Ø (Denmark); Xu, Fu-Liu, E-mail: xufl@urban.pku.edu.cn [MOE Laboratory for Earth Surface Processes, College of Urban and Environmental Sciences, Peking University, Beijing 100871 (China); Zhao, Xiao-Li, E-mail: zhaoxiaoli_zxl@126.com [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China)

2014-10-15

The residual levels of polycyclic aromatic hydrocarbons (PAHs) in the water, suspended particular matter (SPM) and sediment from Lake Chaohu were measured with a gas chromatograph–mass spectrometer (GC–MS). The spatial–temporal distributions and the SPM–water partition of PAHs and their influencing factors were investigated. The potential sources and contributions of PAHs in the sediment were estimated by positive matrix factorization (PMF) and probabilistic stable isotopic analysis (PSIA). The results showed that the average residual levels of total PAHs (PAH16) in the water, SPM and sediment were 170.7 ± 70.8 ng/L, 210.7 ± 160.7 ng/L and 908.5 ± 1878.1 ng/g dry weight, respectively. The same spatial distribution trend of PAH16 in the water, SPM and sediment was found from high to low: river inflows > western lake > eastern lake > water source area. There was an obvious seasonal trend of PAH16 in the water, while no obvious seasonal trend was found in the SPM. The residues and distributions of PAHs in the water, SPM and sediment relied heavily on carbon content. Significant Pearson correlations were found between LogK{sub oc} and LogK{sub ow} as well as some hydro-meteorological factors. Three major sources of PAHs including coal and biomass combustions, and vehicle emissions were identified. - Highlights: • Highest residual level of total PAHs in the SPM was detected. • Similar spatial trend of PAH16 in the water, SPM and sediment. • PAHs distributions in the water-sediment system relied heavily on organic carbon. • Correlations between LogK{sub oc} and LogK{sub ow} as well as hydro-meteorological factors. • Coal and biomass combustions and vehicle emissions were three major sources of PAHs.

Polycyclic aromatic hydrocarbon (PAH) contamination of surface sediments and oysters from the inter-tidal areas of Dar es Salaam, Tanzania

International Nuclear Information System (INIS)

Gaspare, Lydia; Machiwa, John F.; Mdachi, S.J.M.; Streck, Georg; Brack, Werner

2009-01-01

Surface sediment and oyster samples from the inter-tidal areas of Dar es Salaam were analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) including the 16 compounds prioritized by US-EPA using GC/MS. The total concentration of PAHs in the sediment ranged from 78 to 25,000 ng/g dry weight, while oyster concentrations ranged from 170 to 650 ng/g dry weight. Hazards due to sediment contamination were assessed using Equilibrium Partitioning Sediment Benchmarks and Threshold Effect Levels. Diagnostic indices and principle component analysis were used to identify possible sources. Interestingly, no correlation between sediment and oyster concentrations at the same sites was found. This is supported by completely different contamination patterns, suggesting different sources for both matrices. Hazard assessment revealed possible effects at six out of eight sites on the benthic communities and oyster populations. The contribution of PAH intake via oyster consumption to carcinogenic risks in humans seems to be low. - PAH contamination may pose hazards to benthos but limited risks to humans

Polycyclic aromatic hydrocarbon (PAH) contamination of surface sediments and oysters from the inter-tidal areas of Dar es Salaam, Tanzania

Energy Technology Data Exchange (ETDEWEB)

Gaspare, Lydia; Machiwa, John F. [Department of Aquatic Environment and Conservation, University of Dar es Salaam, P.O. Box 60091, Dar es Salaam (Tanzania, United Republic of); Mdachi, S.J.M. [Department of Chemistry, University of Dar es Salaam, P.O. Box 35062, Dar es Salaam (Tanzania, United Republic of); Streck, Georg [UFZ Helmholtz Centre for Environmental Research Leipzig-Halle, Department of Effect-Directed Analysis, Permoserstrasse 15, 04318 Leipzig (Germany); Brack, Werner [UFZ Helmholtz Centre for Environmental Research Leipzig-Halle, Department of Effect-Directed Analysis, Permoserstrasse 15, 04318 Leipzig (Germany)], E-mail: werner.brack@ufz.de

2009-01-15

Surface sediment and oyster samples from the inter-tidal areas of Dar es Salaam were analyzed for 23 polycyclic aromatic hydrocarbons (PAHs) including the 16 compounds prioritized by US-EPA using GC/MS. The total concentration of PAHs in the sediment ranged from 78 to 25,000 ng/g dry weight, while oyster concentrations ranged from 170 to 650 ng/g dry weight. Hazards due to sediment contamination were assessed using Equilibrium Partitioning Sediment Benchmarks and Threshold Effect Levels. Diagnostic indices and principle component analysis were used to identify possible sources. Interestingly, no correlation between sediment and oyster concentrations at the same sites was found. This is supported by completely different contamination patterns, suggesting different sources for both matrices. Hazard assessment revealed possible effects at six out of eight sites on the benthic communities and oyster populations. The contribution of PAH intake via oyster consumption to carcinogenic risks in humans seems to be low. - PAH contamination may pose hazards to benthos but limited risks to humans.

The equilibrium sedimentation of hyaluronic acid and of two synthetic polymers

Science.gov (United States)

Nichol, L. W.; Ogston, A. G.; Preston, B. N.

1967-01-01

1. The method of equilibrium sedimentation has been investigated as an alternative to osmotic-pressure measurement for determining thermodynamic properties of polymer solutions at relatively high concentrations. 2. The simplifications that must be made in the theoretical treatment are discussed. 3. Measurements have been made on samples of polyethylene glycol, neutralized polymethacrylic acid and hyaluronic acid. With the first and third, values of the `non-ideality coefficients' have been obtained that agree with those obtained from osmotic measurements on the same materials. 4. Evidence has been obtained of the presence in hyaluronic acid preparations of a fraction that has either a lower degree of thermodynamic non-ideality or a higher density increment than the bulk of the sample. This fraction is not protein. ImagesFig. 3.Fig. 4.Fig. 5.Fig. 7.Fig. 8.Fig. 9.Fig. 11.Fig. 12.Fig. 13.Fig. 14. PMID:6029600

Equilibrium partitioning of drug molecules between aqueous and amino acid ester-based ionic liquids

International Nuclear Information System (INIS)

Jing, Jun; Li, Zhiyong; Pei, Yuanchao; Wang, Huiyong; Wang, Jianji

2013-01-01

Highlights: ► Partition coefficients of twelve drug molecules in ILs have been determined. ► The possible mechanism has been investigated from 13 C NMR measurements. ► Hydrophobic π–π interaction is the main driving force for the partitioning of drug molecules. -- Abstract: In this work, a series of novel room temperature ionic liquids (ILs) have been synthesized with cheap, naturally α-amino acid ester as cations and bis(trifluoromethylsulfonyl)imide as anion. The glass transition temperature and thermal decomposition temperature of these ILs, partition coefficients of some coumarins and purine alkaloids between water and the amino acid ester-based ILs at T = 298.15 K, and Gibbs energy, enthalpy and entropy changes for the transfer of caffeine and 6,7-dihydroxycoumarin from water to [LeuC 2 ][Tf 2 N] have been determined. It is shown that these ILs are highly effective materials for the extraction of drug compounds like coumarin, 4-hydroxycoumarin, 7-hydroxycoumarin, 3-aminocoumarin, coumarin-3-carboxylic acid, 6,7-dihydroxycoumarin, 6,7-dihydroxy-4-methylcoumarin, caffeine, theobromine, theophylline, inosine, and 2,6-diaminopurine. The partition process is driven by enthalpy term, and partition coefficients of the drug molecules increase with the increase of hydrophobicity of both the drug molecules and the ILs. Furthermore, the possible partition mechanism has been investigated from 13 C NMR measurements

Chlor-alkali industrial contamination and riverine transport of mercury: Distribution and partitioning of mercury between water, suspended matter, and bottom sediment of the Thur River, France

International Nuclear Information System (INIS)

Hissler, Christophe; Probst, Jean-Luc

2006-01-01

Total dissolved and total particulate Hg mass balances were estimated during one hydrological period (July 2001-June 2002) in the Thur River basin, which is heavily polluted by chlor-alkali industrial activity. The seasonal variations of the Hg dynamics in the aquatic environment were assessed using total Hg concentrations in bottom sediment and suspended matter, and total and reactive dissolved Hg concentrations in the water. The impact of the chlor-alkali plant (CAP) remains the largest concern for Hg contamination of this river system. Upstream from the CAP, the Hg partitioning between dissolved and particulate phases was principally controlled by the dissolved fraction due to snow melting during spring high flow, while during low flow, Hg was primarily adsorbed onto particulates. Downstream from the CAP, the Hg partitioning is controlled by the concentration of dissolved organic and inorganic ligands and by the total suspended sediment (TSS) concentrations. Nevertheless, the particulate fluxes were five times higher than the dissolved ones. Most of the total annual flux of Hg supplied by the CAP to the river is transported to the outlet of the catchment (total Hg flux: 70 μg m -2 a -1 ). Downstream from the CAP, the bottom sediment, mainly composed of coarse sediment (>63 μm) and depleted in organic matter, has a weak capacity to trap Hg in the river channel and the stock of Hg is low (4 mg m -2 ) showing that the residence time of Hg in this river is short

Toxicological benchmarks for screening contaminants of potential concern for effects on sediment-associated biota: 1994 Revision. Environmental Restoration Program

International Nuclear Information System (INIS)

Hull, R.N.; Suter, G.W. II

1994-06-01

Because a hazardous waste site may contain hundreds of chemicals, it is important to screen contaminants of potential concern for the ecological risk assessment. Often this screening is done as part of a Screening Assessment, the purpose of which is to evaluate the available data, identify data gaps, and screen contaminants of potential concern. Screening may be accomplished by using a set of toxicological benchmarks. These benchmarks are helpful in determining whether contaminants warrant further assessment or are at a level that requires no further attention. If a chemical concentration or the reported detection limit exceeds a proposed lower benchmark, more analysis is needed to determine the hazards posed by that chemical. If, however, the chemical concentration falls below the lower benchmark value, the chemical may be eliminated from further study. This report briefly describes three categories of approaches to the development of sediment quality benchmarks. These approaches are based on analytical chemistry, toxicity test and field survey data. A fourth integrative approach incorporates all three types of data. The equilibrium partitioning approach is recommended for screening nonpolar organic contaminants of concern in sediments. For inorganics, the National Oceanic and Atmospheric Administration has developed benchmarks that may be used for screening. There are supplemental benchmarks from the province of Ontario, the state of Wisconsin, and US Environmental Protection Agency Region V. Pore water analysis is recommended for polar organic compounds; comparisons are then made against water quality benchmarks. This report is an update of a prior report. It contains revised ER-L and ER-M values, the five EPA proposed sediment quality criteria, and benchmarks calculated for several nonionic organic chemicals using equilibrium partitioning

Equilibrium thermodynamics of the partitioning of non-steroidal anti-inflammatory drugs into human erythrocyte ghost membranes

International Nuclear Information System (INIS)

Omran, Ahmed A.

2013-01-01

Graphical abstract: Bar diagram representing thermodynamic parameters obtained for the partitioning of NSAIDs into human erythrocyte ghost membranes at physiological pH; 7.4. Highlights: • Partition coefficients of NSAIDs into HEG membranes were determined. • Thermodynamic parameters were evaluated and successfully analyzed. • Partitioning of NSAIDs into HEG membranes was exothermic. • Partitioning of NSAIDs into HEG is spontaneous with negative free energy values. • Identical partitioning enthalpy–entropy driven compensation mechanism was shown. -- Abstract: In this work,second derivative spectrophotometry was applied for determining the partition coefficients (K p s) of four non-steroidal anti-inflammatory drugs (NSAIDs; flufenamic, meclofenamic, mefenamic and niflumic acids) into human erythrocyte ghost (HEG) membranes over a temperature range from (283.2 to 313.2) K. The proposed method allowed the evaluation and direct analyses of thermodynamic parameters; enthalpy (ΔH W→M ), Gibbs energy (ΔG W→M ) and entropy (ΔS W→M ) changes of the partitioning of NSAIDs into HEG membranes. The partitioning of NSAIDs between polar aqueous phase and non-polar lipid bilayer HEG membrane phase was exothermic with negative (ΔH W→M ) which compensated for the changes in (ΔS W→M ). The negative values of (ΔG W→M ) revealed that the partitioning of NSAIDs into HEG, owing to their transfer from polar aqueous phase and non-polar HEG phase is spontaneous. The enthalpy–entropy correlation analysis resulted in a good linearity that suggests an identical partitioning enthalpy–entropy driven compensation mechanism for the studied NSAIDs

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments.

Science.gov (United States)

Ahmadi, Fardin; Sparham, Chris; Pawliszyn, Janusz

2017-11-01

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log K DOC ) ranged from 20 to 98% and 3.71-6.72, respectively. Furthermore, sediment-water partition coefficients (K d ), organic-carbon normalized partition coefficients (Log K OC ), and DOC distribution coefficients (Log K DOC ) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31-5.24 and 4.52-5.75 Lkg -1 , respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable binding

Impact of sediment organic matter quality on the fate and effects of fluoranthene in the infaunal brittle star Amphiura filiformis

DEFF Research Database (Denmark)

Selck, Henriette; Granberg, Maria E; Forbes, Valery E.

2005-01-01

Hydrophobic contaminants, such as polycyclic aromatic hydrocarbons (PAHs) readily adsorb to organic matter. The aim of this study was to determine the importance of the quality of sedimentary organic matter for the uptake, biotransformation and toxicity of the PAH, fluoranthene (Flu......), in the infaunal brittle star Amphiura filiformis. Brittle stars were exposed to a base sediment covered by a 2 cm Flu-spiked top layer (30 mug Flu/g dry wt. sed.), enriched to the same total organic carbon content with either refractory or labile organic matter. The labile carbon source was concentrated green...... to equilibrium partitioning between organism lipid content and organic content of the sediment. Biotransformation of Flu by brittle stars was very limited and unaffected by organic matter quality. A. filiformis contributed to the downward transport of Flu from the surface sediment to the burrow lining...

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

Energy Technology Data Exchange (ETDEWEB)

Wilson, Brittan [University of Massachusetts, Department of Environment, Earth and Ocean Sciences, 100 Morrissey Blvd., Boston, MA 02125 (United States); Chen, Robert F. [University of Massachusetts, Department of Environment, Earth and Ocean Sciences, 100 Morrissey Blvd., Boston, MA 02125 (United States); Cantwell, Mark [NHEERL, Atlantic Ecology Division, US Environmental Protection Agency, 27 Tarzwell Drive, Narragansett, RI 02882 (United States); Gontz, Allen; Jun, Zhu; Olsen, Curtis R. [University of Massachusetts, Department of Environment, Earth and Ocean Sciences, 100 Morrissey Blvd., Boston, MA 02125 (United States)

2009-07-01

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 {+-} 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 {+-} 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k{sub d} {approx} 10{sup 4}, consistent with laboratory estimates.

The partitioning of Triclosan between aqueous and particulate bound phases in the Hudson River Estuary

International Nuclear Information System (INIS)

Wilson, Brittan; Chen, Robert F.; Cantwell, Mark; Gontz, Allen; Zhu Jun; Olsen, Curtis R.

2009-01-01

The distribution of Triclosan within the Hudson River Estuary can be explained by a balance among the overall effluent inputs from municipal sewage treatment facilities, dilution of Triclosan concentrations in the water column with freshwater and seawater inputs, removal of Triclosan from the water column by adsorption to particles, and loss to photodegradation. This study shows that an average water column concentration of 3 ± 2 ng/l (in the lower Hudson River Estuary) is consistent with an estimate for dilution of average wastewater concentrations with seawater and calculated rates of adsorption of Triclosan to particles. An average Triclosan sediment concentration of 26 ± 11 ng/g would be in equilibrium with the overlying water column if Triclosan has a particle-to-water partitioning coefficient of k d ∼ 10 4 , consistent with laboratory estimates.

A study of chemical equilibrium of tri-component mixtures of hydrogen isotopes

International Nuclear Information System (INIS)

Cristescu, Ioana; Cristescu, I.; Peculea, M.

1998-01-01

In this paper we present a model for computing the equilibrium constants for chemical reactions between hydrogen's isotopes as function of temperature. The equilibrium constants were expressed with the aid of Gibbs potential and the partition function of the mixture. We assessed the partition function for hydrogen's isotopes having in view that some nuclei are fermions and other bosons. As results we plotted the values of equilibrium constants as function of temperature. Knowing these values we determined the deuterium distribution on species (for mixture H 2 -HD-D 2 ) as function of total deuterium concentration and the tritium distribution on species (for mixtures D 2 -DT-T 2 and H 2 -HT-T 2 ) as function of total tritium concentration. (authors)

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon

International Nuclear Information System (INIS)

Choi, Hyeok; Lawal, Wasiu; Al-Abed, Souhail R.

2015-01-01

Highlights: • Problematic aged real PCBs-contaminated sediment (WHS) was examined. • Performance of reactive activated carbon (RAC) impregnated with Pd–ZVI was tested. • Fate and transport of PCBs bound to WHS in the presence of RAC was fully traced. • Direct mixing configuration was compared with compartment configuration. • Results reflected real world complexities associated with slow desorption of PCBs. - Abstract: Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon

Energy Technology Data Exchange (ETDEWEB)

Choi, Hyeok, E-mail: hchoi@uta.edu [Department of Civil Engineering, The University of Texas at Arlington, 416 Yates Street, Arlington, TX 76019-0308 (United States); Environmental and Earth Sciences Program, The University of Texas at Arlington, 500 Yates Street, Arlington, TX 76019-0049 (United States); Lawal, Wasiu [Environmental and Earth Sciences Program, The University of Texas at Arlington, 500 Yates Street, Arlington, TX 76019-0049 (United States); Al-Abed, Souhail R. [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 W. Martin Luther King Dr., Cincinnati, OH 45268 (United States)

2015-04-28

Highlights: • Problematic aged real PCBs-contaminated sediment (WHS) was examined. • Performance of reactive activated carbon (RAC) impregnated with Pd–ZVI was tested. • Fate and transport of PCBs bound to WHS in the presence of RAC was fully traced. • Direct mixing configuration was compared with compartment configuration. • Results reflected real world complexities associated with slow desorption of PCBs. - Abstract: Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls.

Predicted effectiveness of in-situ activated carbon amendment for field sediment sites with variable site- and compound-specific characteristics

Energy Technology Data Exchange (ETDEWEB)

Choi, Yongju, E-mail: ychoi81@snu.ac.kr [Department of Civil and Environmental Engineering, Seoul National University, Seoul 151-744 (Korea, Republic of); Cho, Yeo-Myoung; Luthy, Richard G. [Department of Civil and Environmental Engineering, Stanford University, Stanford, CA 94305-4020 (United States); Werner, David [School of Civil Engineering and Geosciences, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom)

2016-01-15

Highlights: • The model accounts for the heterogeneity of AC distribution in field applications. • AC amendment effectiveness is predicted for ten sediment sites. • An HOC mass transfer model and calibrated parameters provide reliable predictions. • AC amendment is predicted to be effective for most sites. • K{sub ow}, K{sub d}, and equilibrium-based calculations are useful indicators. - Abstract: A growing body of evidence shows that the effectiveness of in-situ activated carbon (AC) amendment to treat hydrophobic organic contaminants (HOCs) in sediments can be reliably predicted using a mass transfer modeling approach. This study analyzes available field data for characterizing AC-sediment distribution after mechanical mixing of AC into sediment. Those distributions are used to develop an HOC mass transfer model that accounts for plausible heterogeneities resulting from mixing of AC into sediment. The model is applied to ten field sites in the U.S. and Europe with 2–3 representative HOCs from each site using site- and HOC-specific model parameters collected from the literature. The model predicts that the AC amendment reduces the pore-water HOC concentrations by more than 95% fifteen years after AC deployment for 18 of the 25 total simulated cases when the AC is applied at doses of 1.5 times sediment total organic carbon content with an upper limit of 5 dry wt%. The predicted effectiveness shows negative correlation with the HOC octanol–water partitioning coefficients and the sediment-water distribution coefficients, and positive correlation with the effectiveness calculated based on equilibrium coefficients of sediment and AC, suggesting the possibility for use of the values for screening-level assessments.

Predicted effectiveness of in-situ activated carbon amendment for field sediment sites with variable site- and compound-specific characteristics

International Nuclear Information System (INIS)

Choi, Yongju; Cho, Yeo-Myoung; Luthy, Richard G.; Werner, David

2016-01-01

Highlights: • The model accounts for the heterogeneity of AC distribution in field applications. • AC amendment effectiveness is predicted for ten sediment sites. • An HOC mass transfer model and calibrated parameters provide reliable predictions. • AC amendment is predicted to be effective for most sites. • K ow , K d , and equilibrium-based calculations are useful indicators. - Abstract: A growing body of evidence shows that the effectiveness of in-situ activated carbon (AC) amendment to treat hydrophobic organic contaminants (HOCs) in sediments can be reliably predicted using a mass transfer modeling approach. This study analyzes available field data for characterizing AC-sediment distribution after mechanical mixing of AC into sediment. Those distributions are used to develop an HOC mass transfer model that accounts for plausible heterogeneities resulting from mixing of AC into sediment. The model is applied to ten field sites in the U.S. and Europe with 2–3 representative HOCs from each site using site- and HOC-specific model parameters collected from the literature. The model predicts that the AC amendment reduces the pore-water HOC concentrations by more than 95% fifteen years after AC deployment for 18 of the 25 total simulated cases when the AC is applied at doses of 1.5 times sediment total organic carbon content with an upper limit of 5 dry wt%. The predicted effectiveness shows negative correlation with the HOC octanol–water partitioning coefficients and the sediment-water distribution coefficients, and positive correlation with the effectiveness calculated based on equilibrium coefficients of sediment and AC, suggesting the possibility for use of the values for screening-level assessments.

Desorption, partitioning, and dechlorination characteristics of PCBs in sediments in interaction with reactive activated carbon.

Science.gov (United States)

Choi, Hyeok; Lawal, Wasiu; Al-Abed, Souhail R

2015-04-28

Sediment (WHS) in Waukegan Harbor, Illinois, heavily contaminated and aged with polychlorinated biphenyls (PCBs), was treated with reactive activated carbon (RAC) impregnated with palladized iron nanoparticles. Lab test proceeded in a direct mixing configuration of RAC and WHS. A compartment configuration, where RAC was physically separated from WHS, was also designed to trace the sequential transport and fate of PCBs, including desorption, adsorption, dechlorination, and re-partitioning. PCBs, once desorbed from WHS, were immediately sequestrated to RAC and subject to dechlorination. Direct mixing of WHS with RAC was one-order of magnitude more effective for dechlorination than compartment configuration. Compared to their desorption-followed by-adsorption route, direct physical contact of RAC with PCBs bound to WHS exhibited negligible contribution to the availability of PCBs for dechlorination reaction. Addition of RAC even in compartment configuration facilitated PCBs desorption from WHS. However, slow desorption of PCBs limited overall performance, resulting in a five-order of magnitude lower dechlorination yield when compared with treatment of purely aqueous PCBs. The low dechlorination yield reflected real world complexities in treating 3.19% organic carbon-containing WHS aged with PCBs for 40 years. These observations were further supported when compared with results on clean Cesar Creek sediment spiked with 2-chlorinated biphenyls. Copyright © 2015 Elsevier B.V. All rights reserved.

Dissipation and the relaxation to equilibrium

International Nuclear Information System (INIS)

Evans, Denis J; Williams, Stephen R; Searles, Debra J

2009-01-01

Using the recently derived dissipation theorem and a corollary of the transient fluctuation theorem (TFT), namely the second-law inequality, we derive the unique time independent, equilibrium phase space distribution function for an ergodic Hamiltonian system in contact with a remote heat bath. We prove under very general conditions that any deviation from this equilibrium distribution breaks the time independence of the distribution. Provided temporal correlations decay, we show that any nonequilibrium distribution that is an even function of the momenta eventually relaxes (not necessarily monotonically) to the equilibrium distribution. Finally we prove that the negative logarithm of the microscopic partition function is equal to the thermodynamic Helmholtz free energy divided by the thermodynamic temperature and Boltzmann's constant. Our results complement and extend the findings of modern ergodic theory and show the importance of dissipation in the process of relaxation towards equilibrium

Sorption of radon-222 to natural sediments

International Nuclear Information System (INIS)

Wong, C.S.; Chin, Y.P.; Gschwend, P.M.

1992-01-01

The sorption of radon to sediments was investigated, since this may affect the use of porewater radon profiles for estimating bed irrigation rates. Batch experiments showed that radon has an organic-carbon-normalized sediment-water partition coefficient (K oc , L kg oc -1 ) of 21.1 ± 2.9 for a Boston Harbor sediment, 25.3 ± 2.1 for a Charles River sediment, and 22.4 ± 2.6 for a Buzzards Bay sediment. These values are in close agreement with predictions using radon's octanol-water partition coefficient (K ow ), which was measured to be 32.4 ± 1.5. Temperature and ionic strength effects on K oc were estimated to be small. Given rapid sorption kinetics, the authors suggest that slurry stripping techniques used by many investigators to measure 222 Rn in sediment samples collect both sorbed and dissolved radon. Sorption effects were included in a transport model to obtain revised estimates of irrigation rates from existing literature profiles. Irrigation rates had to be increased over previously reported values in proportion to the sediment organic matter content

Partitioning of organochlorine pesticides from water to polyethylene passive samplers

International Nuclear Information System (INIS)

Hale, Sarah E.; Martin, Timothy J.; Goss, Kai-Uwe; Arp, Hans Peter H.; Werner, David

2010-01-01

The mass transfer rates and equilibrium partitioning behaviour of 14 diverse organochlorine pesticides (OCP) between water and polyethylene (PE) passive samplers, cut from custom made PE sheets and commercial polyethylene plastic bags, were quantified. Overall mass transfer coefficients, k O , estimated PE membrane diffusion coefficients, D PE , and PE-water partitioning coefficients, K PE-water, are reported. In addition, the partitioning of three polycyclic aromatic hydrocarbons (PAHs) from water to PE is quantified and compared with literature values. K PE-water values agreed mostly within a factor of two for both passive samplers and also with literature values for the reference PAHs. As PE is expected to exhibit similar sorption behaviour to long-chain alkanes, PE-water partitioning coefficients were compared to hexadecane-water partitioning coefficients estimated with the SPARC online calculator, COSMOtherm and a polyparameter linear free energy relationship based on the Abraham approach. The best correlation for all compounds tested was with COSMOtherm estimated hexadecane-water partitioning coefficients. - The partitioning of organochlorine pesticides between single phase polyethylene passive samplers and water is quantified.

Interactions of radionuclides with sediments and suspended particles

International Nuclear Information System (INIS)

Carpenter, R.

1997-01-01

This chapter reviews fundamental principles of the rates and extents of radionuclide uptake by sedimentary and suspended particles, defines sediment-water partition coefficients, and shows how they can explain first order features of radionuclide partitioning in aquatic environments. It then explains how sediment accumulation and mixing rates can be calculated from profiles of radionuclide activity measured in sediment cores. Such rates can be combined with profiles of other chemicals to establish the extent of temporal changes in chemical composition of the overlying water body. Since sediment processing and counting in the laboratory take much longer than the time required to collect the sample, suggestions are made to ensure that the sediment samples are not ruined or comprised during collection and handling in the field, and so are worth all the subsequent time and effort to analyze. (author)

Temperature dependence of the particle/gas partition coefficient: An application to predict indoor gas-phase concentrations of semi-volatile organic compounds

Energy Technology Data Exchange (ETDEWEB)

Wei, Wenjuan, E-mail: Wenjuan.Wei@cstb.fr [University of Paris-Est, Scientific and Technical Center for Building (CSTB), Health and Comfort Department, French Indoor Air Quality Observatory (OQAI), 84 Avenue Jean Jaurès, Champs sur Marne, 77447 Marne la Vallée Cedex 2 (France); Mandin, Corinne [University of Paris-Est, Scientific and Technical Center for Building (CSTB), Health and Comfort Department, French Indoor Air Quality Observatory (OQAI), 84 Avenue Jean Jaurès, Champs sur Marne, 77447 Marne la Vallée Cedex 2 (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); Blanchard, Olivier [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Mercier, Fabien [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Pelletier, Maud [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); Le Bot, Barbara [EHESP-School of Public Health, Sorbonne Paris Cité, Rennes (France); LERES-Environment and Health Research Laboratory (Irset and EHESP Technologic Platform), Rennes (France); INSERM-U1085, Irset-Research Institute for Environmental and Occupational Health, Rennes (France); and others

2016-09-01

The indoor gas-phase concentrations of semi-volatile organic compounds (SVOCs) can be predicted from their respective concentrations in airborne particles by applying the particle/gas partitioning equilibrium. The temperature used for partitioning is often set to 25 °C. However, indoor temperatures frequently differ from this reference value. This assumption may result in errors in the predicted equilibrium gas-phase SVOC concentrations. To improve the prediction model, the temperature dependence of the particle/gas partition coefficient must be addressed. In this paper, a theoretical relationship between the particle/gas partition coefficient and temperature was developed based on the SVOC absorptive mechanism. The SVOC particle/gas partition coefficients predicted by employing the derived theoretical relationship agree well with the experimental data retrieved from the literature (R > 0.93). The influence of temperature on the equilibrium gas-phase SVOC concentration was quantified by a dimensionless analysis of the derived relationship between the SVOC particle/gas partition coefficient and temperature. The predicted equilibrium gas-phase SVOC concentration decreased by between 31% and 53% when the temperature was lowered by 6 °C, while it increased by up to 750% when the indoor temperature increased from 15 °C to 30 °C. - Highlights: • A theoretical relationship between K{sub p} and temperature was developed. • The relationship was based on the SVOC absorptive mechanism. • The temperature impact was quantified by a dimensionless analysis.

Emerging investigator series: development and application of polymeric electrospun nanofiber mats as equilibrium-passive sampler media for organic compounds.

Science.gov (United States)

Qian, Jiajie; Jennings, Brandon; Cwiertny, David M; Martinez, Andres

2017-11-15

We fabricated a suite of polymeric electrospun nanofiber mats (ENMs) and investigated their performance as next-generation passive sampler media for environmental monitoring of organic compounds. Electrospinning of common polymers [e.g., polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polystyrene (PS), among others] yielded ENMs with reproducible control of nanofiber diameters (from 50 to 340 nm). The ENM performance was investigated initially with model hydrophilic (aniline and nitrobenzene) and hydrophobic (selected PCB congeners and dioxin) compounds, generally revealing fast chemical uptake into all of these ENMs, which was well described by a one compartment, first-order kinetic model. Typical times to reach 90% equilibrium (t 90% ) were ≤7 days under mixing conditions for all the ENMs and equilibrium timescales suggest that ENMs may be used in the field as an equilibrium-passive sampler, at least for our model compounds. Equilibrium partitioning coefficients (K ENM-W , L kg -1 ) averaged 2 and 4.7 log units for the hydrophilic and hydrophobic analytes, respectively. PAN, PMMA and PS were prioritized for additional studies because they exhibited not only the greatest capacity for simultaneous uptake of the entire model suite (log K ENM-W ∼1.5-6.2), but also fast uptake. For these optimized ENMs, the rates of uptake into PAN and PMMA were limited by aqueous phase diffusion to the nanofiber surface, and the rate-determining step for PS was analyte specific. Sorption isotherms also revealed that the environmental application of these optimized ENMs would occur within the linear uptake regime. We examined the ENM performance for the measurement of pore water concentrations from spiked soil and freshwater sediments. Soil and sediment studies not only yielded reproducible pore water concentrations and comparable values to other passive sampler materials, but also provided practical insights into ENM stability and fouling in such systems

Unconsolidated sediment distribution patterns in the KwaZulu-Natal ...

African Journals Online (AJOL)

Seasonal changes in sediment distribution patterns are small, being restricted to seaward fining on the inner shelf off the fluvial sources. Sediment distribution reflects a partitioning between sediment populations that are currentinfluenced and relict (palimpsest) populations associated with submerged shorelines.

Sediment pore water distribution coefficients of PCB congeners in enriched black carbon sediment

International Nuclear Information System (INIS)

Martinez, Andres; O'Sullivan, Colin; Reible, Danny; Hornbuckle, Keri C.

2013-01-01

More than 2300 sediment pore water distribution coefficients (K PCBids ) of 93 polychlorinated biphenyls (PCBs) were measured and modeled from sediments from Indiana Harbor and Ship Canal. K PCBids were calculated from previously reported bulk sediment values and newly analyzed pore water. PCBs in pore waters were measured using SPME PDMS-fiber and ∑PCB ranged from 41 to 1500 ng L −1 . The resulting K PCBids were ∼1 log unit lower in comparison to other reported values. A simple model for the K PCBid consisted of the product of the organic carbon fraction and the octanol–water partition coefficient and provided an excellent prediction for the measured values, with a mean square error of 0.09 ± 0.06. Although black carbon content is very high in these sediments and was expected to play an important role in the distribution of PCBs, no improvement was obtained when a two-carbon model was used. -- Highlights: •PCB sediment-pore water distribution coefficients were measured and modeled. •Distribution coefficients were lower in comparison to other reported values. •Organic carbon fraction times the K OW yielded the best prediction model. •The incorporation of black carbon into a model did not improve the results. -- The organic carbon fraction times the octanol–water partition coefficient yielded the best prediction model for the sediment pore water distribution coefficient of PCBs

Aquatic Nutrient Simulation Modules (NSMs) Developed for Hydrologic and Hydraulic Models

Science.gov (United States)

2016-02-01

deter- mined by a linear equilibrium partitioning isotherm. In the sediment bed, if the optional sediment diagenesis module is included (see Chapter... opal , sediment and seawater in the central equatorial Pacific. Geochimica et Cosmochimica 37:2257–2282. Jobson, H. E. 1977. Bed conduction

Partition coefficient n-octanol/water of propranolol and atenolol at different temperatures: Experimental and theoretical studies

International Nuclear Information System (INIS)

Mohsen-Nia, M.; Ebrahimabadi, A.H.; Niknahad, B.

2012-01-01

Highlights: ► n-Octanol/water partition coefficients of propranolol and atenolol were measured. ► The effect of temperature on the partition coefficient was studied. ► The equilibrium data were correlated using the NRTL and UNIQUAC activity models. ► The binary interaction parameters of the activity models were reported. ► It is concluded that propranolol is more hydrophobic than the atenolol at 298.15 K. - Abstract: The n-octanol/water partition coefficients of propranolol and atenolol were experimentally determined by ultraviolet (UV) spectroscopy at T = (298.15, 310.15 and 314.15) K. All measurements were made at the maximum wavelength corresponding to maximum absorption. The results showed that the n-octanol/water partition coefficients of propranolol and atenolol increase with the increase of temperature. The experimental data of this work were also used to examine the phase equilibrium correlating capability of some liquid-phase models. The equilibrium experimental data were correlated using the NRTL and UNIQUAC activity coefficient models and the binary interaction parameters were reported. The average root-mea n-square deviations (RMSD) between the experimental and calculated mass fractions of the (n-octanol + propranolol + water) and (n-octanol + atenolol + water) systems were determined. From the partition coefficients obtained, it is concluded that propranolol (log P ow = 3.12 ± 0.14) is more hydrophobic than the atenolol (log P ow = 0.16 ± 0.01) at T = 298.15 K.

Partitioning of Nanoparticles into Organic Phases and Model Cells

Energy Technology Data Exchange (ETDEWEB)

Posner, J.D.; Westerhoff, P.; Hou, W-C.

2011-08-25

dissolved substances" or "more like colloids" as the division between behaviors of macromolecules versus colloids remains ill-defined. Below we detail our work on two broadly defined objectives: (i) Partitioning of ENP into octanol, lipid bilayer, and water, and (ii) disruption of lipid bilayers by ENPs. We have found that the partitioning of NP reaches pseudo-equilibrium distributions between water and organic phases. The equilibrium partitioning most strongly depends on the particle surface charge, which leads us to the conclusion that electrostatic interactions are critical to understanding the fate of NP in the environment. We also show that the kinetic rate at which particle partition is a function of their size (small particles partition faster by number) as can be predicted from simple DLVO models. We have found that particle number density is the most effective dosimetry to present our results and provide quantitative comparison across experiments and experimental platforms. Cumulatively, our work shows that lipid bilayers are a more effective organic phase than octanol because of the definable surface area and ease of interpretation of the results. Our early comparison of NP partitioning between water and lipids suggest that this measurement can be predictive of bioaccumulation in aquatic organisms. We have shown that nanoparticle disrupt lipid bilayer membranes and detail how NP-bilayer interaction leads to the malfunction of lipid bilayers in regulating the fluxes of ionic charges and molecules. Our results show that the disruption of the lipid membranes is similar to that of toxin melittin, except single particles can disrupt a bilayer. We show that only a single particle is required to disrupt a 150 nm DOPC liposome. The equilibrium leakage of membranes is a function of the particle number density and particle surface charge, consistent with results from our partitioning experiments. Our disruption experiments with varying surface functionality show that

Resolving and modelling trace metal partitioning in a freshwater sediment

International Nuclear Information System (INIS)

Devallois, V.; Boyer, P.; Coulomb, B.; Boudenne, J. L.

2009-01-01

Elevated concentrations of trace metals in sediments pose toxicological risks to biota and may impair water quality. the sediment-water interface is the site where gradients in physical, chemical and biological properties are the greatest. Both chemical and microbiological transformation processes are responsible for cycling elements between water and sediments. (Author)

A Non-Equilibrium Sediment Transport Model for Dam Break Flow over Moveable Bed Based on Non-Uniform Rectangular Mesh

Directory of Open Access Journals (Sweden)

Gangfeng Wu

2018-05-01

Full Text Available The use of multiple-level non-uniform rectangular mesh in coupled flow and sediment transport modeling is preferred to achieve high accuracy in important region without increasing computational cost greatly. Here, a robust coupled hydrodynamic and non-equilibrium sediment transport model is developed on non-uniform rectangular mesh to simulate dam break flow over movable beds. The enhanced shallow water and sediment transport equations are adopted to consider the mass and momentum exchange between the flow phase and sediment phase. The flux at the interface is calculated by the positivity preserving central upwind scheme, which belongs to Godunov-type Riemann-problem-solver-free central schemes and is less expensive than other popular Riemann solvers while still capable of tracking wet/dry fronts accurately. The nonnegative water depth reconstruction method is used to achieve second-order accuracy in space. The model was first verified against two laboratory experiments of dam break flow over irregular fixed bed. Then the quantitative performance of the model was further investigated by comparing the computational results with measurement data of dam break flow over movable bed. The good agreements between the measurements and the numerical simulations are found for the flow depth, velocity and bed changes.

Availability of polycyclic aromatic hydrocarbons to earthworms (Eisenia andrei, Oligochaeta) in field-polluted soils and soil-sediment mixtures.

Science.gov (United States)

Jager, Tjalling; Baerselman, Rob; Dijkman, Ellen; de Groot, Arthur C; Hogendoorn, Elbert A; de Jong, Ad; Kruitbosch, Jantien A W; Peijnenburg, Willie J G M

2003-04-01

The bioavailability of polycyclic aromatic hydrocarbons (PAHs) for earthworms (Eisenia andrei) was experimentally determined in seven field-polluted soils and 15 soil-sediment mixtures. The pore-water concentration of most PAHs was higher than predicted. However, most of the compound was associated with dissolved organic carbon (DOC) and not directly available for uptake by earthworms. The apparent sorption could be reasonably predicted on the basis of interactions with DOC; however, the biota-soil accumulation factors (BSAFs) for earthworms were up to two orders of magnitude lower than predicted by equilibrium partitioning. The large variability between sites was not fully explained by differences in sorption. Experimental results indicate that the pool of freely dissolved PAHs in the pore water became partially depleted because of uptake by the earthworms and that bioaccumulation is thus also influenced by the kinetics of PAH desorption and mass transport. A pilot study with Lumbricus rubellus showed that steady-state body residues were well correlated to E. andrei. Current results show that depositing dredge spoil on land may lead to increased bioavailability of the lower-molecular-weight PAHs. However, risk assessment can conservatively rely on equilibrium partitioning, but accurate prediction requires quantification of the kinetics of bioavailability.

Evaluation of Near-Surface Gases in Marine Sediments to Assess Subsurface Petroleum Gas Generation and Entrapment

Directory of Open Access Journals (Sweden)

Michael A. Abrams

2017-05-01

Full Text Available Gases contained within near-surface marine sediments can be derived from multiple sources: shallow microbial activity, thermal cracking of organic matter and inorganic materials, or magmatic-mantle degassing. Each origin will display a distinctive hydrocarbon and non-hydrocarbon composition as well as compound-specific isotope signature and thus the interpretation of origin should be relatively straightforward. Unfortunately, this is not always the case due to in situ microbial alteration, non-equilibrium phase partitioning, mixing, and fractionation related to the gas extraction method. Sediment gases can reside in the interstitial spaces, bound to mineral or organic surfaces and/or entrapped in carbonate inclusions. The interstitial sediment gases are contained within the sediment pore space, either dissolved in the pore waters (solute or as free (vapour gas. The bound gases are believed to be attached to organic and/or mineral surfaces, entrapped in structured water or entrapped in authigenic carbonate inclusions. The purpose of this paper is to provide a review of the gas types found within shallow marine sediments and examine issues related to gas sampling and extraction. In addition, the paper will discuss how to recognise mixing, alteration and fractionation issues to best interpret the seabed geochemical results and determine gas origin to assess subsurface petroleum gas generation and entrapment.

Trace element distribution in different chemical fractions of False Bay sediments

International Nuclear Information System (INIS)

Rosental, R.

1984-05-01

Trace metals in the aquatic environment are generally concentrated on solid geochemical phases which eventually become incorporated into estuarine and marine sediments. The mechanism of trace metal concentration is believed to be adsorption on various geochemical phases, such as hydrous metal oxides, clays and organic matter. Metals in estuarine sediments can thus be expected to be partitioned between different phases, depending on the concentration of the phase and the strength of the adsorption bond. The bioavailability of sediment-bound metals to deposit-feeding organisms will depend on trace metal partitioning and the kinetics of biological metal uptake from each geochemical phase. The major objective of this study was to establish an analytical procedure involving sequential chemical extractions for the partitioning of particulate trace metals in sediment samples, collected from False Bay. Eight metals were examined, i.e. Cd, Cu, Cr, Fe, Mn, Ni, Pb and Zn. X-ray diffraction was also used in the study

Partition of ruthenium-106 between the fresh water environment and crayfish

International Nuclear Information System (INIS)

Berg, G.G.; Ginsberg, E.

1976-01-01

Crayfish of two species, Orconectes obscurus and Cambarus robustus, were identified in West Valley, New York, in streams contaminated with radioactive wastes. 106 Ru accounted for over 90% of the gamma radioactivity in specimens collected in 1972, and had higher concentrations in the crayfish than in fish from that site. Crayfish are suggested as indicator organisms for 106 Ru. In subsequent aquarium experiments, crayfish exposed to water labeled with inorganic complexes of 106 Ru concentrated the dissolved ruthenium an average of 9 x and accumulated 50% of the equilibrium body burden in approximately 10 hr, with the bulk of the isotope bound at the surface of the exoskeleton. If food was also exposed to the labeled water, uptake was faster and high concentrations were found in the digestive gland, which showed concentration factors in excess of 25 x. Releases were slower and bimodal, with approximately 10% of body burden remaining after 1 or 2 months in repeated changes of water. Data describe the partition of 106 Ru to colloidal aggregates and organically-bound sediments, and its availability for bioconcentration. (author)

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: environmental legacy after twelve years of the Gulf war oil spill.

Science.gov (United States)

Bejarano, Adriana C; Michel, Jacqueline

2010-05-01

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU(FCV,43)). Samples were assigned to risk categories according to ESBTU(FCV,43) values: no-risk (1 - 2 - 3 - 5). Sixty seven percent of samples had ESBTU(FCV,43) > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30 - oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War. Copyright 2009 Elsevier Ltd. All rights reserved.

Modelling of Sediment Transport in Beris Fishery Port

Directory of Open Access Journals (Sweden)

Samira Ardani

2015-06-01

Full Text Available In this paper, the large amount of sedimentation and the resultant shoreline advancements at the breakwaters of Beris Fishery Port are studied. A series of numerical modeling of waves, sediment transport, and shoreline changes were conducted to predict the complicated equilibrium shoreline. The outputs show that the nearshore directions of wave components are not perpendicular to the coast which reveals the existence of longshore currents and consequently sediment transport along the bay. Considering the dynamic equilibrium condition of the bay, the effect of the existing sediment resources in the studied area is also investigated. The study also shows that in spite of the change of the diffraction point of Beris Bay after the construction of the fishery port, the bay is approaching its dynamic equilibrium condition, and the shoreline advancement behind secondary breakwater will stop before blocking the entrance of the port. The probable solutions to overcome the sedimentation problem at the main breakwater are also discussed.

Functional and physical molecular size of the chicken hepatic lectin determined by radiation inactivation and sedimentation equilibrium analysis

International Nuclear Information System (INIS)

Steer, C.J.; Osborne, J.C. Jr.; Kempner, E.S.

1990-01-01

Radiation inactivation and sedimentation equilibrium analysis were used to determine the functional and physical size of the chicken hepatic membrane receptor that binds N-acetylglucosamine-terminated glycoproteins. Purified plasma membranes from chicken liver were irradiated with high energy electrons and assayed for 125I-agalactoorosomucoid binding. Increasing the dose of ionizing radiation resulted in a monoexponential decay in binding activity due to a progressive loss of binding sites. The molecular mass of the chicken lectin, determined in situ by target analysis, was 69,000 +/- 9,000 Da. When the same irradiated membranes were solubilized in Brij 58 and assayed, the binding protein exhibited a target size of 62,000 +/- 4,000 Da; in Triton X-100, the functional size of the receptor was 85,000 +/- 10,000 Da. Sedimentation equilibrium measurements of the purified binding protein yielded a lower limit molecular weight of 79,000 +/- 7,000. However, the solubilized lectin was detected as a heterogeneous population of oligomers with molecular weights as high as 450,000. Addition of calcium or calcium plus N-acetylglucosamine decreased the higher molecular weight species, but the lower limit molecular weights remained invariant. Similar results were determined when the chicken lectin was solubilized in Brij 58, C12E9, or 3-[(3-cholamidopropyl)dimethylammonio]-1-propane-sulfonic acid (CHAPS). Results from the present study suggest that in the plasma membrane, the functional species of the chicken hepatic lectin exists as a trimer. However, in detergent solution, the purified receptor forms a heterogeneous population of irreversible oligomers that exhibit binding activity proportional to size

Bioavailability of Antibiotics at Soil-Water Interfaces: A Comparison of Measured Activities and Equilibrium Partitioning Estimates.

Science.gov (United States)

Menz, Jakob; Müller, Julia; Olsson, Oliver; Kümmerer, Klaus

2018-06-05

There are growing concerns that antibiotic pollution impacts environmental microbiota and facilitates the propagation of antibiotic resistance. However, the prediction or analytical determination of bioavailable concentrations of antibiotics in soil is still subject to great uncertainty. Biological assays are increasingly recognized as valuable complementary tools that allow a more direct determination of the residual antibiotic activity. This study assessed the bioavailability of structurally diverse antibiotics at a soil-water interface applying activity-based analyses in conjunction with equilibrium partitioning (EqP) modeling. The activity against Gram-positive and Gram-negative bacteria of nine antibiotics from different classes was determined in the presence and absence of standard soil (LUFA St. 2.2). The addition of soil affected the activity of different antibiotics to highly varying degrees. Moreover, a highly significant correlation ( p < 0.0001) between the experimentally observed and the EqP-derived log EC 50 (half-maximal effective concentration) values was observed. The innovative experimental design of this study provided new insights on the bioavailability of antibiotics at soil-water interfaces. EqP appears to be applicable to a broad range of antibiotics for the purpose of screening-level risk assessment. However, EqP estimates cannot replace soil-specific ecotoxicity testing in higher-tier assessments, since their accuracy is still compromised by a number of factors.

Prospective Environmental Risk Assessment for Sediment-Bound Organic Chemicals: A Proposal for Tiered Effect Assessment.

Science.gov (United States)

Diepens, Noël J; Koelmans, Albert A; Baveco, Hans; van den Brink, Paul J; van den Heuvel-Greve, Martine J; Brock, Theo C M

A broadly accepted framework for prospective environmental risk assessment (ERA) of sediment-bound organic chemicals is currently lacking. Such a framework requires clear protection goals, evidence-based concepts that link exposure to effects and a transparent tiered-effect assessment. In this paper, we provide a tiered prospective sediment ERA procedure for organic chemicals in sediment, with a focus on the applicable European regulations and the underlying data requirements. Using the ecosystem services concept, we derived specific protection goals for ecosystem service providing units: microorganisms, benthic algae, sediment-rooted macrophytes, benthic invertebrates and benthic vertebrates. Triggers for sediment toxicity testing are discussed.We recommend a tiered approach (Tier 0 through Tier 3). Tier-0 is a cost-effective screening based on chronic water-exposure toxicity data for pelagic species and equilibrium partitioning. Tier-1 is based on spiked sediment laboratory toxicity tests with standard benthic test species and standardised test methods. If comparable chronic toxicity data for both standard and additional benthic test species are available, the Species Sensitivity Distribution (SSD) approach is a more viable Tier-2 option than the geometric mean approach. This paper includes criteria for accepting results of sediment-spiked single species toxicity tests in prospective ERA, and for the application of the SSD approach. We propose micro/mesocosm experiments with spiked sediment, to study colonisation success by benthic organisms, as a Tier-3 option. Ecological effect models can be used to supplement the experimental tiers. A strategy for unifying information from various tiers by experimental work and exposure-and effect modelling is provided.

Anharmonic effects in the quantum cluster equilibrium method

Science.gov (United States)

von Domaros, Michael; Perlt, Eva

2017-03-01

The well-established quantum cluster equilibrium (QCE) model provides a statistical thermodynamic framework to apply high-level ab initio calculations of finite cluster structures to macroscopic liquid phases using the partition function. So far, the harmonic approximation has been applied throughout the calculations. In this article, we apply an important correction in the evaluation of the one-particle partition function and account for anharmonicity. Therefore, we implemented an analytical approximation to the Morse partition function and the derivatives of its logarithm with respect to temperature, which are required for the evaluation of thermodynamic quantities. This anharmonic QCE approach has been applied to liquid hydrogen chloride and cluster distributions, and the molar volume, the volumetric thermal expansion coefficient, and the isobaric heat capacity have been calculated. An improved description for all properties is observed if anharmonic effects are considered.

Biological and chemical characterization of metal bioavailability in sediments from Lake Roosevelt, Columbia River, Washington, USA

Science.gov (United States)

Besser, J.M.; Brumbaugh, W.G.; Ivey, C.D.; Ingersoll, C.G.; Moran, P.W.

2008-01-01

We studied the bioavailability and toxicity of copper, zinc, arsenic, cadmium, and lead in sediments from Lake Roosevelt (LR), a reservoir on the Columbia River in Washington, USA that receives inputs of metals from an upstream smelter facility. We characterized chronic sediment toxicity, metal bioaccumulation, and metal concentrations in sediment and pore water from eight study sites: one site upstream in the Columbia River, six sites in the reservoir, and a reference site in an uncontaminated tributary. Total recoverable metal concentrations in LR sediments generally decreased from upstream to downstream in the study area, but sediments from two sites in the reservoir had metal concentrations much lower than adjacent reservoir sites and similar to the reference site, apparently due to erosion of uncontaminated bank soils. Concentrations of acid-volatile sulfide in LR sediments were too low to provide strong controls on metal bioavailability, and selective sediment extractions indicated that metals in most LR sediments were primarily associated with iron and manganese oxides. Oligochaetes (Lumbriculus variegatus) accumulated greatest concentrations of copper from the river sediment, and greatest concentrations of arsenic, cadmium, and lead from reservoir sediments. Chronic toxic effects on amphipods (Hyalella azteca; reduced survival) and midge larvae (Chironomus dilutus; reduced growth) in whole-sediment exposures were generally consistent with predictions of metal toxicity based on empirical and equilibrium partitioning-based sediment quality guidelines. Elevated metal concentrations in pore waters of some LR sediments suggested that metals released from iron and manganese oxides under anoxic conditions contributed to metal bioaccumulation and toxicity. Results of both chemical and biological assays indicate that metals in sediments from both riverine and reservoir habitats of Lake Roosevelt are available to benthic invertebrates. These findings will be used as

Evaluation of in situ capping with clean soils to control phosphate release from sediments

Energy Technology Data Exchange (ETDEWEB)

Xu, Di [State Key Laboratory of Lake Science and Environment, Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing 210008 (China); Ding, Shiming, E-mail: smding@niglas.ac.cn [State Key Laboratory of Lake Science and Environment, Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing 210008 (China); Sun, Qin [College of Environmental Science and Engineering, Hohai University, Nanjing (China); Zhong, Jicheng [State Key Laboratory of Lake Science and Environment, Nanjing Institute of Geography and Limnology, Chinese Academy of Sciences, Nanjing 210008 (China); Wu, Wei; Jia, Fei [College of Environmental Science and Engineering, Hohai University, Nanjing (China)

2012-11-01

Evaluation of in situ capping with clean soils to control phosphate release from the sediments of a eutrophic bay in Lake Taihu was performed after 18 months of capping. The concentrations of dissolved reactive phosphate (DRP) in pore waters and DRP resupply from native sediments and capped sediments were determined using high-resolution dialysis (HR-Peeper) and a Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique. The adsorption isotherm of these sediments was further investigated using a modified Langmuir model. The results showed low concentrations of DRP in pore waters with a low resupply from the sediments for sustaining pore water DRP concentration after capping. The calculated flux to the overlying water following the capping treatment was approximately half of that for the native sediments, implying that the capping reduced the release of phosphate from the sediments. The low resupply of the sediments after capping was further demonstrated by larger partitioning coefficient (K{sub p}) values and greater adsorption capacity (Q{sub max}) values, while zero equilibrium concentrations (EPC{sub 0}s) were similar to those in native sediments. The larger K{sub p} and Q{sub max} were attributed to higher active Fe and Al introduced by the capping, indicating that the binding of phosphate onto the active Fe and Al played a critical role in reducing the internal loading of phosphorous. Highlights: Black-Right-Pointing-Pointer Evaluation of capping with soils was performed through high-resolution sampling. Black-Right-Pointing-Pointer Capping decreased the concentrations of DRP in pore waters and its release to waters. Black-Right-Pointing-Pointer Capping decreased the resupply of pore water DRP from the sediments. Black-Right-Pointing-Pointer Capped sediments had stronger abilities to adsorb and retain P. Black-Right-Pointing-Pointer Active Fe and Al introduced by capping played a critical role.

Evaluation of in situ capping with clean soils to control phosphate release from sediments

International Nuclear Information System (INIS)

Xu, Di; Ding, Shiming; Sun, Qin; Zhong, Jicheng; Wu, Wei; Jia, Fei

2012-01-01

Evaluation of in situ capping with clean soils to control phosphate release from the sediments of a eutrophic bay in Lake Taihu was performed after 18 months of capping. The concentrations of dissolved reactive phosphate (DRP) in pore waters and DRP resupply from native sediments and capped sediments were determined using high-resolution dialysis (HR-Peeper) and a Zr-oxide diffusive gradients in thin films (Zr-oxide DGT) technique. The adsorption isotherm of these sediments was further investigated using a modified Langmuir model. The results showed low concentrations of DRP in pore waters with a low resupply from the sediments for sustaining pore water DRP concentration after capping. The calculated flux to the overlying water following the capping treatment was approximately half of that for the native sediments, implying that the capping reduced the release of phosphate from the sediments. The low resupply of the sediments after capping was further demonstrated by larger partitioning coefficient (K p ) values and greater adsorption capacity (Q max ) values, while zero equilibrium concentrations (EPC 0 s) were similar to those in native sediments. The larger K p and Q max were attributed to higher active Fe and Al introduced by the capping, indicating that the binding of phosphate onto the active Fe and Al played a critical role in reducing the internal loading of phosphorous. Highlights: ► Evaluation of capping with soils was performed through high-resolution sampling. ► Capping decreased the concentrations of DRP in pore waters and its release to waters. ► Capping decreased the resupply of pore water DRP from the sediments. ► Capped sediments had stronger abilities to adsorb and retain P. ► Active Fe and Al introduced by capping played a critical role.

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

Energy Technology Data Exchange (ETDEWEB)

Bejarano, Adriana C., E-mail: ABejarano@researchplanning.co [Research Planning Inc., 1121 Park St., Columbia, SC 29201 (United States); Michel, Jacqueline [Research Planning Inc., 1121 Park St., Columbia, SC 29201 (United States)

2010-05-15

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU{sub FCV,43}). Samples were assigned to risk categories according to ESBTU{sub FCV,43} values: no-risk (<=1), low (>1-<=2), low-medium (>2-<=3), medium (>3-<=5) and high-risk (>5). Sixty seven percent of samples had ESBTU{sub FCV,43} > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War. - Risk Assessment of PAHs in shoreline sediments 12 years after the Gulf War oil spill.

Large-scale risk assessment of polycyclic aromatic hydrocarbons in shoreline sediments from Saudi Arabia: Environmental legacy after twelve years of the Gulf war oil spill

International Nuclear Information System (INIS)

Bejarano, Adriana C.; Michel, Jacqueline

2010-01-01

A large-scale assessment of polycyclic aromatic hydrocarbons (PAHs) from the 1991 Gulf War oil spill was performed for 2002-2003 sediment samples (n = 1679) collected from habitats along the shoreline of Saudi Arabia. Benthic sediment toxicity was characterized using the Equilibrium Partitioning Sediment Benchmark Toxic Unit approach for 43 PAHs (ESBTU FCV,43 ). Samples were assigned to risk categories according to ESBTU FCV,43 values: no-risk (≤1), low (>1-≤2), low-medium (>2-≤3), medium (>3-≤5) and high-risk (>5). Sixty seven percent of samples had ESBTU FCV,43 > 1 indicating potential adverse ecological effects. Sediments from the 0-30 cm layer from tidal flats, and the >30-<60 cm layer from heavily oiled halophytes and mangroves had high frequency of high-risk samples. No-risk samples were characterized by chrysene enrichment and depletion of lighter molecular weight PAHs, while high-risk samples showed little oil weathering and PAH patterns similar to 1993 samples. North of Safaniya sediments were not likely to pose adverse ecological effects contrary to sediments south of Tanaqib. Landscape and geomorphology has played a role on the distribution and persistence in sediments of oil from the Gulf War. - Risk Assessment of PAHs in shoreline sediments 12 years after the Gulf War oil spill.

Quantum Statistical Mechanics, L-Series and Anabelian Geometry I: Partition Functions

NARCIS (Netherlands)

Marcolli, Matilde; Cornelissen, Gunther

2014-01-01

The zeta function of a number field can be interpreted as the partition function of an associated quantum statistical mechanical (QSM) system, built from abelian class field theory. We introduce a general notion of isomorphism of QSM-systems and prove that it preserves (extremal) KMS equilibrium

Asymptotic expansion of a partition function related to the sinh-model

CERN Document Server

Borot, Gaëtan; Kozlowski, Karol K

2016-01-01

This book elaborates on the asymptotic behaviour, when N is large, of certain N-dimensional integrals which typically occur in random matrices, or in 1+1 dimensional quantum integrable models solvable by the quantum separation of variables. The introduction presents the underpinning motivations for this problem, a historical overview, and a summary of the strategy, which is applicable in greater generality. The core aims at proving an expansion up to o(1) for the logarithm of the partition function of the sinh-model. This is achieved by a combination of potential theory and large deviation theory so as to grasp the leading asymptotics described by an equilibrium measure, the Riemann-Hilbert approach to truncated Wiener-Hopf in order to analyse the equilibrium measure, the Schwinger-Dyson equations and the boostrap method to finally obtain an expansion of correlation functions and the one of the partition function. This book is addressed to researchers working in random matrices, statistical physics or integra...

Screening-level ecological and human health risk assessment of polycyclic aromatic hydrocarbons in stormwater detention pond sediments of Coastal South Carolina, USA

Energy Technology Data Exchange (ETDEWEB)

Weinstein, John E., E-mail: john.weinstein@citadel.edu [Department of Biology, The Citadel, Charleston, SC (United States); Crawford, Kevin D. [Department of Chemistry, University of Wisconsin-Oshkosh, Oshkosh, WI (United States); Garner, Thomas R. [Institute of Environmental Toxicology, Clemson University, Pendleton, SC (United States); Flemming, Alan J. [South Carolina Department of Health and Environmental Control, Charleston, SC (United States)

2010-06-15

Screening-level ecological and human health assessments were performed for polycyclic aromatic hydrocarbon (PAH) contamination in the sediments of 19 stormwater detention ponds located in coastal South Carolina. For ecological screening benchmarks, we used threshold and probable effect concentrations (TEC and PEC) derived from consensus-based sediment quality guidelines for individual PAH analytes and equilibrium partitioning sediment benchmarks-toxic units ({Sigma}ESB-TU) derived for PAH mixtures. For human health benchmarks, we used preliminary remediation goals (PRGs). Sediments of five stormwater ponds (four commercial ponds and one residential pond with a large drainage area) exceeded PEC values for several PAH analytes and the {Sigma}ESB-TU safe value of 1 for PAH mixtures. These same five stormwater ponds also exceeded the PRG values for five carcinogenic PAH analytes. These results suggest that the PAH levels in sediments from certain commercial and residential ponds have the potential to pose moderate to high risks for adverse, chronic effects to benthic organisms in situ and an increased risk of cancer to humans ex situ following excavation and on-site disposal. We recommend that sediment from these stormwater ponds be tested prior to excavation to determine the appropriate method of disposal. We also recommend that regulatory agencies enforce guidelines for periodic sediment removal as this should reduce both in situ and ex situ risks resulting from sediment PAH exposure.

Screening-level ecological and human health risk assessment of polycyclic aromatic hydrocarbons in stormwater detention pond sediments of Coastal South Carolina, USA

International Nuclear Information System (INIS)

Weinstein, John E.; Crawford, Kevin D.; Garner, Thomas R.; Flemming, Alan J.

2010-01-01

Screening-level ecological and human health assessments were performed for polycyclic aromatic hydrocarbon (PAH) contamination in the sediments of 19 stormwater detention ponds located in coastal South Carolina. For ecological screening benchmarks, we used threshold and probable effect concentrations (TEC and PEC) derived from consensus-based sediment quality guidelines for individual PAH analytes and equilibrium partitioning sediment benchmarks-toxic units (ΣESB-TU) derived for PAH mixtures. For human health benchmarks, we used preliminary remediation goals (PRGs). Sediments of five stormwater ponds (four commercial ponds and one residential pond with a large drainage area) exceeded PEC values for several PAH analytes and the ΣESB-TU safe value of 1 for PAH mixtures. These same five stormwater ponds also exceeded the PRG values for five carcinogenic PAH analytes. These results suggest that the PAH levels in sediments from certain commercial and residential ponds have the potential to pose moderate to high risks for adverse, chronic effects to benthic organisms in situ and an increased risk of cancer to humans ex situ following excavation and on-site disposal. We recommend that sediment from these stormwater ponds be tested prior to excavation to determine the appropriate method of disposal. We also recommend that regulatory agencies enforce guidelines for periodic sediment removal as this should reduce both in situ and ex situ risks resulting from sediment PAH exposure.

Development and application of freshwater sediment-toxicity benchmarks for currently used pesticides

Science.gov (United States)

Nowell, Lisa H.; Norman, Julia E.; Ingersoll, Christopher G.; Moran, Patrick W.

2016-01-01

Sediment-toxicity benchmarks are needed to interpret the biological significance of currently used pesticides detected in whole sediments. Two types of freshwater sediment benchmarks for pesticides were developed using spiked-sediment bioassay (SSB) data from the literature. These benchmarks can be used to interpret sediment-toxicity data or to assess the potential toxicity of pesticides in whole sediment. The Likely Effect Benchmark (LEB) defines a pesticide concentration in whole sediment above which there is a high probability of adverse effects on benthic invertebrates, and the Threshold Effect Benchmark (TEB) defines a concentration below which adverse effects are unlikely. For compounds without available SSBs, benchmarks were estimated using equilibrium partitioning (EqP). When a sediment sample contains a pesticide mixture, benchmark quotients can be summed for all detected pesticides to produce an indicator of potential toxicity for that mixture. Benchmarks were developed for 48 pesticide compounds using SSB data and 81 compounds using the EqP approach. In an example application, data for pesticides measured in sediment from 197 streams across the United States were evaluated using these benchmarks, and compared to measured toxicity from whole-sediment toxicity tests conducted with the amphipod Hyalella azteca (28-d exposures) and the midge Chironomus dilutus (10-d exposures). Amphipod survival, weight, and biomass were significantly and inversely related to summed benchmark quotients, whereas midge survival, weight, and biomass showed no relationship to benchmarks. Samples with LEB exceedances were rare (n = 3), but all were toxic to amphipods (i.e., significantly different from control). Significant toxicity to amphipods was observed for 72% of samples exceeding one or more TEBs, compared to 18% of samples below all TEBs. Factors affecting toxicity below TEBs may include the presence of contaminants other than pesticides, physical

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations

Energy Technology Data Exchange (ETDEWEB)

Liu, Jing-yong, E-mail: www053991@126.com [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China); Li, Xiao-ming [Guangdong Testing Institute of Product Quality Supervision, Guangzhou 510330 (China); Chen, Tao [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Luo, Guang-qian [State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan 430074 (China); Xie, Wu-ming; Wang, Yu-jie; Zhuo, Zhong-xu; Fu, Jie-wen [School of Environmental Science and Engineering, Guangdong University of Technology, Guangzhou 510006 (China)

2015-04-15

Highlights: • A thermodynamic equilibrium calculation was carried out. • Effects of three types of sulfurs on Pb distribution were investigated. • The mechanism for three types of sulfurs acting on Pb partitioning were proposed. • Lead partitioning and species in bottom ash and fly ash were identified. - Abstract: Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na{sub 2}S and Na{sub 2}SO{sub 4}) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na{sub 2}SO{sub 4} and Na{sub 2}S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO{sub 4}(s) at low temperatures (<1000 K). The equilibrium calculation prediction also suggested that SiO{sub 2}, CaO, TiO{sub 2}, and Al{sub 2}O{sub 3} containing materials function as condensed phase solids in the temperature range of 800–1100 K as sorbents to stabilize Pb. However, in the presence of sulfur or chlorine or the co-existence of sulfur and chlorine, these sorbents were inactive. The effect of sulfur on Pb partitioning in the sludge incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the

Spatio-temporal evaluation of emerging contaminants and their partitioning along a Brazilian watershed.

Science.gov (United States)

de Sousa, Diana Nara Ribeiro; Mozeto, Antonio Aparecido; Carneiro, Renato Lajarim; Fadini, Pedro Sergio

2018-02-01

The occurrence, partitioning, and spatio-temporal distribution of seven pharmaceuticals for human use, three steroid hormones and one personal care product were determined in surface water, suspended particulate matter (SPM), and sediment of Piraí Creek and Jundiaí River (Jundiaí River Basin, São Paulo, Brazil). The maximum average detected concentrations of the compounds in the Piraí River samples were contaminants most frequently detected in sediment and SPM samples. Triclosan had the highest average proportion of SPM as opposed to in the aqueous phase (> 75%). Contaminants with acid functional groups showed, in general, a lower tendency to bind to particulate matter and sediments. In addition, hydrophobicity had an important effect on their environmental partitioning. The spatial distribution of contaminants along the Jundiaí River was mainly affected by the higher concentration of contaminants in water samples collected downstream from a sewage treatment plant (STP). The results obtained here clearly showed the importance of the analysis of some contaminants in the whole water, meaning both dissolved and particulate compartments in the water, and that the partitioning is ruled by a set of parameters associated to the physicochemical characteristics of contaminants and the matrix properties of the studied, which need be considered in an integrated approach to understand the fate of emerging chemical contaminants in aquatic environments.

Wigner expansions for partition functions of nonrelativistic and relativistic oscillator systems

Science.gov (United States)

Zylka, Christian; Vojta, Guenter

1993-01-01

The equilibrium quantum statistics of various anharmonic oscillator systems including relativistic systems is considered within the Wigner phase space formalism. For this purpose the Wigner series expansion for the partition function is generalized to include relativistic corrections. The new series for partition functions and all thermodynamic potentials yield quantum corrections in terms of powers of h(sup 2) and relativistic corrections given by Kelvin functions (modified Hankel functions) K(sub nu)(mc(sup 2)/kT). As applications, the symmetric Toda oscillator, isotonic and singular anharmonic oscillators, and hindered rotators, i.e. oscillators with cosine potential, are addressed.

Modelling Chemical Equilibrium Partitioning with the GEMS-PSI Code

Energy Technology Data Exchange (ETDEWEB)

Kulik, D.; Berner, U.; Curti, E

2004-03-01

Sorption, co-precipitation and re-crystallisation are important retention processes for dissolved contaminants (radionuclides) migrating through the sub-surface. The retention of elements is usually measured by empirical partition coefficients (Kd), which vary in response to many factors: temperature, solid/liquid ratio, total contaminant loading, water composition, host-mineral composition, etc. The Kd values can be predicted for in-situ conditions from thermodynamic modelling of solid solution, aqueous solution or sorption equilibria, provided that stoichiometry, thermodynamic stability and mixing properties of the pure components are known (Example 1). Unknown thermodynamic properties can be retrieved from experimental Kd values using inverse modelling techniques (Example 2). An efficient, advanced tool for performing both tasks is the Gibbs Energy Minimization (GEM) approach, implemented in the user-friendly GEM-Selector (GEMS) program package, which includes the Nagra-PSI chemical thermodynamic database. The package is being further developed at PSI and used extensively in studies relating to nuclear waste disposal. (author)

Modelling Chemical Equilibrium Partitioning with the GEMS-PSI Code

International Nuclear Information System (INIS)

Kulik, D.; Berner, U.; Curti, E.

2004-01-01

Sorption, co-precipitation and re-crystallisation are important retention processes for dissolved contaminants (radionuclides) migrating through the sub-surface. The retention of elements is usually measured by empirical partition coefficients (Kd), which vary in response to many factors: temperature, solid/liquid ratio, total contaminant loading, water composition, host-mineral composition, etc. The Kd values can be predicted for in-situ conditions from thermodynamic modelling of solid solution, aqueous solution or sorption equilibria, provided that stoichiometry, thermodynamic stability and mixing properties of the pure components are known (Example 1). Unknown thermodynamic properties can be retrieved from experimental Kd values using inverse modelling techniques (Example 2). An efficient, advanced tool for performing both tasks is the Gibbs Energy Minimization (GEM) approach, implemented in the user-friendly GEM-Selector (GEMS) program package, which includes the Nagra-PSI chemical thermodynamic database. The package is being further developed at PSI and used extensively in studies relating to nuclear waste disposal. (author)

Solid/liquid partition coefficients (Kd) and plant/soil concentration ratios (CR) for selected soils, tills and sediments at Forsmark

International Nuclear Information System (INIS)

Sheppard, Steve; Sohlenius, Gustav; Omberg, Lars-Gunnar; Borgiel, Mikael; Grolander, Sara; Norden, Sara

2011-11-01

Solid/liquid partition coefficients (K d ) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. To indicate the uptake of radionuclides in biota concentration ratios (CR) between soil and biota are used. This report summarized K d data for regolith and marine sediments based on concentrations of 69 indigenous stable elements measured from samples collected at the Forsmark site and CR data concerning cereals growing on these soils. The samples included 50 regolith samples from agricultural land and wetlands, 8 samples of till collected at different depths, and two marine sediment samples. In addition, cereal grains, stems and roots were collected from 4 sites for calculation of CRs. The regolith samples represented the major 5 deposits, which can be used as arable land, at the site (clayey till, glacial clay, clay gyttja and peat (cultivated and undisturbed)). K d values were generally lower for peat compared to clay soils. There were also clear differences in K d resulting from differences in soil chemistry within each regolith type. Soil pH was the most important factor, and K d values for many elements were lower in acidic clay soils compared to basic clay soils. Although there were only a few samples of sandy till and marine sediment, the K d values were generally consistent with the corresponding regolith K d values. Of the different cereal parts the grain always had the lowest CR. In most cases, the root CR was significantly higher than the grain CR, whereas only for a few elements were the grain and stem CR values different

Sediment quality criteria: A review with recommendations for developing criteria for the Hanford Site

Energy Technology Data Exchange (ETDEWEB)

Driver, C.J.

1994-05-01

Criteria for determining the quality of liver sediment are necessary to ensure that concentrations of contaminants in aquatic systems are within acceptable limits for the protection of aquatic and human life. Such criteria should facilitate decision-making about remediation, handling, and disposal of contaminants. Several approaches to the development of sediment quality criteria (SQC) have been described and include both descriptive and numerical methods. However, no single method measures all impacts at all times to all organisms (U.S. EPA 1992b). The U.S. EPA`s interest is primarily in establishing chemically based, numerical SQC that are applicable nation-wide (Shea 1988). Of the approaches proposed for SQC development, only three are being considered for numerical SQC on a national level. These approaches include an Equilibrium Partitioning Approach, a site-specific method using bioassays (the Apparent Effects Threshold Approach), and an approach similar to EPA`s water quality criteria (Pavlou and Weston 1984). Although national (or even regional) criteria address a number of political, litigative, and engineering needs, some researchers feel that protection of benthic communities require site-specific, biologically based criteria (Baudo et al. 1990). This is particularly true for areas where complex mixtures of contaminants are present in sediments. Other scientifically valid and accepted procedures for freshwater SQC include a background concentration approach, methods using field or spiked bioassays, a screening level concentration approach, the Apparent Effects Threshold Approach, the Sediment Quality Triad, the International Joint Commission Sediment Assessment Strategy, and the National Status and Trends Program Approach. The various sediment assessment approaches are evaluated for application to the Hanford Reach and recommendations for Hanford Site sediment quality criteria are discussed.

Evolution of organic aerosol mass spectra upon heating: implications for OA phase and partitioning behavior

Energy Technology Data Exchange (ETDEWEB)

UC Davis; Cappa, Christopher D.; Wilson, Kevin R.

2010-10-28

Vacuum Ultraviolet (VUV) photoionization mass spectrometry has been used to measure the evolution of chemical composition for two distinct organic aerosol types as they are passed through a thermodenuder at different temperatures. The two organic aerosol types considered are primary lubricating oil (LO) aerosol and secondary aerosol from the alpha-pinene + O3 reaction (alphaP). The evolution of the VUV mass spectra for the two aerosol types with temperature are observed to differ dramatically. For LO particles, the spectra exhibit distinct changes with temperature in which the lower m/z peaks, corresponding to compounds with higher vapor pressures, disappear more rapidly than the high m/z peaks. In contrast, the alphaP aerosol spectrum is essentially unchanged by temperature even though the particles experience significant mass loss due to evaporation. The variations in the LO spectra are found to be quantitatively in agreement with expectations from absorptive partitioning theory whereas the alphaP spectra suggest that the evaporation of alphaP derived aerosol appears to not be governed by partitioning theory. We postulate that this difference arises from the alphaP particles existing as in a glassy state instead of having the expected liquid-like behavior. To reconcile these observations with decades of aerosol growth measurements, which indicate that OA formation is described by equilibrium partitioning, we present a conceptual model wherein the secondary OA is formed and then rapidly converted from an absorbing form to a non-absorbing form. The results suggest that although OA growth may be describable by equilibrium partitioning theory, the properties of organic aerosol once formed may differ significantly from the properties determined in the equilibrium framework.

Derivation of the chemical-equilibrium rate coefficient using scattering theory

Science.gov (United States)

Mickens, R. E.

1977-01-01

Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

A New Measure for Transported Suspended Sediment

Science.gov (United States)

Yang, Q.

2017-12-01

Non-uniform suspended sediment plays an important role in many geographical and biological processes. Despite extensive study, understanding to it seems to stagnate when times to consider non-uniformity and non-equilibrium scenarios comes. Due to unsatisfactory reproducibility, large-scaled flume seems to be incompetent to conduct more fundamental research in this area. To push the realm a step further, experiment to find how suspended sediment exchanges is conducted in a new validated equipment, in which turbulence is motivated by oscillating grids. Analysis shows that 1) suspended sediment exchange is constrained by ωS invariance, 2) ωS of the suspended sediment that certain flow regime could support is unique regardless of the sediment gradation and 3) the more turbulent the flow, the higher ωS of the suspension the flow could achieve. A new measure for suspended sediment ωS, the work required to sustain sediment in suspension transport mode if multiplied by gravitational acceleration, is thus proposed to better describe the dynamics of transported suspended sediment. Except for the further understanding towards suspended sediment transportation mechanics, with this energy measure, a strategy to distribute total transport capacity to different fractions could be derived and rational calculation of non-uniform sediment transport capacity under non-equilibrium conditions be possible.

Predicting solute partitioning in lipid bilayers: Free energies and partition coefficients from molecular dynamics simulations and COSMOmic

Science.gov (United States)

Jakobtorweihen, S.; Zuniga, A. Chaides; Ingram, T.; Gerlach, T.; Keil, F. J.; Smirnova, I.

2014-07-01

Quantitative predictions of biomembrane/water partition coefficients are important, as they are a key property in pharmaceutical applications and toxicological studies. Molecular dynamics (MD) simulations are used to calculate free energy profiles for different solutes in lipid bilayers. How to calculate partition coefficients from these profiles is discussed in detail and different definitions of partition coefficients are compared. Importantly, it is shown that the calculated coefficients are in quantitative agreement with experimental results. Furthermore, we compare free energy profiles from MD simulations to profiles obtained by the recent method COSMOmic, which is an extension of the conductor-like screening model for realistic solvation to micelles and biomembranes. The free energy profiles from these molecular methods are in good agreement. Additionally, solute orientations calculated with MD and COSMOmic are compared and again a good agreement is found. Four different solutes are investigated in detail: 4-ethylphenol, propanol, 5-phenylvaleric acid, and dibenz[a,h]anthracene, whereby the latter belongs to the class of polycyclic aromatic hydrocarbons. The convergence of the free energy profiles from biased MD simulations is discussed and the results are shown to be comparable to equilibrium MD simulations. For 5-phenylvaleric acid the influence of the carboxyl group dihedral angle on free energy profiles is analyzed with MD simulations.

Predicting solute partitioning in lipid bilayers: Free energies and partition coefficients from molecular dynamics simulations and COSMOmic

International Nuclear Information System (INIS)

Jakobtorweihen, S.; Ingram, T.; Gerlach, T.; Smirnova, I.; Zuniga, A. Chaides; Keil, F. J.

2014-01-01

Quantitative predictions of biomembrane/water partition coefficients are important, as they are a key property in pharmaceutical applications and toxicological studies. Molecular dynamics (MD) simulations are used to calculate free energy profiles for different solutes in lipid bilayers. How to calculate partition coefficients from these profiles is discussed in detail and different definitions of partition coefficients are compared. Importantly, it is shown that the calculated coefficients are in quantitative agreement with experimental results. Furthermore, we compare free energy profiles from MD simulations to profiles obtained by the recent method COSMOmic, which is an extension of the conductor-like screening model for realistic solvation to micelles and biomembranes. The free energy profiles from these molecular methods are in good agreement. Additionally, solute orientations calculated with MD and COSMOmic are compared and again a good agreement is found. Four different solutes are investigated in detail: 4-ethylphenol, propanol, 5-phenylvaleric acid, and dibenz[a,h]anthracene, whereby the latter belongs to the class of polycyclic aromatic hydrocarbons. The convergence of the free energy profiles from biased MD simulations is discussed and the results are shown to be comparable to equilibrium MD simulations. For 5-phenylvaleric acid the influence of the carboxyl group dihedral angle on free energy profiles is analyzed with MD simulations

Geochemical modeling of reactions and partitioning of trace metals and radionuclides during titration of contaminated acidic sediments.

Science.gov (United States)

Zhang, Fan; Luo, Wensui; Parker, Jack C; Spalding, Brian P; Brooks, Scott C; Watson, David B; Jardine, Philip M; Gu, Baohua

2008-11-01

Many geochemical reactions that control aqueous metal concentrations are directly affected by solution pH. However, changes in solution pH are strongly buffered by various aqueous phase and solid phase precipitation/dissolution and adsorption/desorption reactions. The ability to predict acid-base behavior of the soil-solution system is thus critical to predict metal transport under variable pH conditions. This studywas undertaken to develop a practical generic geochemical modeling approach to predict aqueous and solid phase concentrations of metals and anions during conditions of acid or base additions. The method of Spalding and Spalding was utilized to model soil buffer capacity and pH-dependent cation exchange capacity by treating aquifer solids as a polyprotic acid. To simulate the dynamic and pH-dependent anion exchange capacity, the aquifer solids were simultaneously treated as a polyprotic base controlled by mineral precipitation/ dissolution reactions. An equilibrium reaction model that describes aqueous complexation, precipitation, sorption and soil buffering with pH-dependent ion exchange was developed using HydroGeoChem v5.0 (HGC5). Comparison of model results with experimental titration data of pH, Al, Ca, Mg, Sr, Mn, Ni, Co, and SO4(2-) for contaminated sediments indicated close agreement suggesting that the model could potentially be used to predictthe acid-base behavior of the sediment-solution system under variable pH conditions.

Environmental controls on the speciation and distribution of mercury in surface sediments of a tropical estuary, India

Digital Repository Service at National Institute of Oceanography (India)

Chakraborty, P.; Babu, P.V.R.

in the total Hg content in the sediments. Total organic carbon in the sediments played an important role in controlling Hg partitioning in the system. Uncomplexed Hg binding ligands were available in the sediments...

Investigations into the differential reactivity of endogenous and exogenous mercury species in coastal sediments.

Science.gov (United States)

Bouchet, S; Rodriguez-Gonzalez, P; Bridou, R; Monperrus, M; Tessier, E; Anschutz, P; Guyoneaud, R; Amouroux, D

2013-03-01

Stable isotopic tracer methodologies now allow the evaluation of the reactivity of the endogenous (ambient) and exogenous (added) Hg to further predict the potential effect of Hg inputs in ecosystems. The differential reactivity of endogenous and exogenous Hg was compared in superficial sediments collected in a coastal lagoon (Arcachon Bay) and in an estuary (Adour River) from the Bay of Biscay (SW France). All Hg species (gaseous, aqueous, and solid fraction) and ancillary data were measured during time course slurry experiments under variable redox conditions. The average endogenous methylation yield was higher in the estuarine (1.2 %) than in the lagoonal sediment (0.5 %), although both methylation and demethylation rates were higher in the lagoonal sediment in relation with a higher sulfate-reducing activity. Demethylation was overall more consistent than methylation in both sediments. The endogenous and exogenous Hg behaviors were always correlated but the exogenous inorganic Hg (IHg) partitioning into water was 2.0-4.3 times higher than the endogenous one. Its methylation was just slightly higher (1.4) in the estuarine sediment while the difference in the lagoonal sediment was much larger (3.6). The relative endogenous and exogenous methylation yields were not correlated to IHg partitioning, demonstrating that the bioavailable species distributions were different for the two IHg pools. In both sediments, the exogenous IHg partitioning equaled the endogenous one within a week, while its higher methylation lasted for months. Such results provide an original assessment approach to compare coastal sediment response to Hg inputs.

Dynamics of herbicide transport and partitioning under event flow conditions in the lower Burdekin region, Australia

International Nuclear Information System (INIS)

Davis, Aaron M.; Lewis, Stephen E.; Bainbridge, Zoë T.; Glendenning, Lionel; Turner, Ryan D.R.; Brodie, Jon E.

2012-01-01

This study examined the temporal variability in herbicide delivery to the Great Barrier Reef (GBR) lagoon (Australia) from one of the GBR catchment’s major sugarcane growing regions. Annual loads of measured herbicides were consistently in the order of 200+ kg. Atrazine, it’s degradate desethylatrazine, and diuron contributed approximately 90% of annual herbicide load, with early ‘first-flush’ events accounting for the majority of herbicide loads leaving the catchment. Assessment of herbicide water–sediment partitioning in flood runoff highlighted the majority of herbicides were transported in predominantly dissolved form, although a considerable fraction of diuron was transported in particulate-bound form (ca. 33%). Diuron was also the herbicide demonstrating the highest concentrations and frequency of detection in sediments collected from catchment waterways and adjacent estuarine–marine environments, an outcome aligning with previous research. Herbicide physico-chemical properties appear to play a crucial role in partitioning between water column and sediment habitat types in GBR receiving ecosystems.

Sediment Supply as a Control on Plant-Morphodynamic Interactions

Science.gov (United States)

Manners, R.; Wilcox, A. C.; Kui, L.; Stella, J. C.; Lightbody, A.; Sklar, L. S.

2014-12-01

The caliber and quantity of sediment delivered to a channel influences its size and shape, yet we know little about how the sediment supply affects rivers whose geomorphic form is influenced by riparian vegetation. We present results from flume experiments that test the impact of sediment supply on plant-morphodynamic interactions. We introduced two sediment supply conditions to a 28-meter long, sand bedded flume (60 cm wide and 71 cm deep) at the UC-Berkeley Richmond Field Station: equilibrium (balance between sediment transport and supply) and deficit (transport exceeds sediment supply). We conducted ten runs with different riparian seedling configurations (individual plants or patches) and species (tamarisk or cottonwood), and stem and leaf density (0.003-0.47 cm2/cm2), under both sediment supply conditions. Plant species, size, and configuration were important in predicting the topographic adjustments that occurred during our experiments. These influences may be attributed to differences in plant morphology; tamarisk is shrubby while cottonwood is more tree-like, with a single stem and leaves concentrated higher on the plant. The plant-morphodynamic relationship, however, differed for the two sediment supply conditions. During sediment equilibrium, only patches of cottonwood served as sediment sinks compared to an unvegetated bed, but tamarisk patches had no impact on the sediment mass balance. During sediment deficit, in contrast, tamarisk patches accumulated more sediment than unvegetated beds. Stem and leaf density also controlled changes in bed elevation. During equilibrium conditions, increasing the density of cottonwood stems and leaves resulted in greater bed degradation. Conversely, aggradation occurred with increases in the density of tamarisk. For sediment deficit conditions, the relationship between stem and leaf density and the rate of bed change was negative for both species (i.e., higher density resulted in faster rate of scour). The shifting

Water dimers in the atmosphere III: equilibrium constant from a flexible potential.

Science.gov (United States)

Scribano, Yohann; Goldman, Nir; Saykally, R J; Leforestier, Claude

2006-04-27

We present new results for the water dimer equilibrium constant K(p)(T) in the range 190-390 K, using a flexible potential energy surface fitted to spectroscopical data. The increased numerical complexity due to explicit consideration of the monomer vibrations is handled via an adiabatic (6 + 6)d decoupling between intra- and intermolecular modes. The convergence of the canonical partition function of the dimer is ensured by computing all energy levels up to dissociation for total angular momentum values J = 0-5 and using an extrapolation scheme to higher values. The newly calculated values for K(p)(T) are in very good agreement with available experimental data at room temperature. At higher temperatures, an analysis of the convergence of the partition function reveals that quasi-bound states are likely to contribute to the equilibrium constant. Additional thermodynamical quantities (deltaG, deltaH, deltaS, and C(p)) have also been determined and fit to quadratic expressions a + bT + cT2.

The distribution of triclosan and methyl-triclosan in marine sediments of Barker Inlet, South Australia.

Science.gov (United States)

Fernandes, Milena; Shareef, Ali; Kookana, Rai; Gaylard, Sam; Hoare, Sonja; Kildea, Tim

2011-04-01

In this work, we investigated the transport and burial of triclosan and its methylated derivative, in surface sediments near the mouth of Barker Inlet in South Australia. The most likely source of this commonly used bactericide to the area is a wastewater outfall discharging at the confluence of the inlet with marine waters. Triclosan was detected in all samples, at concentrations (5-27 μg kg(-1)) comparable to values found in other surface sediments under the influence of marine wastewater outfalls. Its dispersal was closely associated with fine and organic-rich fractions of the sediments. Methyl-triclosan was detected in approximately half of the samples at concentrations compound was linked to both wastewater discharges and biological methylation of the parent compound. Wastewater-borne methyl-triclosan had a smaller spatial footprint than triclosan and was mostly deposited in close proximity to the outfall. In situ methylation of triclosan likely occurs at deeper depositional sites, whereas the absence of methyl-triclosan from shallower sediments was potentially explained by photodegradation of the parent compound. Based on partition equilibrium, a concentration of triclosan in the order of 1 μg L(-1) was estimated in sediment porewaters, a value lower than the threshold reported for harmful effects to occur in the couple of species of marine phytoplankton investigated to date. Methyl-triclosan presents a greater potential for bioaccumulation than triclosan, but the implications of its occurrence to aquatic ecosystem health are difficult to predict given the lack of ecotoxicological data in the current literature.

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

Science.gov (United States)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

Equilibrium expert: an add-in to Microsoft Excel for multiple binding equilibrium simulations and parameter estimations.

Science.gov (United States)

Raguin, Olivier; Gruaz-Guyon, Anne; Barbet, Jacques

2002-11-01

An add-in to Microsoft Excel was developed to simulate multiple binding equilibriums. A partition function, readily written even when the equilibrium is complex, describes the experimental system. It involves the concentrations of the different free molecular species and of the different complexes present in the experiment. As a result, the software is not restricted to a series of predefined experimental setups but can handle a large variety of problems involving up to nine independent molecular species. Binding parameters are estimated by nonlinear least-square fitting of experimental measurements as supplied by the user. The fitting process allows user-defined weighting of the experimental data. The flexibility of the software and the way it may be used to describe common experimental situations and to deal with usual problems such as tracer reactivity or nonspecific binding is demonstrated by a few examples. The software is available free of charge upon request.

Dehydration and melting experiments constrain the fate of subducted sediments

Science.gov (United States)

Johnson, Marie C.; Plank, Terry

2000-12-01

Geochemical tracers demonstrate that elements are cycled from subducted sediments into the arc melting regime at subduction zones, although the transfer mechanism is poorly understood. Are key elements (Th, Be, Rb) lost during sediment dehydration or is sediment melting required? To investigate this question, we conducted phase equilibria and trace element partitioning experiments on a pelagic red clay for conditions appropriate to the slab beneath arc volcanoes (2-4 GPa, 600°-1000°C). Using both piston cylinders and multianvils, we determined the solidus, phase stabilities, and major element compositions of coexisting phases. The solidus (H2O + Cl fluid-saturated) was located at 775 ± 25°C at 2 GPa, 810 ± 15°C at 3 GPa, and 1025 ± 25°C at 4 GPa with noevidence for complete miscibility between melt and fluid. This sediment composition produces a profusion of phases both above and below the solidus: garnet, jadeitic pyroxene, alkali-rich amphibole, phengite, biotite, magnetite, coesite, kyanite, apatite, zircon, Cl-rich fluids, and peraluminous to peralkaline granitic melts. At 2 GPa the phengite dehydration solidus is at 800°-825°C, while biotite breaks down between 850° and 900°C. To explore trace element partitioning across the solidus at 2 GPa, we used diamonds to trap fluids and melts. Both the bulk sediment residues and diamond traps were analyzed postexperiment by inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES) for 40 elements for which we calculated bulk partition coefficients (D = Csolid/Cfluid). Below the solidus, Rb, Sr, Ba, and Pb showed the greatest mobility (D ˜ 0.5-1.0), while at the solidus, Th and Be became notably partitioned into the melt (D values changing from >2.0 to oceanic crust dehydration) may provide new constraints on the next generation of thermal/geodynamical models of subduction zones.

Real-Time Measurements of Gas/Particle Partitioning of Semivolatile Organic Compounds into Different Probe Particles in a Teflon Chamber

Science.gov (United States)

Liu, X.; Day, D. A.; Ziemann, P. J.; Krechmer, J. E.; Jimenez, J. L.

2017-12-01

The partitioning of semivolatile organic compounds (SVOCs) into and out of particles plays an essential role in secondary organic aerosol (SOA) formation and evolution. Most atmospheric models treat the gas/particle partitioning as an equilibrium between bulk gas and particle phases, despite potential kinetic limitations and differences in thermodynamics as a function of SOA and pre-existing OA composition. This study directly measures the partitioning of oxidized compounds in a Teflon chamber in the presence of single component seeds of different phases and polarities, including oleic acid, squalane, dioctyl sebacate, pentaethylene glycol, dry/wet ammonium sulfate, and dry/wet sucrose. The oxidized compounds are generated by a fast OH oxidation of a series of alkanols under high nitric oxide conditions. The observed SOA mass enhancements are highest with oleic acid, and lowest with wet ammonium sulfate and sucrose. A chemical ionization mass spectrometer (CIMS) was used to measure the decay of gas-phase organic nitrates, which reflects uptake by particles and chamber walls. We observed clear changes in equilibrium timescales with varying seed concentrations and in equilibrium gas-phase concentrations across different seeds. In general, the gas evolution can be reproduced by a kinetic box model that considers partitioning and evaporation with particles and chamber walls, except for the wet sucrose system. The accommodation coefficient and saturation mass concentration of each species in the presence of each seed are derived using the model. The changes in particle size distributions and composition monitored by a scanning mobility particle sizer (SMPS) and a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) are investigated to probe the SOA formation mechanism. Based on these results, the applicability of partitioning theory to these systems and the relevant quantitative parameters, including the dependencies on seed particle composition, will

Coding Partitions

Directory of Open Access Journals (Sweden)

Fabio Burderi

2007-05-01

Full Text Available Motivated by the study of decipherability conditions for codes weaker than Unique Decipherability (UD, we introduce the notion of coding partition. Such a notion generalizes that of UD code and, for codes that are not UD, allows to recover the ``unique decipherability" at the level of the classes of the partition. By tacking into account the natural order between the partitions, we define the characteristic partition of a code X as the finest coding partition of X. This leads to introduce the canonical decomposition of a code in at most one unambiguouscomponent and other (if any totally ambiguouscomponents. In the case the code is finite, we give an algorithm for computing its canonical partition. This, in particular, allows to decide whether a given partition of a finite code X is a coding partition. This last problem is then approached in the case the code is a rational set. We prove its decidability under the hypothesis that the partition contains a finite number of classes and each class is a rational set. Moreover we conjecture that the canonical partition satisfies such a hypothesis. Finally we consider also some relationships between coding partitions and varieties of codes.

Assessing metal contamination in recent creek sediments using fractionation technique along Mumbai coast, India

Digital Repository Service at National Institute of Oceanography (India)

Fernandes, L.L.; Nayak, G.N.

nitrogen) and sediment components (sand, silt, clay). A sequential extraction procedure was also applied to understand the partitioning of trace metals among the different fractions of the sediment. Together with this data, pollution indices were also...

Partitioning, bioavailability and origin of heavy metals from the Nador Lagoon sediments (Morocco) as a basis for their management

Science.gov (United States)

González, I.; Águila, E.; Galán, E.

2007-08-01

Nador Lagoon sediments show low trace element concentrations, and, in relation to the lagoon geochemical baseline, only some anomalies for As, Cd, Cu and Pb in the NW of the lagoon deserve to be outstanding. The distribution of major, minor and trace elements in the lagoon allows a breakdown in four zones. Between “Beni Ensar” and “Atelouane” (zone A), a quite confined zone rich in organic matter and S, the most important trace-element anomalies (As, Cd, Co, Cu, Mn, Pb, Zn) were found, mainly around industry and old mining activities. In the surrounding of the city of Nador (zone B), the anomalies correspond to Mn, Cu and Zn. The coastal barrier and Kebdana channel (zone C) show moderately concentrations of Cd, Cr and Ni at specific sites. The less polluted area is the SE of the lagoon (zone D), with no outstanding anomaly. In lagoon sediments, metal bioavailability is very low. The metal partitioning patterns show that Cu, Pb and Zn present a low availability because they are bounded to the residual, non-mobile phases of the sediments. Only in some sites, the fraction was associated with organic matter, which could be liberated easily. Arsenic is concentrated in both the residual phases and the organic matter, the latter being more available. Cadmium is mainly concentrated in some samples in the interchangeable fraction, which could be considered as a potentially toxic element because it is easily released. Concerning the origin of these trace elements, those found in zone A correspond mostly to a natural source by weathering of mount Gourougou volcanic rocks (As, Co, Cu, Pb and Zn), and to an anthropogenic origin (Cd) owing to the presence of industry and old mines. In zone B, contributions of Cu and Zn enter the lagoon through soil weathering and river-borne, and as anthropogenic pollution from urban wastes. In zone C the most important pollutant is Cd deduced to be of anthropogenic origin from the close industry and intensive agriculture area. In spite

Influence of intensive fishing on the partitioning of mercury and methylmercury in three lakes of Northern Quebec

Energy Technology Data Exchange (ETDEWEB)

Surette, Celine [COMERN, Universite du Quebec a Montreal, c.p. 8888, succ. Centre-Ville, Montreal, Quebec, H3C 3P8 (Canada)]. E-mail: surettc@umoncton.ca; Lucotte, Marc [COMERN, Universite du Quebec a Montreal, c.p. 8888, succ. Centre-Ville, Montreal, Quebec, H3C 3P8 (Canada); Tremblay, A. [Environment Unit, Dams and Environment Direction, Hydro-Quebec Production 75 Rene-Levesque West, 10th floor, Montreal, Quebec, H2Z 1A4 (Canada)

2006-09-01

It has been demonstrated that intensive fishing, i.e., removing more than 25% of the fish biomass, can reduce mercury levels in predator fish in a lake. We test here the hypothesis that, by removing an important part of the fish biomass from a lake, a significant amount of methylmercury can be eliminated, therefore reducing the mercury available to the remaining biota, at least in the short term. A mass burden approach is used to evaluate the partitioning of total mercury and methylmercury in natural lake ecosystems. Three small natural lakes from the James Bay territory, in northern Quebec, Canada, were selected for intensive fishing. Mercury (Hg) and methylmercury (MeHg) concentrations were evaluated for sediments, water column (dissolved fraction and suspended particulate matter), plankton, aquatic invertebrates, and fish. Biomasses were determined for fish, plankton, and aquatic invertebrates. Two case scenarios are presented using different mercury contributions from the sediment component (1 cm depth, and no sediment). Our results for the scenario including the sediment contribution show that lake sediments represent over 98% of the total mercury while the biotic components represent less than 0.1% of the same burden. For methylmercury, fish account for up to 5% of the burden, while sediments make up 84.6% to 93.1%. If we put aside the sediment contribution, the methylmercury in fish partitioning can represent up to 48%. As for invertebrates, they can account for up to 48% of the total MeHg burden. We do not observe any change in the partitionings or the quantities of Hg and MeHg before and after fishing in either of the two case scenarios even when we do not take into account dynamics of the ecosystems. This will be all the more the case when the dynamics of the system are included in the analyses. Therefore, biological parameters such as growth rates or fish diet must be considered.

Influence of intensive fishing on the partitioning of mercury and methylmercury in three lakes of Northern Quebec

International Nuclear Information System (INIS)

Surette, Celine; Lucotte, Marc; Tremblay, A.

2006-01-01

It has been demonstrated that intensive fishing, i.e., removing more than 25% of the fish biomass, can reduce mercury levels in predator fish in a lake. We test here the hypothesis that, by removing an important part of the fish biomass from a lake, a significant amount of methylmercury can be eliminated, therefore reducing the mercury available to the remaining biota, at least in the short term. A mass burden approach is used to evaluate the partitioning of total mercury and methylmercury in natural lake ecosystems. Three small natural lakes from the James Bay territory, in northern Quebec, Canada, were selected for intensive fishing. Mercury (Hg) and methylmercury (MeHg) concentrations were evaluated for sediments, water column (dissolved fraction and suspended particulate matter), plankton, aquatic invertebrates, and fish. Biomasses were determined for fish, plankton, and aquatic invertebrates. Two case scenarios are presented using different mercury contributions from the sediment component (1 cm depth, and no sediment). Our results for the scenario including the sediment contribution show that lake sediments represent over 98% of the total mercury while the biotic components represent less than 0.1% of the same burden. For methylmercury, fish account for up to 5% of the burden, while sediments make up 84.6% to 93.1%. If we put aside the sediment contribution, the methylmercury in fish partitioning can represent up to 48%. As for invertebrates, they can account for up to 48% of the total MeHg burden. We do not observe any change in the partitionings or the quantities of Hg and MeHg before and after fishing in either of the two case scenarios even when we do not take into account dynamics of the ecosystems. This will be all the more the case when the dynamics of the system are included in the analyses. Therefore, biological parameters such as growth rates or fish diet must be considered

Characterizing particle-scale equilibrium adsorption and kinetics of uranium(VI) desorption from U-contaminated sediments

Science.gov (United States)

Stoliker, Deborah L.; Liu, Chongxuan; Kent, Douglas B.; Zachara, John M.

2013-01-01

Rates of U(VI) release from individual dry-sieved size fractions of a field-aggregated, field-contaminated composite sediment from the seasonally saturated lower vadose zone of the Hanford 300-Area were examined in flow-through reactors to maintain quasi-constant chemical conditions. The principal source of variability in equilibrium U(VI) adsorption properties of the various size fractions was the impact of variable chemistry on adsorption. This source of variability was represented using surface complexation models (SCMs) with different stoichiometric coefficients with respect to hydrogen ion and carbonate concentrations for the different size fractions. A reactive transport model incorporating equilibrium expressions for cation exchange and calcite dissolution, along with rate expressions for aerobic respiration and silica dissolution, described the temporal evolution of solute concentrations observed during the flow-through reactor experiments. Kinetic U(VI) desorption was well described using a multirate SCM with an assumed lognormal distribution for the mass-transfer rate coefficients. The estimated mean and standard deviation of the rate coefficients were the same for all Micropore volumes, assessed using t-plots to analyze N2 desorption data, were also the same for all dry-sieved micropore volumes and mass-transfer rate properties. Pore volumes for dry-sieved size fractions exceeded values for the corresponding wet-sieved fractions. We hypothesize that repeated field wetting and drying cycles lead to the formation of aggregates and/or coatings containing (micro)pore networks which provided an additional mass-transfer resistance over that associated with individual particles. The 2–8 mm fraction exhibited a larger average and standard deviation in the distribution of mass-transfer rate coefficients, possibly caused by the abundance of microporous basaltic rock fragments.

Partitioning sediment flux by provenance and tracing erosion patterns in Taiwan

Science.gov (United States)

Resentini, Alberto; Goren, Liran; Castelltort, Sébastien; Garzanti, Eduardo

2017-07-01

We critically evaluate the potential and limitations of an alternative way to calculate erosion rates based on petrographic and mineralogical fingerprints of fluvial sediments coupled with gauged sediment fluxes. Our approach allows us to apportion sediment loads to different lithological units, and consequently to discriminate erosion rates in different tectonic domains within each catchment. Our provenance data on modern Taiwanese sands indicate focused erosion in the Backbone Range and Tananao Complex of the retrowedge. Lower rates are inferred for the northern part of the island characterized by tectonic extension and for the western foothills in the prowedge. The principal factor of uncertainty affecting our estimates is the inevitably inaccurate evaluation of total sediment load, because only the suspended flux was measured. Another is the assumption that suspended load and bed load are derived from the same sources in fixed proportions. Additional errors are caused by the insufficiently precise definition of lithologically similar compositional end-members and by the temporal variability of sediment composition at the outlet of each catchment related to the spatial variability of erosional processes and triggering agents such as earthquakes, typhoons, and landslides. To evaluate the robustness of our findings, we applied a morphometric technique based on the stream-power model. The results obtained are broadly consistent, with local discrepancies ascribed to poorly constrained assumptions and choices of scaling parameters. Our local erosion estimates are consistent with GPS uplift rates measured on a decadal timescale and generally higher than basin-wide results inferred from cosmogenic-nuclide and thermochronology data.

Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

Science.gov (United States)

Piper, David Z.; Bau, Michael

2013-01-01

The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

Organochlorines in benthic invertebrates and sediments from the Dutch Wadden Sea; identification of individual PCB components

Science.gov (United States)

Duinker, J. C.; Hillebrand, M. T. J.; Boon, J. P.

Concentrations of organochlorines were determined in Macoma balthica, Arenicola marina, Crangon crangon and sediments from the Dutch Wadden Sea. Maximum concentrations of (total) PCB, γ-HCH and dieldrin were found in the western part; a pronounced maximum of HCB was found in the western part. Concentrations of PCB, p,p'-DDD and p,p'-DDE in sediment were correlated with the percentage of particles metabolism, were lower in Crangon. The patterns of pentachloro- and higher chlorinated biphenyls were equal in Macoma, Arenicola and sediments. Since these components are not found in solution, they must be taken up from sediment and food. The results are in agreement with partitioning between body lipids and water as the dominant mechanism determining concentrations of persistent lipophilic contaminants in the animals. Partitioning with the ambient water may also determine the concentrations in the sediment.

Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain).

Science.gov (United States)

Gomez-Gonzalez, M A; Garcia-Guinea, J; Laborda, F; Garrido, F

2015-12-01

Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. Copyright © 2015 Elsevier B.V. All rights reserved.

Polycyclic aromatic hydrocarbons in urban atmosphere of Guangzhou, China: Size distribution characteristics and size-resolved gas-particle partitioning

Science.gov (United States)

Yu, Huan; Yu, Jian Zhen

2012-07-01

Size distributions of thirteen polycyclic aromatic hydrocarbons (PAHs), elemental carbon (EC), and organic carbon (OC) in the range of 0.01-18 μm were measured using a nano Micro-Orifice Uniform Deposit Impactor (nano-MOUDI) in an urban location in Guangzhou, China in July 2006. PAH size distributions were fit with five modes and the respective mass median aerodynamic diameters (MMAD) are: Aitken mode (MMAD: ˜0.05 μm), three accumulation modes AMI, AMII, AMIII (MMAD: 0.13-0.17 μm, 0.4-0.45 μm, and 0.9-1.2 μm, respectively), and coarse mode (MMAD: 4-6 μm). Seven-ring PAH was mainly in AMII and AMIII. Five- and six-ring PAHs were found to be abundant in all the three AM. Three- and four-ring PAHs had a significant presence in the coarse mode in addition to the three AM. Size-resolved gas-particle partition coefficients of PAHs (Kp) were estimated using measured EC and OC data. The Kp values of a given PAH could differ by a factor of up to ˜7 on particles in different size modes, with the highest Kp associated with the AMI particles and the lowest Kp associated with the coarse mode particles. Comparison of calculated overall Kp with measured Kp values in Guangzhou by Yang et al. (2010) shows that adsorption on EC appeared to be the dominant mechanism driving the gas-particle partitioning of three- and four-ring PAHs while absorption in OM played a dominant role for five- and six-ring PAHs. The calculated equilibrium timescales of repartitioning indicate that five- to seven-ring PAHs could not achieve equilibrium partitioning within their typical residence time in urban atmospheres, while three- and four-ring PAHs could readily reach new equilibrium states in particles of all sizes. A partitioning flux is therefore proposed to replace the equilibrium assumption in modeling PAH transport and fate.

Partitioning of hydrophobic organic contaminants between polymer and lipids for two silicones and low density polyethylene

NARCIS (Netherlands)

Smedes, F.; Rusina, T.P.; Beeltje, H.; Mayer, P.

2017-01-01

Polymers are increasingly used for passive sampling of neutral hydrophobic organic substances (HOC) in environmental media including water, air, soil, sediment and even biological tissue. The equilibrium concentration of HOC in the polymer can be measured and then converted into equilibrium

Phase equilibrium condition of marine carbon dioxide hydrate

International Nuclear Information System (INIS)

Sun, Shi-Cai; Liu, Chang-Ling; Ye, Yu-Guang

2013-01-01

Highlights: ► CO 2 hydrate phase equilibrium was studied in simulated marine sediments. ► CO 2 hydrate equilibrium temperature in NaCl and submarine pore water was depressed. ► Coarse-grained silica sand does not affect CO 2 hydrate phase equilibrium. ► The relationship between equilibrium temperature and freezing point was discussed. - Abstract: The phase equilibrium of ocean carbon dioxide hydrate should be understood for ocean storage of carbon dioxide. In this paper, the isochoric multi-step heating dissociation method was employed to investigate the phase equilibrium of carbon dioxide hydrate in a variety of systems (NaCl solution, submarine pore water, silica sand + NaCl solution mixture). The experimental results show that the depression in the phase equilibrium temperature of carbon dioxide hydrate in NaCl solution is caused mainly by Cl − ion. The relationship between the equilibrium temperature and freezing point in NaCl solution was discussed. The phase equilibrium temperature of carbon dioxide hydrate in submarine pore water is shifted by −1.1 K to lower temperature region than that in pure water. However, the phase equilibrium temperature of carbon dioxide hydrate in mixture samples of coarsed-grained silica sand and NaCl solution is in agreement with that in NaCl solution with corresponding concentrations. The relationship between the equilibrium temperature and freezing point in mixture samples was also discussed.

PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

International Nuclear Information System (INIS)

Choi, Hyeok; Al-Abed, Souhail R.

2009-01-01

Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K F (L kg -1 ) spanned several orders of magnitude, ranging from log K F of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

PCB congener sorption to carbonaceous sediment components: Macroscopic comparison and characterization of sorption kinetics and mechanism

Energy Technology Data Exchange (ETDEWEB)

Choi, Hyeok [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States); Al-Abed, Souhail R., E-mail: al-abed.souhail@epa.gov [National Risk Management Research Laboratory, U.S. Environmental Protection Agency, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States)

2009-06-15

Sorption of polychlorinated biphenyls (PCBs) to sediment is a key process in determining their mobility, bioavailability, and chemical decomposition in aquatic environments. In order to examine the validity of currently used interpretation approaches for PCBs sorption, comparative results on 2-chlorobiphenyl sorption to carbonaceous components in sediments (activated carbon, carbon black, coal, soot, graphite, flyash, wood) were macroscopically correlated with the structural, morphological, crystallographic, and compositional properties of the carbonaceous components. Since the Freundlich sorption constant, K{sub F} (L kg{sup -1}) spanned several orders of magnitude, ranging from log K{sub F} of 6.13-5.27 for activated carbon, 5.04 for carbon black, 3.83 for coal to 3.08 for wood, organic carbon partitioning approach should be more specifically categorized, considering the various forms, nature and origins of organic carbon in sediment. Sorption rate constants and fraction parameters, which were numerically defined from empirical kinetic model with fast and slow sorption fractions, were closely related to the physicochemical properties of the carbonaceous components. Sorption interpretation approaches with a specific property and viewpoint, such as organic carbon partitioning, soot carbon distribution, or surface area correlation, did not properly explain the overall results on sorption capacity, fast and slow sorption kinetics, and partitioning coefficient. It is also important to emphasize the heterogeneous nature of sediment and the difficulties of encompassing the partitioning among its carbonaceous components.

Geochemical partitioning of Cu and Ni in mangrove sediments: Relationships with their bioavailability

International Nuclear Information System (INIS)

Chakraborty, Parthasarathi; Ramteke, Darwin; Chakraborty, Sucharita

2015-01-01

Highlights: • Metal speciation controls bioavailability in mangrove ecosystem. • Bioavailability of Ni was controlled by Fe/Mn-oxyhydroxide and organic phases • Bioavailability of Cu in mangrove roots was controlled by organic phase in the sediments. • Cu interacts more strongly with organic phases than Ni in mangrove sediment. - Abstract: Sequential extraction study was performed to determine the concentrations of non-residual metal-complexes in the mangrove sediments from the Divar Island, (west coast of India). Accumulation of metal in the mangrove roots (from the same location) was determined and used as an indicator of bioavailability of metal. An attempt was made to establish a mechanistic linkage between the non-residual metal complexes and their bioavailability in the mangrove system. The non-residual fractions of Cu and Ni were mainly associated with Fe/Mn oxyhydroxide and organic phases in the sediments. A part of these metal fractions were bioavailable in the system. These two phases were the major controlling factors for Ni speciation and their bioavailability in the studied sediments. However, Cu was found to interact more strongly with the organic phases than Ni in the mangrove sediments. Organic phases in the mangrove sediments acted as buffer to control the speciation and bioavailability of Cu in the system

Mechanisms and rules of anion partition into ionic liquids: phenolate ions in ionic liquid/water biphasic systems.

Science.gov (United States)

Katsuta, Shoichi; Nakamura, Ko-ichi; Kudo, Yoshihiro; Takeda, Yasuyuki

2012-01-19

It is important to understand the mechanisms and general rules of ion partitioning in hydrophobic ionic liquid (IL)/water biphasic systems in order to predict the extractability of an ionic species with various ILs. In this study, we have investigated the partition of picrate ion (target anion, T(-)) from aqueous sodium picrate solutions into several ILs and the accompanying changes in aqueous concentrations of the IL component cation (C(+)) and anion (A(-)) at 298.2 K. The main ILs examined are 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-methyl-3-octylimidazolium bis(trifluoromethanesulfonyl)amide. The aqueous concentrations of C(+) and A(-) decreased and increased, respectively, with the extraction of T(-) into the IL phase. From the standpoint of equilibrium, the partition behavior of T(-) can be explained both by the anion exchange with A(-) in the IL phase and by the ion pair extraction with C(+) in the aqueous phase. The aqueous concentrations of C(+) and A(-) are governed by the solubility product of the IL (K(sp)). The distribution ratio of T(-) is expressed as a function of Δ[T(-)](W), namely, the difference between the initial and equilibrium concentrations of T(-) in the aqueous phase; the distribution ratio of T(-) is nearly constant when Δ[T(-)](W) < K(sp)(1/2), but decreases with increasing Δ[T(-)](W) in the larger Δ[T(-)](W) region. The equilibrium constants of the ion pair extraction and the ion exchange extraction have been determined for picrate and other phenolate ions whose partition data were previously reported. The dependences of the extraction constants and extractability on the kinds of IL component ions can be quantitatively explained on the basis of the variations of K(sp).

SVOC partitioning between the gas phase and settled dust indoors

Science.gov (United States)

Weschler, Charles J.; Nazaroff, William W.

2010-09-01

Semivolatile organic compounds (SVOCs) are a major class of indoor pollutants. Understanding SVOC partitioning between the gas phase and settled dust is important for characterizing the fate of these species indoors and the pathways by which humans are exposed to them. Such knowledge also helps in crafting measurement programs for epidemiological studies designed to probe potential associations between exposure to these compounds and adverse health effects. In this paper, we analyze published data from nineteen studies that cumulatively report measurements of dustborne and airborne SVOCs in more than a thousand buildings, mostly residences, in seven countries. In aggregate, measured median data are reported in these studies for 66 different SVOCs whose octanol-air partition coefficients ( Koa) span more than five orders of magnitude. We use these data to test a simple equilibrium model for estimating the partitioning of an SVOC between the gas phase and settled dust indoors. The results demonstrate, in central tendency, that a compound's octanol-air partition coefficient is a strong predictor of its abundance in settled dust relative to its gas phase concentration. Using median measured results for each SVOC in each study, dustborne mass fractions predicted using Koa and gas-phase concentrations correlate reasonably well with measured dustborne mass fractions ( R2 = 0.76). Combined with theoretical understanding of SVOC partitioning kinetics, the empirical evidence also suggests that for SVOCs with high Koa values, the mass fraction in settled dust may not have sufficient time to equilibrate with the gas phase concentration.

Characterizing toxicity of metal-contaminated sediments from mining areas

Science.gov (United States)

Besser, John M.; Brumbaugh, William G.; Ingersoll, Christopher G.

2015-01-01

of acid-volatile sulfide (AVS), termed simultaneously-extracted metals (SEM), are widely used to estimate the ‘potentially-bioavailable’ fraction of metals that is not bound to sulfides (i.e., SEM-AVS). Metal concentrations in pore water are widely considered to be direct measures of metal bioavailability, and predictions of toxicity based on pore-water metal concentrations may be further improved by modeling interactions of metals with other pore-water constituents using Biotic Ligand Models. Data from sediment toxicity tests and metal analyses has provided the basis for development of sediment quality guidelines, which estimate thresholds for toxicity of metals in sediments. Empirical guidelines such as Probable Effects Concentrations or (PECs) are based on associations between sediment metal concentrations and occurrence of toxic effects in large datasets. PECs do not model bioavailable metals, but they can be used to estimate the toxicity of metal mixtures using by calculation of probable effect quotients (PEQ = sediment metal concentration/PEC). In contrast, mechanistic guidelines, such as Equilibrium Partitioning Sediment Benchmarks (ESBs) attempt to predict both bioavailability and mixture toxicity. Application of these simple bioavailability models requires more extensive chemical characterization of sediments or pore water, compared to empirical guidelines, but may provide more reliable estimates of metal toxicity across a wide range of sediment types.

Evaluation of toxicity to the amphipod, Hyalella azteca, and to the midge, Chironomus dilutus; and bioaccumulation by the oligochaete, Lumbriculus variegatus, with exposure to PCB-contaminated sediments from Anniston, Alabama

Science.gov (United States)

Ingersoll, Christopher G.; Steevens, Jeffery A.; MacDonald, Donald D.; Brumbaugh, William G.; Coady, Matthew R.; Farrar, J. Daniel; Lotufo, Guilherme R.; Kemble, Nile E.; Kunz, James L.; Stanley, Jacob K.; Sinclair, Jesse A.; Ingersoll, Christopher G.; Steevens, Jeffery A.; MacDonald, Donald D.

2014-01-01

characterization of samples of whole sediment included analyses of grain size, TOC, and nutrients. Organic chemical characterization of samples of whole sediment included PCB homologs and select (13) PCB congeners, parent and alkylated polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides, and polychlorinated dibenzo-p-dioxins; and dibenzofurans. The PCB aroclors analyzed included 1016, 1221, 1232, 1242, 1248, 1254, 1260, 1262 and 1268. Analyses of whole sediment also included total metals, simultaneously extracted metals, and acid volatile sulfide. Chemical characterization of samples of pore water isolated from samples of whole sediment at the start of the sediment toxicity exposures or at the start of the sediment bioaccumulation exposures included metals, major cations, major anions, dissolved organic carbon, and additional water-quality characteristics. Concentrations of metals or PCBs in pore water during the sediment toxicity exposures or during sediment bioaccumulation exposures also were determined using peeper samples (for metals) or solid-phase microextraction (SPME) samplers (for PCBs). The bioavailability and bioaccumulation of PCBs in 14 sediment samples were investigated using SPME passive samplers and the 28-d L. variegatus whole-sediment bioaccumulation exposures In general the accumulation of PCBs consistently was predicted through the use of organic carbon normalization and equilibrium partitioning. In these sediments, PCB homologs were accumulated differently based on bioavailability and potential to accumulate in oligochaetes. As part of this assessment homolog specific biota sediment accumulation factor values were developed that could be applied across the larger site to predict tissue levels of PCBs. The whole-sediment toxicity tests done with H. azteca and C. dilutus met the established ASTM and USEPA test acceptability criteria. The most responsive H. azteca endpoints were day 42 survival normalized young per female and day 28 biomass and

On the relativistic partition function of ideal gases

International Nuclear Information System (INIS)

Sinyukov, Yu.M.

1983-01-01

The covariant partition function method for ideal Boltzmann and Bose gases is developed within quantum field theory. This method is a basis to describe the statistical and thermodynamical properties of the gases in canonical, grand canonical and pressure ensembles in an arbitrary inertial system. It is shown that when statistical systems are described relativistically it is very important to take into account the boundary conditions. This is due to the fact that an equilibrium system is not closed mechanically. The results may find application in hadron physics. (orig.)

The calculation of isotopic partition function ratios by a perturbation theory technique

International Nuclear Information System (INIS)

Singh, G.; Wolfsberg, M.

1975-01-01

The vibrational Hamiltonian of a molecule in the harmonic approximation, H = (1/2) Σ (g/subi/jp/subi/p/subj/ + f/subi/jq/subi/q/subj/), has been divided into a diagonal part (terms with i=j) and an off-diagonal part (inot-equalj), which is regarded as the perturbation. The vibrational partition function of the molecule is then calculated by Schwinger perturbation theory as the partition function of the unperturbed problem, corresponding to a collection of oscillators with frequencies 2πν/subi/' = (f/subi/ig/subi/i)/sup 1 / 2 /, plus perturbation correction terms which are calculated to second order. With the usual assumptions of isotope effect calculations that the molecular translations and rotations are classical and separable from the vibrations, the perturbation formulation of the vibrational partition function is easily transformed into a perturbation theory formulation of (reduced) isotopic partition function ratios. If, for example, the molecular potential function is expressed in terms of the displacements of bond stretches and bond angle bends from their respective equilibrium values, the unperturbed partition function ratio corresponds to the isotope effect expected for noninteracting bond-stretch and bond-angle-bend oscillators. Detailed comparison is made for a number of molecular systems of perturbation theory calculations of partition functions and isotopic partition function ratios with exact calculations carried out by actually obtaining the normal mode vibrational frequencies of the vibrational Hamiltonian. Good agreement is found. The utility of the perturbation theory formulation resides in the fact that it permits one to look at isotope effects in a very simple manner; some demonstrations are given

Determining metal origins and availability in fluvial deposits by analysis of geochemical baselines and solid-solution partitioning measurements and modelling.

Science.gov (United States)

Vijver, Martina G; Spijker, Job; Vink, Jos P M; Posthuma, Leo

2008-12-01

Metals in floodplain soils and sediments (deposits) can originate from lithogenic and anthropogenic sources, and their availability for uptake in biota is hypothesized to depend on both origin and local sediment conditions. In criteria-based environmental risk assessments, these issues are often neglected, implying local risks to be often over-estimated. Current problem definitions in river basin management tend to require a refined, site-specific focus, resulting in a need to address both aspects. This paper focuses on the determination of local environmental availabilities of metals in fluvial deposits by addressing both the origins of the metals and their partitioning over the solid and solution phases. The environmental availability of metals is assumed to be a key force influencing exposure levels in field soils and sediments. Anthropogenic enrichments of Cu, Zn and Pb in top layers could be distinguished from lithogenic background concentrations and described using an aluminium-proxy. Cd in top layers was attributed to anthropogenic enrichment almost fully. Anthropogenic enrichments for Cu and Zn appeared further to be also represented by cold 2M HNO3 extraction of site samples. For Pb the extractions over-estimated the enrichments. Metal partitioning was measured, and measurements were compared to predictions generated by an empirical regression model and by a mechanistic-kinetic model. The partitioning models predicted metal partitioning in floodplain deposits within about one order of magnitude, though a large inter-sample variability was found for Pb.

Comparison of the sampling rates and partitioning behaviour of polar and non-polar contaminants in the polar organic chemical integrative sampler and a monophasic mixed polymer sampler for application as an equilibrium passive sampler.

Science.gov (United States)

Jeong, Yoonah; Schäffer, Andreas; Smith, Kilian

2018-06-15

In this work, Oasis HLB® beads were embedded in a silicone matrix to make a single phase passive sampler with a higher affinity for polar and ionisable compounds than silicone alone. The applicability of this mixed polymer sampler (MPS) was investigated for 34 aquatic contaminants (log K OW -0.03 to 6.26) in batch experiments. The influence of flow was investigated by comparing uptake under static and stirred conditions. The sampler characteristics of the MPS was assessed in terms of sampling rates (R S ) and sampler-water partition coefficients (K SW ), and these were compared to those of the polar organic chemical integrative sampler (POCIS) as a reference kinetic passive sampler. The MPS was characterized as an equilibrium sampler for both polar and non-polar compounds, with faster uptake rates and a shorter time to reach equilibrium than the POCIS. Water flow rate impacted sampling rates by up to a factor of 12 when comparing static and stirred conditions. In addition, the relative accumulation of compounds in the polyethersulfone (PES) membranes versus the inner Oasis HLB sorbent was compared for the POCIS, and ranged from <1% to 83% depending on the analyte properties. This is indicative of a potentially significant lag-phase for less polar compounds within POCIS. The findings of this study can be used to quantitatively describe the partitioning and kinetic behaviour of MPS and POCIS for a range of aquatic organic contaminants for application in field sampling. Copyright © 2018 Elsevier B.V. All rights reserved.

Geochemistry of zinc in the sediments of the western continental shelf and slope of India

Digital Repository Service at National Institute of Oceanography (India)

Murty, P.S.N.; Paropkari, A.L.; Rao, Ch.M.

The bulk geochemistry of zinc in the sediments of the western continental shelf and slope of India and also the partition geochemistry of the sediments of the shelf and slope regions between Ratnagiri and Mangalore have been studied. The studies...

Solid/liquid partition coefficients (K{sub d}) and plant/soil concentration ratios (CR) for selected soils, tills and sediments at Forsmark

Energy Technology Data Exchange (ETDEWEB)

Sheppard, Steve (ECOMatters Inc. (Canada)); Sohlenius, Gustav (Sveriges geologiska undersoekning (Sweden)); Omberg, Lars-Gunnar (ALS Scandinavia AB (Sweden)); Borgiel, Mikael (Sveriges Vattenekologer AB (Sweden)); Grolander, Sara (Facilia AB (Sweden)); Norden, Sara (Svensk Kaernbraenslehantering AB (Sweden))

2011-11-15

Solid/liquid partition coefficients (K{sub d}) are used to indicate the relative mobility of radionuclides and elements of concern from nuclear fuel waste, as well as from other sources. To indicate the uptake of radionuclides in biota concentration ratios (CR) between soil and biota are used. This report summarized K{sub d} data for regolith and marine sediments based on concentrations of 69 indigenous stable elements measured from samples collected at the Forsmark site and CR data concerning cereals growing on these soils. The samples included 50 regolith samples from agricultural land and wetlands, 8 samples of till collected at different depths, and two marine sediment samples. In addition, cereal grains, stems and roots were collected from 4 sites for calculation of CRs. The regolith samples represented the major 5 deposits, which can be used as arable land, at the site (clayey till, glacial clay, clay gyttja and peat (cultivated and undisturbed)). K{sub d} values were generally lower for peat compared to clay soils. There were also clear differences in K{sub d} resulting from differences in soil chemistry within each regolith type. Soil pH was the most important factor, and K{sub d} values for many elements were lower in acidic clay soils compared to basic clay soils. Although there were only a few samples of sandy till and marine sediment, the K{sub d} values were generally consistent with the corresponding regolith K{sub d} values. Of the different cereal parts the grain always had the lowest CR. In most cases, the root CR was significantly higher than the grain CR, whereas only for a few elements were the grain and stem CR values different

Estimation of polycyclic aromatic hydrocarbon concentrations in the water column based on tissue residues in mussels and salmon: An equilibrium partitioning approach

International Nuclear Information System (INIS)

Neff, J.M.; Burns, W.A.

1996-01-01

Equilibrium partitioning was used to estimate concentrations of dissolved polycyclic aromatic hydrocarbons (PAHs) in the water column from PAH residues in tissues of mussels and juvenile pink salmon collected from coastal marine waters affected by the Exxon Valdez oil spill. Estimated concentrations were within factors of 2 to 5 for fish and 5 to 10 for mussels of average total dissolved and particulate PAHs measured in concurrent water samples. Temporal trends of estimated and measured water-column PAH concentrations were comparable. Water-column PAH concentrations estimated from residues in tissues of mussels (Mytilus trossulus) were higher than estimates based on residues in tissues of juvenile pink salmon (Oncorhynchus gorbuscha). Possible reasons for this difference include seasonal variations in mussel lipid content, differences in PAH uptake and depuration rates between fish and mussels, differences in how fish and mussels interact with particulate oil, and possible short exposure times for juvenile pink salmon. All of these factors may play a role. In any event, estimates of dissolved PAHs in the water column, based on PAH residues in either fish or mussel tissue, confirm that PAH concentrations generally did not exceed water quality standards for protection of marine life

[Speciation and Risk Characteristics of Heavy Metals in the Sediments of the Yangtze Estuary].

Science.gov (United States)

Yin, Su; Feng, Cheng-hong; Li, Yang-yang; Yin, Li-feng; Shen, Zhen-yao

2016-03-15

Based on the investigation on the distribution of total contents and speciation of 8 heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb, Zn) in the surface sediments at 14 typical sites of the Yangtze Estuary during three hydrological seasons ( wet, normal, and dry seasons) , this study applied equilibrium partitioning approach to build the sediment quality guidelines (SQGs) of the Yangtze Estuary, and assessed ecological risks of the heavy metals. The relationship between ecological risk and speciation of heavy metals was also revealed. The results showed that, except for Cd, the residual fraction was the main speciation of heavy metals, especially for As, Cr and Hg, their residual fraction proportions were all over 90%. The sediment quality guidelines of the Yangtze Estuary for As, Cd, Cr, Cu, Hg, Ni, Pb, Zn were 43.29, 0.672, 79.65, 19.08, 0.569, 339.09, 30.87, 411.36 µg · g⁻¹, respectively. Cu had the highest ecological risk to aquatic organisms. The upstream of Yangtze Estuary was mainly affected by Yangtze River runoff, where the risks were relatively high in wet season and relatively low in normal and dry seasons. However, the downstream of the estuary was mainly affected by municipal sewage of cities like Shanghai, where the risks were relatively high, especially in normal and dry seasons. There were three different relationships between the ecological risks and speciation of the eight heavy metals.

Equilibrium sampling of environmental pollutants in fish: Comparison with lipid- normalized concentrations and homogenization effects on chemical activity

DEFF Research Database (Denmark)

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha

2011-01-01

of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher...... in the homogenates (statistically significant in 18 of 21 cases, phomogenization increased the chemical activity of the PCBs and decreased the fugacity capacity of the tissue. This observation has implications for equilibrium sampling and partition coefficients determined using tissue...... homogenates....

Estimation of Partition Coefficients of Benzene, Toluene, Ethylbenzene, and ρ-Xylene by Consecutive Extraction with Solid Phase Microextraction

International Nuclear Information System (INIS)

Eom, In Yong

2011-01-01

The results show that the partition coefficients of the BTEX compound can be estimated using the SPME method under the consecutive extraction mode. The proposed technique is much simpler than previously reported methods. Its novelty is that it eliminated the calibration step in the GC/FID, i. e., liquid injection method. The use of the autosampler for the SPME fiber can facilitate the adoption of consecutive extractions; thus, it allows estimation of the partition coefficients of various analytes. Recently, GC/MS has increasingly been used in analytical laboratories; this may facilitate the identification of an unknown analyte as well as the computation of the corresponding partition coefficients with the proposed method. It is very important to use partition coefficients of organic pollutants to predict their fate in the environment. A liquid-liquid extraction technique was used to determine the partition coefficients of organic compounds between water and organic solvent. The concentration of the target compounds must be determined after equilibrium is established between the two phases. The partition coefficients can be estimated using the capacity factors of HPLC and GC

ASSESSING THE MOBILITY OF ARSENIC IN CONTAMINATED SEDIMENTS

Science.gov (United States)

The mobility of arsenic is controlled, in part, by partitioning to mineral surfaces in soils and sediments. Determination of the risk posed to human or ecosystem health by arsenic and identification of remediation technologies that could be employed to eliminate or reduce risk i...

Equilibrium sorptive enrichment on poly(dimethylsiloxane) particles for trace analysis of volatile compounds in gaseous samples

NARCIS (Netherlands)

Baltussen, H.A.; David, F.; Sandra, P.J.F.; Janssen, J.G.M.; Cramers, C.A.M.G.

1999-01-01

A novel approach for sample enrichment, namely, equilibrium sorptive enrichment (ESE), is presented. A packed bed of sorption (or partitioning) material is used to enrich volatiles from gaseous samples. Normally, air sampling is stopped before breakthrough occurs, but this approach is not very

Turbidity Currents With Equilibrium Basal Driving Layers: A Mechanism for Long Runout

Science.gov (United States)

Luchi, R.; Balachandar, S.; Seminara, G.; Parker, G.

2018-02-01

Turbidity currents run out over 100 km in lakes and reservoirs, and over 1,000 km in the ocean. They do so without dissipating themselves via excess entrainment of ambient water. Existing layer-averaged formulations cannot capture this. We use a numerical model to describe the temporal evolution of a turbidity current toward steady state under condition of zero net sediment flux at the bed. The flow self-partitions itself into two layers. The lower "driving layer" approaches an invariant flow thickness, velocity profile, and suspended sediment concentration profile that sequesters nearly all of the suspended sediment. This layer can continue indefinitely at steady state over a constant bed slope. The upper "driven layer" contains a small fraction of the suspended sediment. The devolution of the flow into these two layers likely allows the driving layer to run out long distances.

Partitioning of hydrophobic organic contaminants between polymer and lipids for two silicones and low density polyethylene

DEFF Research Database (Denmark)

Smedes, Foppe; Rusina, Tatsiana P.; Beeltje, Henry

2017-01-01

Polymers are increasingly used for passive sampling of neutral hydrophobic organic substances (HOC) in environmental media including water, air, soil, sediment and even biological tissue. The equilibrium concentration of HOC in the polymer can be measured and then converted into equilibrium conce...... for a thermodynamically sound risk assessment of HOC contained in microplastics....

Unique Path Partitions

DEFF Research Database (Denmark)

Bessenrodt, Christine; Olsson, Jørn Børling; Sellers, James A.

2013-01-01

We give a complete classification of the unique path partitions and study congruence properties of the function which enumerates such partitions.......We give a complete classification of the unique path partitions and study congruence properties of the function which enumerates such partitions....

Native oxy-PAHs, N-PACs, and PAHs in historically contaminated soils from Sweden, Belgium, and France: their soil-porewater partitioning behavior, bioaccumulation in Enchytraeus crypticus, and bioavailability.

Science.gov (United States)

Arp, Hans Peter H; Lundstedt, Staffan; Josefsson, Sarah; Cornelissen, Gerard; Enell, Anja; Allard, Ann-Sofie; Kleja, Dan Berggren

2014-10-07

Soil quality standards are based on partitioning and toxicity data for laboratory-spiked reference soils, instead of real world, historically contaminated soils, which would be more representative. Here 21 diverse historically contaminated soils from Sweden, Belgium, and France were obtained, and the soil-porewater partitioning along with the bioaccumulation in exposed worms (Enchytraeus crypticus) of native polycyclic aromatic compounds (PACs) were quantified. The native PACs investigated were polycyclic aromatic hydrocarbons (PAHs) and, for the first time to be included in such a study, oxygenated-PAHs (oxy-PAHs) and nitrogen containing heterocyclic PACs (N-PACs). The passive sampler polyoxymethylene (POM) was used to measure the equilibrium freely dissolved porewater concentration, Cpw, of all PACs. The obtained organic carbon normalized partitioning coefficients, KTOC, show that sorption of these native PACs is much stronger than observed in laboratory-spiked soils (typically by factors 10 to 100), which has been reported previously for PAHs but here for the first time for oxy-PAHs and N-PACs. A recently developed KTOC model for historically contaminated sediments predicted the 597 unique, native KTOC values in this study within a factor 30 for 100% of the data and a factor 3 for 58% of the data, without calibration. This model assumes that TOC in pyrogenic-impacted areas sorbs similarly to coal tar, rather than octanol as typically assumed. Black carbon (BC) inclusive partitioning models exhibited substantially poorer performance. Regarding bioaccumulation, Cpw combined with liposome-water partition coefficients corresponded better with measured worm lipid concentrations, Clipid (within a factor 10 for 85% of all PACs and soils), than Cpw combined with octanol-water partition coefficients (within a factor 10 for 76% of all PACs and soils). E. crypticus mortality and reproducibility were also quantified. No enhanced mortality was observed in the 21 historically

Organotins in the sediments of the Zuari estuary, west coast of India

Digital Repository Service at National Institute of Oceanography (India)

Jadhav, S.; Bhosle, N.B.; Massanisso, P.; Morabito, R

., Jadhav, S., Harji, R., Sawant, S., Venket, K., Anil, A. C., 2004. Butyltins in water, biofilm and sediments of the west coast of India. Chemosphere 57, 897-907. Burton, E. D., Phillips, I. R., Hawker, D. W., 2004. Sorption and desorption behaviour... of tributyltin with natural sediments. Environmental Science & Technology 38, 6694 – 6700. Burton, E. D., Phillips, I. R., Hawker, D. W., 2005. In-situ partitioning of butyltin species in estuarine sediments. Chemosphere 59, 585 – 592. Burton, E. D., Phillips...

Biogenic methane potential of marine sediments. Application of chemical thermodynamics

Energy Technology Data Exchange (ETDEWEB)

Arning, E.T.; Schulz, H.M. [Helmholtz Centre Potsdam GFZ, Potsdam (Germany); Berk, W. van [Technical Univ. of Clausthal (Germany). Dept. of Hydrogeology

2013-08-01

Accumulations of biogenic methane-dominated gas are widespread and occur in a variety of depositional settings and rock types. However, the potential of biogenic methane remains underexplored. This is mainly due to the fact that quantitative assessments applying numerical modeling techniques for exploration purposes are generally lacking to date. Biogenic methane formation starts in relatively shallow marine sediments below the sulfate reduction zone. When sulfate is exhausted, methanogenesis via the CO{sub 2} reduction pathway is often the dominant biogenic methane formation process in marine sediments (Claypool and Kaplan, 1974). The process can be simplified by the reaction: 2CH{sub 2}O + Ca{sup 2+} + H{sub 2}O {yields} CH{sub 4} + CaCO{sub 3} + 2H{sup +}. The products of early diagenetic reactions initiate coupled equilibrium reactions that induce a new state of chemical equilibrium among minerals, pore water and gas. The driving force of the complex biogeochemical reactions in sedimentary environments during early diagenesis is the irreversible redox-conversion of organic matter. Early diagenetic formation of biogenic methane shortly after deposition ('early diagenesis') was retraced using PHREEQC computer code that is applied to calculate homogenous and heterogeneous mass-action equations in combination with one-dimensional diffusion driven transport (Parkhurst and Appelo, 1999). Our modeling approach incorporates interdependent diagenetic reactions evolving into a diffusive multi-component and multiphase system by means of thermodynamic equilibrium calculations of species distribution (Arning et al., 2011, 2012, 2013). Reaction kinetics of organic carbon conversion is integrated into the set of equilibrium reactions by defining type and amount of converted organic matter in a certain time step. It is the aim (1) to calculate quantitatively thermodynamic equilibrium conditions (composition of pore water, mineral phase and gas phase assemblage) in

Environmental controls on the speciation and distribution of mercury in surface sediments of a tropical estuary, India

International Nuclear Information System (INIS)

Chakraborty, Parthasarathi; Babu, P.V. Raghunadh

2015-01-01

Highlights: • Physico-chemical parameters of water column control Hg speciation in sediments. • Sediments from the middle of the estuary were contaminated by Hg. • Concentrations of Hg were less during the monsoon and post monsoon period. • Salinity, pH of water column may change Hg speciation of the bottom sediments. • TOC in sediments control Hg partitioning in the system. - Abstract: Distribution and speciation of mercury (Hg) in the sediments from a tropical estuary (Godavari estuary) was influenced by the changing physico-chemical parameters of the overlying water column. The sediments from the upstream and downstream of the estuary were uncontaminated but the sediments from the middle of the estuary were contaminated by Hg. The concentrations of Hg became considerably less during the monsoon and post monsoon period. Total Hg concentrations and its speciation (at the middle of the estuary) were dependent on the salinity of the overlying water column. However, salinity had little or no effect on Hg association with organic phases in the sediments at downstream. Increasing pH of the overlying water column corresponded with an increase in the total Hg content in the sediments. Total organic carbon in the sediments played an important role in controlling Hg partitioning in the system. Uncomplexed Hg binding ligands were available in the sediments

Partitioning and interfacial tracers for differentiating NAPL entrapment configuration: column-scale investigation.

Science.gov (United States)

Dai, D; Barranco, F T; Illangasekare, T H

2001-12-15

Research on the use of partitioning and interfacial tracers has led to the development of techniques for estimating subsurface NAPL amount and NAPL-water interfacial area. Although these techniques have been utilized with some success at field sites, current application is limited largely to NAPL at residual saturation, such as for the case of post-remediation settings where mobile NAPL has been removed through product recovery. The goal of this study was to fundamentally evaluate partitioning and interfacial tracer behavior in controlled column-scale test cells for a range of entrapment configurations varying in NAPL saturation, with the results serving as a determinant of technique efficacy (and design protocol) for use with complexly distributed NAPLs, possibly at high saturation, in heterogeneous aquifers. Representative end members of the range of entrapment configurations observed under conditions of natural heterogeneity (an occurrence with residual NAPL saturation [discontinuous blobs] and an occurrence with high NAPL saturation [continuous free-phase LNAPL lens]) were evaluated. Study results indicated accurate prediction (using measured tracer retardation and equilibrium-based computational techniques) of NAPL amount and NAPL-water interfacial area for the case of residual NAPL saturation. For the high-saturation LNAPL lens, results indicated that NAPL-water interfacial area, but not NAPL amount (underpredicted by 35%), can be reasonably determined using conventional computation techniques. Underprediction of NAPL amount lead to an erroneous prediction of NAPL distribution, as indicated by the NAPL morphology index. In light of these results, careful consideration should be given to technique design and critical assumptions before applying equilibrium-based partitioning tracer methodology to settings where NAPLs are complexly entrapped, such as in naturally heterogeneous subsurface formations.

Using Performance Reference Compounds (PRCs) to measure dissolved water concentrations (Cfree) in the water column: Assessing equilibrium models

Science.gov (United States)

Equilibrium-based passive sampling methods are often used in aquatic environmental monitoring to measure hydrophobic organic contaminants (HOCs) and in the subsequent evaluation of their effects on ecological and human health. HOCs freely dissolved in water (Cfree) will partition...

A passive dosing method to determine fugacity capacities and partitioning properties of leaves

DEFF Research Database (Denmark)

Bolinius, Damien Johann; Macleod, Matthew; McLachlan, Michael S.

2016-01-01

The capacity of leaves to take up chemicals from the atmosphere and water influences how contaminants are transferred into food webs and soil. We provide a proof of concept of a passive dosing method to measure leaf/polydimethylsiloxane partition ratios (Kleaf/PDMS) for intact leaves, using...... polychlorinated biphenyls (PCBs) as model chemicals. Rhododendron leaves held in contact with PCB-loaded PDMS reached between 76 and 99% of equilibrium within 4 days for PCBs 3, 4, 28, 52, 101, 118, 138 and 180. Equilibrium Kleaf/PDMS extrapolated from the uptake kinetics measured over 4 days ranged from 0...... the variability in sorptive capacities of leaves that would improve descriptions of uptake of chemicals by leaves in multimedia fate models....

Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain)

International Nuclear Information System (INIS)

Gomez-Gonzalez, M.A.; Garcia-Guinea, J.; Laborda, F.; Garrido, F.

2015-01-01

Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. - Highlights: • Abandoned mine residues are Tl sources in soils of Madrid catchment area. • Tl was associated to quartz and aluminosilicates in both rocks and soils. • Tl was frequently found associated to organic particles and diatom frustules. • Cathodoluminescence is a suitable technique for Tl detection on soils and rocks

Thallium occurrence and partitioning in soils and sediments affected by mining activities in Madrid province (Spain)

Energy Technology Data Exchange (ETDEWEB)

Gomez-Gonzalez, M.A.; Garcia-Guinea, J. [National Museum of Natural Sciences, CSIC, Jose Gutierrez Abascal 2, 28006 Madrid (Spain); Laborda, F. [Group of Analytical Spectroscopy and Sensors Group, Institute of Environmental Sciences, University of Zaragoza, Pedro Cerbuna 12, 50009 Zaragoza (Spain); Garrido, F., E-mail: fernando.garrido@mncn.csic.es [National Museum of Natural Sciences, CSIC, Jose Gutierrez Abascal 2, 28006 Madrid (Spain)

2015-12-01

Thallium (Tl) and its compounds are toxic to biota even at low concentrations but little is known about Tl concentration and speciation in soils. An understanding of the source, mobility, and dispersion of Tl is necessary to evaluate the environmental impact of Tl pollution cases. In this paper, we examine the Tl source and dispersion in two areas affected by abandoned mine facilities whose residues remain dumped on-site affecting to soils and sediments of natural water courses near Madrid city (Spain). Total Tl contents and partitioning in soil solid phases as determined by means of a sequential extraction procedure were also examined in soils along the riverbeds of an ephemeral and a permanent streams collecting water runoff and drainage from the mines wastes. Lastly, electronic microscopy and cathodoluminescence probe are used as a suitable technique for Tl elemental detection on thallium-bearing phases. Tl was found mainly bound to quartz and alumino-phyllosilicates in both rocks and examined soils. Besides, Tl was also frequently found associated to organic particles and diatom frustules in all samples from both mine scenarios. These biogenic silicates may regulate the transfer of Tl into the soil-water system. - Highlights: • Abandoned mine residues are Tl sources in soils of Madrid catchment area. • Tl was associated to quartz and aluminosilicates in both rocks and soils. • Tl was frequently found associated to organic particles and diatom frustules. • Cathodoluminescence is a suitable technique for Tl detection on soils and rocks.

Characterizing toxicity of metal-contaminated sediments from mining areas

International Nuclear Information System (INIS)

Besser, John M.; Brumbaugh, William G.; Ingersoll, Christopher G.

2015-01-01

communities can help document causal relationships between metal contamination and biological effects. Total or total-recoverable metal concentrations in sediments are the most common measure of metal contamination in sediments, but metal concentrations in labile sediment fractions (e.g., determined as part of selective sediment extraction protocols) may better represent metal bioavailability. Metals released by the weak-acid extraction of acid-volatile sulfide (AVS), termed simultaneously-extracted metals (SEM), are widely used to estimate the ‘potentially-bioavailable’ fraction of metals that is not bound to sulfides (i.e., SEM-AVS). Metal concentrations in pore water are widely considered to be direct measures of metal bioavailability, and predictions of toxicity based on pore-water metal concentrations may be further improved by modeling interactions of metals with other pore-water constituents using Biotic Ligand Models. Data from sediment toxicity tests and metal analyses has provided the basis for development of sediment quality guidelines, which estimate thresholds for toxicity of metals in sediments. Empirical guidelines such as Probable Effects Concentrations or (PECs) are based on associations between sediment metal concentrations and occurrence of toxic effects in large datasets. PECs do not model bioavailable metals, but they can be used to estimate the toxicity of metal mixtures using by calculation of probable effect quotients (PEQ = sediment metal concentration/PEC). In contrast, mechanistic guidelines, such as Equilibrium Partitioning Sediment Benchmarks (ESBs) attempt to predict both bioavailability and mixture toxicity. Application of these simple bioavailability models requires more extensive chemical characterization of sediments or pore water, compared to empirical guidelines, but may provide more reliable estimates of metal toxicity across a wide range of sediment types

Sedimentation equilibrium of a small oligomer-forming membrane protein: effect of histidine protonation on pentameric stability.

Science.gov (United States)

Surya, Wahyu; Torres, Jaume

2015-04-02

Analytical ultracentrifugation (AUC) can be used to study reversible interactions between macromolecules over a wide range of interaction strengths and under physiological conditions. This makes AUC a method of choice to quantitatively assess stoichiometry and thermodynamics of homo- and hetero-association that are transient and reversible in biochemical processes. In the modality of sedimentation equilibrium (SE), a balance between diffusion and sedimentation provides a profile as a function of radial distance that depends on a specific association model. Herein, a detailed SE protocol is described to determine the size and monomer-monomer association energy of a small membrane protein oligomer using an analytical ultracentrifuge. AUC-ES is label-free, only based on physical principles, and can be used on both water soluble and membrane proteins. An example is shown of the latter, the small hydrophobic (SH) protein in the human respiratory syncytial virus (hRSV), a 65-amino acid polypeptide with a single α-helical transmembrane (TM) domain that forms pentameric ion channels. NMR-based structural data shows that SH protein has two protonatable His residues in its transmembrane domain that are oriented facing the lumen of the channel. SE experiments have been designed to determine how pH affects association constant and the oligomeric size of SH protein. While the pentameric form was preserved in all cases, its association constant was reduced at low pH. These data are in agreement with a similar pH dependency observed for SH channel activity, consistent with a lumenal orientation of the two His residues in SH protein. The latter may experience electrostatic repulsion and reduced oligomer stability at low pH. In summary, this method is applicable whenever quantitative information on subtle protein-protein association changes in physiological conditions have to be measured.

Adsorption - desorption equilibria of some radionuclides in sediment - sea water system

International Nuclear Information System (INIS)

El-Assy, N.B.; Fattah, A.T.A.; El-Shinawy, R.M.K.; Essa, M.W.A.

1991-01-01

Chemical and physical properties of Suez Canal bottom sediments (SCBS) and sea water at port Tawfeek area, the south entrance of Suez canal, have been studied. The SCBS was separated into its size fractions (natural sediment, sand, silt and clay). These different sediment fractions were allowed to be in equilibrium with 89 Sr, 60 Co and 134 Cs solutions. Desorption studies were carried out on these contaminated sediments. (author) 16 refs.; 1 fig.; 1 tab

Heavy metal distribution and partitioning in the vicinity of the discharge areas of Lisbon drainage basins (Tagus Estuary, Portugal)

Science.gov (United States)

Duarte, Bernardo; Silva, Gilda; Costa, José Lino; Medeiros, João Paulo; Azeda, Carla; Sá, Erica; Metelo, Inês; Costa, Maria José; Caçador, Isabel

2014-10-01

Worldwide estuarine ecosystems are by their privileged geographic location, anthropogenically impacted systems. Heavy metal contamination in estuarine waters and sediments are well known to be one of the most important outcomes driven from human activities. The partitioning of these elements has been widely focused, due to its importance not only on the estuarine biogeochemistry but also on its bioavailability to the trophic webs. As observed in other estuaries, in the Tagus basin, no increase in the partition coefficients with the increasing suspended particulate matter concentrations was observed, mostly due to a permanent dilution process of the suspended matter, rich in heavy metals and less contaminated and resuspended bottom sediments. Another important outcome of this study was the common origin of all the analysed heavy metals, probably due to the large industrialization process that the margins of the Tagus estuary suffered in the past, although no relationship was found with the presence of the different discharge areas. In fact, metal partitioning seems to be mostly influenced by the chemical species in which the pollutant is delivered to the system and on water chemistry, with a higher emphasis on the metal cycling essentially between the particulate and dissolved phase. This partitioning system acquires a relevant importance while evaluating the impacts of marine construction and the associated dredging operations, and consequent changes in the estuarine water chemistry.

Spatial distribution and partitioning behavior of selected poly- and perfluoroalkyl substances in freshwater ecosystems: A French nationwide survey

Energy Technology Data Exchange (ETDEWEB)

Munoz, Gabriel; Giraudel, Jean-Luc [University of Bordeaux, EPOC, UMR 5805, LPTC, 351 Cours de la Libération, F-33400 Talence, France. (France); Botta, Fabrizio; Lestremau, François [INERIS, Parc Technologique Alata, BP2, 60550 Verneuil-en-Halatte, France. (France); Dévier, Marie-Hélène [University of Bordeaux, EPOC, UMR 5805, LPTC, 351 Cours de la Libération, F-33400 Talence, France. (France); Budzinski, Hélène [CNRS, EPOC, UMR 5805, LPTC, 351 Cours de la Libération, F-33400 Talence, France. (France); Labadie, Pierre, E-mail: pierre.labadie@u-bordeaux.fr [CNRS, EPOC, UMR 5805, LPTC, 351 Cours de la Libération, F-33400 Talence, France. (France)

2015-06-01

The spatial distribution and partitioning of 22 poly- and perfluoroalkyl substances (PFASs) in 133 selected rivers and lakes were investigated at a nationwide scale in mainland France. ΣPFASs was in the range < LOD–725 ng L{sup −1} in the dissolved phase (median: 7.9 ng L{sup −1}) and < LOD–25 ng g{sup −1} dry weight (dw) in the sediment (median: 0.48 ng g{sup −1} dw); dissolved PFAS levels were significantly lower at “reference” sites than at urban, rural or industrial sites. Although perfluorooctane sulfonate (PFOS) was found to be the prevalent compound on average, a multivariate analysis based on neural networks revealed noteworthy trends for other compounds at specific locations and, in some cases, at watershed scale. For instance, several sites along the Rhône River displayed a peculiar PFAS signature, perfluoroalkyl carboxylates (PFCAs) often dominating the PFAS profile (e.g., PFCAs > 99% of ΣPFASs in the sediment, likely as a consequence of industrial point source discharge). Several treatments for data below detection limits (non-detects) were used to compute descriptive statistics, differences among groups, and correlations between congeners, as well as log K{sub d} and log K{sub oc} partition coefficients; in that respect, the Regression on Order Statistics (robust ROS) method was preferred for descriptive statistics computation while the Akritas–Theil–Sen estimator was used for regression and correlation analyses. Multiple regression results suggest that PFAS levels in the dissolved phase and sediment characteristics (organic carbon fraction and grain size) may be significant controlling factors of PFAS levels in the sediment. - Highlights: • A large-scale survey of PFASs in 133 French rivers and lakes is reported. • Descriptive statistics, correlations and partitioning coefficients were determined. • Non-detects were taken into account using functions from the NADA R-package. • Hot spots of PFAS contamination were found

Partitioning and source diagnostics of polycyclic aromatic hydrocarbons in rivers in Tianjin, China

International Nuclear Information System (INIS)

Shi, Z.; Tao, S.; Pan, B.; Liu, W.X.; Shen, W.R.

2007-01-01

Water, suspended particulate matter (SPM), and sediment samples were collected from ten rivers in Tianjin and analyzed for 16 polycyclic aromatic hydrocarbons (PAHs), dissolved organic carbon (DOC), particulate organic carbon (POC) in SPM and total organic carbon (TOC) in sediment. The behavior and fate of PAHs influenced by these parameters were examined. Generally, organic carbon was the primary factor controlling the behavior of the 16 PAH species. Partitioning of PAHs between SPM and water phase was studied, and K OC for some PAH species were found to be significantly higher than the predicted values. The source of PAHs contamination was diagnosed by using PAH isomer ratios. Coal combustion was identified to be a long-term and prevailing contamination source for sediment, while sewage/wastewater source could reasonably explain a short-term PAHs contamination of SPM. - Distribution of PAHs among water, suspended solids and sediment was under strong influence of naturally occurring organic carbon

Geochemistry of sediments of the eastern continental shelf of India

Digital Repository Service at National Institute of Oceanography (India)

Mascarenhas, A.; Paropkari, A.L.; Murty, P.S.N.

The bulk and partition geochemistry of Al, Fe, Ti, Mn, Zn, and Cu have been investigated in sediments of the eastern continental shelf of India. The results show that (1) the bulk geochemistry varies from one shelf unit to the other, (2) all...

Analysis of the presence of perfluoroalkyl substances in water, sediment and biota of the Jucar River (E Spain). Sources, partitioning and relationships with water physical characteristics

International Nuclear Information System (INIS)

Campo, Julian; Lorenzo, María; Pérez, Francisca; Picó, Yolanda; Farré, Marinella

2016-01-01

The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4–C14, C16, C18 carboxylate, C4, C6–C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22–11.5 ng g −1 ) and biota (0.63–274 µg kg −1 ) samples were higher than those measured in water (0.04–83.1 ng L −1 ), which might suggest (bio) accumulation. The occurrence of PFAS is related to urban and industrial discharges (Cuenca city in the upper part of basin, and car's factory, and effluents of the sewage treatment plant (STP) of Alzira, in the lower part). Increasing pollution gradients were found. On the other hand, higher contamination levels were observed after regulation dams of the catchment pointing out their importance in the re-distribution of these contaminants. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). PFAS concentrations found in this study can be considered in acceptable levels if compared to existing Regulatory Legislation and, consequently, they do not pose an immediate human health risk. - Highlights: • Distribution of 21 PFASs in water, sediment, biota of Jucar River is established. • PFPeA and PFOS are the predominant but high PFDA levels are related to industry. • PFASs in water and sediment related to the increase in NaCl, conductivity and TDS. • PFAS concentration in sediment/biota suggests (bio)accumulation. • None of the calculated

Estimating fate and transport of multiple contaminants in the vadose zone using a multi-layered soil column and three-phase equilibrium partitioning model

International Nuclear Information System (INIS)

Rucker, Gregory G.

2007-01-01

Soils at waste sites must be evaluated for the potential of residual soil contamination to leach and migrate to the groundwater beneath the disposal area. If migration to the aquifer occurs, contaminants can travel vast distances and pollute drinking water wells, thus exposing human receptors to harmful levels of toxins and carcinogens. To prevent groundwater contamination, a contaminant fate and transport analysis is necessary to assess the migration potential of residual soil contaminants. This type of migration analysis is usually performed using a vadose zone model to account for complex geotechnical and chemical variables including: decay processes, infiltration rate, soil properties, vadose zone thickness, and chemical behavior. The distinct advantage of using a complex model is that less restrictive, but still protective, soil threshold levels may be determined avoiding the unnecessary and costly remediation of marginally contaminated soils. However, the disadvantage of such modeling is the additional cost for data collection and labor required to apply these models. In order to allay these higher costs and to achieve a less restrictive but still protective clean-up level, a multiple contaminant and multi layered soil column equilibrium partitioning model was developed which is faster, simpler and less expensive to use. (authors)

Bacterial communities in the sediments of Dianchi Lake, a partitioned eutrophic waterbody in China.

Directory of Open Access Journals (Sweden)

Yaohui Bai

Full Text Available Bacteria play an important role in the decomposition and cycling of a variety of compounds in freshwater aquatic environments, particularly nutrient-rich eutrophic lakes. A unique Chinese eutrophic lake--Dianchi--was selected for study because it has two separate and distinct basins, Caohai with higher organic carbon levels and Waihai with lower organic carbon levels. Sediment bacterial communities were studied in the two basins using samples collected in each season from June 2010 to March 2011. Barcoded pyrosequencing based on the 16 S rRNA gene found that certain common phyla, Proteobacteria, Bacteroidetes, Firmicutes and Chloroflexi, were dominant in the sediments from both basins. However, from the class to genus level, the dominant bacterial groups found in the sediments were distinct between the two basins. Correlation analysis revealed that, among the environmental parameters examined, total organic carbon (TOC accounted for the greatest proportion of variability in bacterial community. Interestingly, study results suggest that increasing allochthonous organic carbon could enhance bacterial diversity and biomass in the sediment. In addition, analysis of function genes (amoA and nosZ demonstrated that ammonia-oxidizing bacteria (AOB were dominant in sediments, with 99% belonging to Nitrosomonas. Denitrifying bacteria were comparatively diverse and were associated with some cultivatable bacteria.

A novel method for the determination of adsorption partition coefficients of minor gases in a shale sample by headspace gas chromatography.

Science.gov (United States)

Zhang, Chun-Yun; Hu, Hui-Chao; Chai, Xin-Sheng; Pan, Lei; Xiao, Xian-Ming

2013-10-04

A novel method has been developed for the determination of adsorption partition coefficient (Kd) of minor gases in shale. The method uses samples of two different sizes (masses) of the same material, from which the partition coefficient of the gas can be determined from two independent headspace gas chromatographic (HS-GC) measurements. The equilibrium for the model gas (ethane) was achieved in 5h at 120°C. The method also involves establishing an equation based on the Kd at higher equilibrium temperature, from which the Kd at lower temperature can be calculated. Although the HS-GC method requires some time and effort, it is simpler and quicker than the isothermal adsorption method that is in widespread use today. As a result, the method is simple and practical and can be a valuable tool for shale gas-related research and applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Sorption of polycyclic aromatic hydrocarbons to oil contaminated sediments: Unresolved Complex?

NARCIS (Netherlands)

Jonker, M.T.O.; Sinke, A.; Brils, J.M.; Koelmans, A.A.

2003-01-01

Oil is ubiquitous in aquatic sediments and may affect partitioning and bioavailability of hydrophobic organic chemicals (HOCs). In contrast to other sedimentary hydrophobic carbon phases (natural organic matter, soot-like materials), oil residues have hardly received any attention as far as it

Influence of organic carbon and nitrate loading on partitioning between dissimilatory nitrate reduction to ammonium (DNRA) and N2 production

Science.gov (United States)

Hardison, Amber K.; Algar, Christopher K.; Giblin, Anne E.; Rich, Jeremy J.

2015-09-01

Biologically available nitrogen is removed from ecosystems through the microbial processes of anaerobic ammonium oxidation (anammox) or denitrification, while dissimilatory nitrate reduction to ammonium (DNRA) retains it. A mechanistic understanding of controls on partitioning among these pathways is currently lacking. The objective of this study was to conduct a manipulative experiment to determine the influence of organic C and NO3- loading on partitioning. Sediment was collected from a location on the southern New England shelf (78 m water depth) and sieved. Half of the sediment was mixed with freeze-dried phytoplankton and the other half was not. Sediment was then spread into 1.5 mm, "thin discs" closed at the bottom and placed in large aquarium tanks with filtered, N2/CO2 sparged seawater to maintain O2 limited conditions. Half of the discs received high NO3- loading, while the other half received low NO3- loading, resulting in a multifactorial design with four treatments: no C addition, low NO3- (-C-N); C addition, low NO3- (+C-N); no C addition, high NO3- (-C+N); and C addition, high NO3- (+C+N). Sediment discs were incubated in the tanks for 7 weeks, during which time inorganic N (NH4+, NO3-, and NO2-) was monitored, and sediment discs were periodically removed from the tanks to conduct 15N isotope labeling experiments in vials to measure potential rates of anammox, denitrification, and DNRA. Temporal dynamics of inorganic N concentrations in the tanks were indicative of anoxic N metabolism, with strong response of the build up or consumption of the intermediate NO2-, depending on treatments. Vial incubation experiments with added 15NO2- + 14NH4+ indicated significant denitrification and DNRA activity in sediment thin discs, but incubations with added 15NH4+ + 14NO2- indicated anammox was not at all significant. Inorganic N concentrations in the tanks were fit to a reactive transport model assuming different N transformations. Organic C decomposition rates

Abiotic partitioning of clothianidin under simulated rice field conditions.

Science.gov (United States)

Mulligan, Rebecca A; Parikh, Sanjai J; Tjeerdema, Ronald S

2015-10-01

Clothianidin is registered for pre- and post-flood application in Californian rice fields for control of the rice seed midge, Cricotopus sylvestris, and the rice water weevil, Lissorhoptrus oryzophilus. The objective was to characterize air-water and soil-water partitioning of clothianidin under simulated Californian rice field conditions. Clothianidin was confirmed to be non-volatile (from water) via the gas purge method, as no loss from the aqueous phase was observed at 22 and 37 °C; an upper-limit KH value was calculated at 2.9 × 10(-11) Pa m(3) mol(-1) (20 °C). Soil-water partitioning was determined by the batch equilibrium method using four soils collected from rice fields in the Sacramento Valley, and sorption affinity (Kd ), sorbent capacity, desorption and organic-carbon-normalized distribution (Koc ) were determined. Values for pH, cation exchange capacity and organic matter content ranged from 4.5 to 6.6, from 5.9 to 37.9 and from 1.25 to 1.97% respectively. The log Koc values (22 and 37 °C) ranged from 2.6 to 2.7, while sorption capacity was low at 22 °C and decreased further at 37 °C. Hysteresis was observed in soils at both temperatures, suggesting that bound residues do not readily desorb. Soil-water and air-water partitioning will not significantly reduce offsite transport of clothianidin from flooded rice fields via drainage. © 2014 Society of Chemical Industry.

A physically based catchment partitioning method for hydrological analysis

Science.gov (United States)

Menduni, Giovanni; Riboni, Vittoria

2000-07-01

We propose a partitioning method for the topographic surface, which is particularly suitable for hydrological distributed modelling and shallow-landslide distributed modelling. The model provides variable mesh size and appears to be a natural evolution of contour-based digital terrain models. The proposed method allows the drainage network to be derived from the contour lines. The single channels are calculated via a search for the steepest downslope lines. Then, for each network node, the contributing area is determined by means of a search for both steepest upslope and downslope lines. This leads to the basin being partitioned into physically based finite elements delimited by irregular polygons. In particular, the distributed computation of local geomorphological parameters (i.e. aspect, average slope and elevation, main stream length, concentration time, etc.) can be performed easily for each single element. The contributing area system, together with the information on the distribution of geomorphological parameters provide a useful tool for distributed hydrological modelling and simulation of environmental processes such as erosion, sediment transport and shallow landslides.

Analysis of the presence of perfluoroalkyl substances in water, sediment and biota of the Jucar River (E Spain). Sources, partitioning and relationships with water physical characteristics

Energy Technology Data Exchange (ETDEWEB)

Campo, Julian, E-mail: Julian.Campo@uv.es [Environmental Forensic and Landscape Chemistry Research Group. Desertification Research Centre - CIDE (Spanish Council for Scientific Research, University of Valencia, Generalitat Valenciana), Carretera Moncada - Náquera km 4.5 (Campus IVIA), Moncada, 46113 Valencia (Spain); Earth Surface Science, Institute for Biodiversity and Ecosystems Dynamics, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (Netherlands); Lorenzo, María [Food and Environmental Safety Research Group (SAMA–UV), Centro de Investigaciones sobre Desertificación (CIDE, UV–CSIC–GV) and Facultat de Farmàcia, Universitat de València, Av. Vicent Andrés Estellés s/n, Burjassot, 46100 Valencia (Spain); Pérez, Francisca [Department of Environmental Chemistry (IDAEA-CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); Picó, Yolanda [Food and Environmental Safety Research Group (SAMA–UV), Centro de Investigaciones sobre Desertificación (CIDE, UV–CSIC–GV) and Facultat de Farmàcia, Universitat de València, Av. Vicent Andrés Estellés s/n, Burjassot, 46100 Valencia (Spain); Farré, Marinella [Department of Environmental Chemistry (IDAEA-CSIC), Jordi Girona 18-26, 08034 Barcelona (Spain); and others

2016-05-15

The presence, sources and partitioning of 21 perfluoroalkyl substances (PFASs: C4–C14, C16, C18 carboxylate, C4, C6–C10 sulfonates and C8 sulfonamide) were assessed in water, sediment, and biota of the Jucar River basin (E Spain). Considering the three matrices, perfluoropentanoate (PFPeA) and perfluorooctane sulfonate (PFOS) were the most frequent compounds, being remarkable the high occurrence of short-chain PFASs (C≤8), which are intended to replace the long-chain ones in several industrial and commercial applications. In general, all samples were contaminated with at least one PFAS, with the exception of three fish samples. Mean concentrations detected in sediments (0.22–11.5 ng g{sup −1}) and biota (0.63–274 µg kg{sup −1}) samples were higher than those measured in water (0.04–83.1 ng L{sup −1}), which might suggest (bio) accumulation. The occurrence of PFAS is related to urban and industrial discharges (Cuenca city in the upper part of basin, and car's factory, and effluents of the sewage treatment plant (STP) of Alzira, in the lower part). Increasing pollution gradients were found. On the other hand, higher contamination levels were observed after regulation dams of the catchment pointing out their importance in the re-distribution of these contaminants. None of the hazard quotients (HQ) calculated indicate potential risk for the different tropic levels considered (algae, Daphnia sp. and fish). PFAS concentrations found in this study can be considered in acceptable levels if compared to existing Regulatory Legislation and, consequently, they do not pose an immediate human health risk. - Highlights: • Distribution of 21 PFASs in water, sediment, biota of Jucar River is established. • PFPeA and PFOS are the predominant but high PFDA levels are related to industry. • PFASs in water and sediment related to the increase in NaCl, conductivity and TDS. • PFAS concentration in sediment/biota suggests (bio)accumulation. • None of the

Energy Gradients Structure Microbial Communities Across Sediment Horizons in Deep Marine Sediments of the South China Sea

Science.gov (United States)

Graw, Michael F.; D'Angelo, Grace; Borchers, Matthew; Thurber, Andrew R.; Johnson, Joel E.; Zhang, Chuanlun; Liu, Haodong; Colwell, Frederick S.

2018-01-01

The deep marine subsurface is a heterogeneous environment in which the assembly of microbial communities is thought to be controlled by a combination of organic matter deposition, electron acceptor availability, and sedimentology. However, the relative importance of these factors in structuring microbial communities in marine sediments remains unclear. The South China Sea (SCS) experiences significant variability in sedimentation across the basin and features discrete changes in sedimentology as a result of episodic deposition of turbidites and volcanic ashes within lithogenic clays and siliceous or calcareous ooze deposits throughout the basin's history. Deep subsurface microbial communities were recently sampled by the International Ocean Discovery Program (IODP) at three locations in the SCS with sedimentation rates of 5, 12, and 20 cm per thousand years. Here, we used Illumina sequencing of the 16S ribosomal RNA gene to characterize deep subsurface microbial communities from distinct sediment types at these sites. Communities across all sites were dominated by several poorly characterized taxa implicated in organic matter degradation, including Atribacteria, Dehalococcoidia, and Aerophobetes. Sulfate-reducing bacteria comprised only 4% of the community across sulfate-bearing sediments from multiple cores and did not change in abundance in sediments from the methanogenic zone at the site with the lowest sedimentation rate. Microbial communities were significantly structured by sediment age and the availability of sulfate as an electron acceptor in pore waters. However, microbial communities demonstrated no partitioning based on the sediment type they inhabited. These results indicate that microbial communities in the SCS are structured by the availability of electron donors and acceptors rather than sedimentological characteristics. PMID:29696012

Development of long-lived radionuclides partitioning technology - Experimental/theoretical study of phase equilibria for multicomponent multiphase systems

Energy Technology Data Exchange (ETDEWEB)

Lee, Chul Soo; Lee, Se Il; Sim, Yeon Sik; Park, Sung Bin; Yang, Sung Oh; Park, Ji Yong [Korea University, Seoul (Korea, Republic of)

1995-08-01

In various partitioning processes, rare earth elements and actinide elements are separated from other elements in the first stage. They are then separated into rare earth groups and actinde groups. The first stage is accomplished by solvent extraction using DEHPA, by precipitation using oxalic= acid, or by cation exchange. The second stage is carried out by selective back-extraction or by selective elution using DTPA. In these processes the equilibria is governed by the concentrations of nitric acid, of solvents, and of precipitants among others. In this study various distribution coefficients in partitioning processes were experimentally determined. And thermodynamic models were proposed to calculate distribution coefficients with experimentally determined equilibrium constants. 32 refs., 11 tabs., 23 figs. (author)

Study of 137Cs e 60Co sorption in sediments from Saco de Piraquara de Fora, Angra dos Reis and its application for environmental monitoring

International Nuclear Information System (INIS)

Ferreira, Ingryd Marques

2016-01-01

Both the suspended solid particles and the bed sediments sorb radionuclides, released in water systems. Sorption is usually represented mathematically by the distribution coefficient that is based in equilibrium between phases. Here the adsorption/desorption kinetics of 60 Co and 137 Cs in sea water were simulated by batch equilibrium experiments with sediments in two points (PT - 01, PT - 02) from Saco de Piraquara de Fora inlet (SPF). For both radionuclides, partition coefficient values (Kd) for the sampling point PT - 02 (509 and 385 L/kg for 60 Co and 137 Cs, respectively) were higher than the values determined for PT - 01 one (426 and 182 L/kg for 137 Cs and 60 Co, respectively). The higher values of Kd of PT-02 reflects the higher CEC (71,4 cmolc.dm 3 ) and content of mud < 63 μm (87%) when compared to PT-01 (CEC of 39,5 cmol c .dm 3 ) and mud (55%). In comparison with the values reported in the literature, the found Kd values are low, which may be related to the predominance of kaolinite, which is a clay of low sorption capacity. The Kd values with an increase in temperature of 23 deg C to 27 deg C were similar ( 60 Co in PT-02 and 137 Cs in both sediment) or 27 ° C values were higher ( 60 Co the PT-01). With increasing temperature to 31 °C Kd values for the two radionuclides showed a decrease. However, increasing temperature increases the desorption of the two radionuclides for both sediments The sorption process is spontaneous and favorable for both sediments and the model of sorption can be fitted by both Freundlich and Langmuir sorption isotherms. The maximum amount of 60 Co that can be sorbed on sediments were 1,64 10 -5 moles/g (4,12 10 10 Bq/g) and 2,79 10 -5 moles/g (7,03 10 10 Bq/g) to PT-01 and PT-02, respectively, and of 137 Cs 1,99 10 -6 moles/g (9,70 10 8 Bq/g) and 6,60 10 -6 mol/g (2,87 10 9 Bq/g ) to PT-01 and PT-02. Two areas in SPF can potentially accumulate 137 Cs: sediments located near the effluent discharge and the area located north

Determination and partitioning of metals in sediments along the Suez Canal by sequential extraction

Science.gov (United States)

Abd El-Azim, H.; El-Moselhy, Kh. M.

2005-06-01

The application of sequential extraction technique was used to determine the chemical association of heavy metals in five different chemical phases (exchangeable F1, bound to carbonate F2, bound to Fe-Mn oxides F3, bound to organic matter F4 and residual F5) for sediment samples collected from the Suez Canal. From the obtained data, it can be seen that the surplus of metal contaminants introduced into the sediment from sources usually exists in relatively unstable chemical forms. A high proportion of the studied metals remained in the residual fraction. Most of remaining portion of metals was bound to ferromanganese oxides fraction. The low concentrations of metals in the exchangeable fraction indicated that the sediments of Suez Canal were relatively unpolluted.

Water-level fluctuations influence sediment porewater ...

Science.gov (United States)

Reservoirs typically have elevated fish mercury (Hg) levels compared to natural lakes and rivers. A unique feature of reservoirs is water-level management which can result in sediment exposure to the air. The objective of this study is to identify how reservoir water-level fluctuations impact Hg cycling, particularly the formation of the more toxic and bioaccumulative methylmercury (MeHg). Total-Hg (THg), MeHg, stable isotope methylation rates and several ancillary parameters were measured in reservoir sediments (including some in porewater and overlying water) that are seasonally and permanently inundated. The results showed that sediment and porewater MeHg concentrations were over 3-times higher in areas experiencing water-level fluctuations compared to permanently inundated sediments. Analysis of the data suggest that the enhanced breakdown of organic matter in sediments experiencing water-level fluctuations has a two-fold effect on stimulating Hg methylation: 1) it increases the partitioning of inorganic Hg from the solid phase into the porewater phase (lower log Kd values) where it is more bioavailable for methylation; and 2) it increases dissolved organic carbon (DOC) in the porewater which can stimulate the microbial community that can methylate Hg. Sulfate concentrations and cycling were enhanced in the seasonally inundated sediments and may have also contributed to increased MeHg production. Overall, our results suggest that reservoir management a

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

International Nuclear Information System (INIS)

Midorikawa, Sayaka; Arai, Takaomi; Harino, Hiroya; Ohji, Madoka; Nguyen Duc Cu; Miyazaki, Nobuyuki

2004-01-01

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g -1 dry wt and those in clams ranged from 1.4 to 56 ng g -1 wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g -1 dry wt), Cua Luc (15 ng g -1 dry wt), Sam Son (6.3 ng g -1 dry wt), and Tra Co (5.5 ng g -1 dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g -1 wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT

Partitioning and Dissolution Behavior of Metal-based Engineered Nanoparticles in Sediment and Soil Suspensions

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Koetsem F. Van

2013-04-01

Full Text Available Nowadays engineered nanoparticles are being used in a whole range of commercial applications and are therefore expected to inevitably find their way into the environment where their fate and behavior are still largely unknown. The objective of this study was to investigate the behavior and fate of a number of engineered nanoparticles (CeO2, SnO2, Ag in sediment and soil suspensions. In particular, the association of nanoparticles with solid phases, the kinetics of these interactions, and the solubility of the nanoparticulate matter in sediment and soil suspensions were studied. Four different sediments and three different soils were sampled at various locations in Flanders (Belgium, dried, grinded and characterized. Sediment and soil suspensions were prepared with Milli-Q water (1/10 S/L, spiked with the different metallic nanoparticles or corresponding ions, and continuously shaken for 24 hours. At regular time intervals, samples of the suspensions were collected and centrifuged at 500 or 2000 rpm, or left for gravitational settling. The supernatant was analyzed for total metal contents after aqua regia digestion and for dissolved metal ions after centrifugal ultrafiltration. In a second experiment, the impact of centrifugation speed on the amount of suspended matter in the supernatant was also studied. Relations between soil or sediment properties, suspended matter and metals in the supernatant were investigated. First data already point towards a strong association of nanoparticles with suspended material. The remaining data are still being collected and will be presented at the conference.

Landscape self organisation: Modelling Sediment trains

Science.gov (United States)

Schoorl, J. M.; Temme, A. J. A. M.; Veldkamp, A.

2012-04-01

Rivers tend to develop towards an equilibrium length profile, independently of exogenous factors. In general, although still under debate, this so-called self-organisation is assumed to be caused by simple feedbacks between sedimentation and erosion. Erosion correlates positively with gradient and discharge and sedimentation negatively. With the LAPSUS model, which was run for the catchment of the Sabinal, a small river in the South of Spain, this interplay of erosion and sedimentation results in sediment pulses (sequences of incision and sedimentation through time). These pulses are visualised in a short movie ( see http://www.youtube.com/watch?v=V5LDUMvYZxU). In this case the LAPSUS model run did not take climate, base level nor tectonics into account. Therefore, these pulses can be considered independent of them. Furthermore, different scenarios show that the existence of the pulses is independent of precipitation, erodibility and sedimentation rate, although they control the number and shape of the pulses. A fieldwork check showed the plausibility of the occurrence of these sediment pulses. We conclude that the pulses as modelled with LAPSUS are indeed the consequence of the feedbacks between erosion and sedimentation and are not depending on exogenous factors. Keywords: Landscape self-organisation, Erosion, Deposition, LAPSUS, Modelling

Thermodynamic Properties of Chromium Adsorption by Sediments ...

African Journals Online (AJOL)

The adsorption of Chromium from aqueous solution using river Watari sediment as an adsorbent was modeled. The influence of initial pH, solution temperature, adsorbent and adsorbate concentrations on the adsorption efficiency was investigated using batch equilibrium assays. From the results obtained for the adsorption ...

Effectiveness of water-air and octanol-air partition coefficients to predict lipophilic flavor release behavior from O/W emulsions.

Science.gov (United States)

Tamaru, Shunji; Igura, Noriyuki; Shimoda, Mitsuya

2018-01-15

Flavor release from food matrices depends on the partition of volatile flavor compounds between the food matrix and the vapor phase. Thus, we herein investigated the relationship between released flavor concentrations and three different partition coefficients, namely octanol-water, octanol-air, and water-air, which represented the oil, water, and air phases present in emulsions. Limonene, 2-methylpyrazine, nonanal, benzaldehyde, ethyl benzoate, α-terpineol, benzyl alcohol, and octanoic acid were employed. The released concentrations of these flavor compounds from oil-in-water (O/W) emulsions were measured under equilibrium using static headspace gas chromatography. The results indicated that water-air and octanol-air partition coefficients correlated with the logarithms of the released concentrations in the headspace for highly lipophilic flavor compounds. Moreover, the same tendency was observed over various oil volume ratios in the emulsions. Our findings therefore suggest that octanol-air and water-air partition coefficients can be used to predict the released concentration of lipophilic flavor compounds from O/W emulsions. Copyright © 2017 Elsevier Ltd. All rights reserved.

Geochemistry of the continental margin sediments of the central west coast of India

Digital Repository Service at National Institute of Oceanography (India)

Rao, Ch.M.; Murty, P.S.N.

organic carbonI~ntent{< I%J and organic carbon rich (upto 12%) carbonate sediments in the slope regionl The b'ulk and partition geocfiemistry of the surface sediments renect the complex intermixture of several sedimentary components (lithogenic. authigenic.... The elements Fe, Mn, Ni, Cu, Zn and Sr :ue determined using a Hilger and Watts Model M 1550 atomic absorption spectrophotometer. Titanium and Phosphorus are detennined on all samples by colorimeter (Riley, 1958; Strickland and Parsons, 1971). Following bulk...

Metal pollution in a contaminated bay: Relationship between metal geochemical fractionation in sediments and accumulation in a polychaete

International Nuclear Information System (INIS)

Fan, Wenhong; Xu, Zhizhen; Wang, Wen-Xiong

2014-01-01

Jinzhou Bay in Northern China has been seriously contaminated with metals due to the impacts of smelting activities. In this study, we investigated the relationship between metal accumulation in a deposit-feeding polychaete Neanthes japonica and metal concentration and geochemical fractionation (Cd, Cu, Pb, Zn and Ni) in sediments of Jinzhou Bay. Compared with the historical data, metals in the more mobile geochemical fraction (exchangeable and carbonate fractions) were gradually partitioned into the more stable fraction (Fe–Mn oxides) over time. Metal concentration and geochemical fractionation in sediment significantly affected metal bioavailability and accumulation in polychaetes, except for Ni. Metal accumulation in polychaetes was significantly influenced by Fe or Mn content, and to a lesser degree by organic matter. Prediction of metal bioaccumulation in polychaetes was greatly improved by normalizing metal concentrations to Mn content in sediment. The geochemical fractionation of metals in sediments including the exchangeable, organic matter and Fe–Mn oxides were important in controlling the sediment metal bioavailability to polychaetes. - Highlights: • Metals in contaminated sediments gradually partitioned into the more stable phase over time. • Metal accumulation in polychaetes was more significantly influenced by Fe/Mn content than by organic matter. • Prediction of metal bioaccumulation greatly improved by normalizing metals to Mn content in sediment. • Metals in exchangeable, organic matter and Fe–Mn oxides were important in controlling their bioavailability. - Prediction of metal bioaccumulation in polychaetes was significantly improved by normalizing metal concentrations to Mn content in sediment

Influence of salinity intrusion on the speciation and partitioning of mercury in the Mekong River Delta

Science.gov (United States)

Noh, Seam; Choi, Mijin; Kim, Eunhee; Dan, Nguyen Phuoc; Thanh, Bui Xuan; Ha, Nguyen Thi Van; Sthiannopkao, Suthipong; Han, Seunghee

2013-04-01

The lower Mekong and Saigon River Basins are dominated by distinctive monsoon seasons, dry and rainy seasons. Most of the Mekong River is a freshwater region during the rainy season, whereas during the dry season, salt water intrudes approximately 70 km inland. To understand the role of salinity intrusion controlling Hg behavior in the Mekong and Saigon River Basins, Hg and monomethylmercury (MMHg) in surface water and sediment of the Mekong River and in sediment of the Saigon River were investigated in the dry season. Sediment Hg distribution, ranging from 0.12 to 0.76 nmol g-1, was mainly controlled by organic carbon distribution in the Mekong River; however, the location of point sources was more important in the Saigon River (0.21-0.65 nmol g-1). The MMHg concentrations in Mekong (0.16-6.1 pmol g-1) and Saigon (0.70-8.7 pmol g-1) sediment typically showed significant increases in the estuarine head, with sharp increases of acid volatile sulfide. Unfiltered Hg (4.6-222 pM) and filtered Hg (1.2-14 pM) in the Mekong River increased in the estuarine zone due to enhanced particle loads. Conversely, unfiltered MMHg (0.056-0.39 pM) and filtered MMHg (0.020-0.17 pM) was similar between freshwater and estuarine zones, which was associated with mixing dilution of particulate MMHg by organic- and MMHg-depleted resuspended sediment. Partitioning of Hg between water and suspended particle showed tight correlation with the partitioning of organic carbon across study sites, while that of MMHg implied influences of chloride: enhanced chloride in addition to organic matter depletion decreased particulate MMHg in the estuarine zone. Primary production was an important determinant of inter-annual variation of particulate Hg and sediment MMHg. The bloom year showed relatively low particulate Hg with low C/N ratio, indicating biodilution of Hg. In contrast, the percentage of MMHg in sediment increased significantly in the bloom year, likely due to greater availability of

Evaluating the environmental fate of pharmaceuticals using a level III model based on poly-parameter linear free energy relationships

International Nuclear Information System (INIS)

Zukowska, Barbara; Breivik, Knut; Wania, Frank

2006-01-01

We recently proposed how to expand the applicability of multimedia models towards polar organic chemicals by expressing environmental phase partitioning with the help of poly-parameter linear free energy relationships (PP-LFERs). Here we elaborate on this approach by applying it to three pharmaceutical substances. A PP-LFER-based version of a Level III fugacity model calculates overall persistence, concentrations and intermedia fluxes of polar and non-polar organic chemicals between air, water, soil and sediments at steady-state. Illustrative modeling results for the pharmaceuticals within a defined coastal region are presented and discussed. The model results are highly sensitive to the degradation rate in water and the equilibrium partitioning between organic carbon and water, suggesting that an accurate description of this particular partitioning equilibrium is essential in order to obtain reliable predictions of environmental fate. The PP-LFER based modeling approach furthermore illustrates that the greatest mobility in aqueous phases may be experienced by pharmaceuticals that combines a small molecular size with strong H-acceptor properties

Evaluating the environmental fate of pharmaceuticals using a level III model based on poly-parameter linear free energy relationships

Energy Technology Data Exchange (ETDEWEB)

Zukowska, Barbara [Department of Analytical Chemistry, Chemical Faculty, Gdansk University of Technology, 11/12 G. Narutowicza St., 80-952 Gdansk (Poland); Breivik, Knut [NILU- Norwegian Institute for Air Research, P.O. Box 100, NO-2027 Kjeller (Norway)]. E-mail: knut.breivik@nilu.no; Wania, Frank [Department of Physical and Environmental Sciences, University of Toronto at Scarborough, 1265 Military Trail, Scarborough, Ontario, M1C 1A4 (Canada)

2006-04-15

We recently proposed how to expand the applicability of multimedia models towards polar organic chemicals by expressing environmental phase partitioning with the help of poly-parameter linear free energy relationships (PP-LFERs). Here we elaborate on this approach by applying it to three pharmaceutical substances. A PP-LFER-based version of a Level III fugacity model calculates overall persistence, concentrations and intermedia fluxes of polar and non-polar organic chemicals between air, water, soil and sediments at steady-state. Illustrative modeling results for the pharmaceuticals within a defined coastal region are presented and discussed. The model results are highly sensitive to the degradation rate in water and the equilibrium partitioning between organic carbon and water, suggesting that an accurate description of this particular partitioning equilibrium is essential in order to obtain reliable predictions of environmental fate. The PP-LFER based modeling approach furthermore illustrates that the greatest mobility in aqueous phases may be experienced by pharmaceuticals that combines a small molecular size with strong H-acceptor properties.

Estimating the in situ sediment-porewater distribution of PAHs and chlorinated aromatic hydrocarbons in anthropogenic impacted sediments

Energy Technology Data Exchange (ETDEWEB)

Hans Peter H. Arp; Gijs D. Breedveld; Gerard Cornelissen [Norwegian Geotechnical Institute (NGI), Oslo (Norway). Department of Environmental Engineering

2009-08-15

It has become increasingly apparent that the in situ sediment-porewater distribution behavior of organic compounds within anthropogenic impacted sediments is quite diverse, and challenging to generalize. Traditional models based on octanol-water partitioning generally overestimate native porewater concentrations, and modern approaches accounting for multiple carbon fractions, including black carbon, appear sediment specific. To assess the diversity of this sorption behavior, we collected all peer-reviewed total organic carbon (TOC)-normalized in situ sediment-porewater distribution coefficients, K{sub TOC}, for impacted sediments. This entailed several hundreds of data for PAHs, PCBs, PCDD/Fs, and chlorinated benzenes, covering a large variety of sediments, locations, and experimental methods. Compound-specific KTOC could range up to over 3 orders of magnitude. Output from various predictive models for individual carbonaceous phases found in impacted sediments, based on peer-reviewed polyparameter linear free energy relationships (PP-LFERs), Raoult's Law, and the SPARC online-calculator, were tested to see if any of the models could consistently predict literature K{sub TOC} values within a factor of 30 (i.e. about 1.5 orders of magnitude, or half the range of K{sub TOC} values). The Raoult's Law model and coal tar PP-LFER achieved the sought-after accuracy for all tested compound classes, and are recommended for general, regional-scale modeling purposes. As impacted sediment-porewater distribution models are unlikely to get more accurate than this, this review underpins that the only way to accurately obtain accurate porewater concentrations is to measure them directly, and not infer them from sediment concentrations. 86 refs., 2 figs., 3 tabs.

Energy Gradients Structure Microbial Communities Across Sediment Horizons in Deep Marine Sediments of the South China Sea

Directory of Open Access Journals (Sweden)

Michael F. Graw

2018-04-01

Full Text Available The deep marine subsurface is a heterogeneous environment in which the assembly of microbial communities is thought to be controlled by a combination of organic matter deposition, electron acceptor availability, and sedimentology. However, the relative importance of these factors in structuring microbial communities in marine sediments remains unclear. The South China Sea (SCS experiences significant variability in sedimentation across the basin and features discrete changes in sedimentology as a result of episodic deposition of turbidites and volcanic ashes within lithogenic clays and siliceous or calcareous ooze deposits throughout the basin's history. Deep subsurface microbial communities were recently sampled by the International Ocean Discovery Program (IODP at three locations in the SCS with sedimentation rates of 5, 12, and 20 cm per thousand years. Here, we used Illumina sequencing of the 16S ribosomal RNA gene to characterize deep subsurface microbial communities from distinct sediment types at these sites. Communities across all sites were dominated by several poorly characterized taxa implicated in organic matter degradation, including Atribacteria, Dehalococcoidia, and Aerophobetes. Sulfate-reducing bacteria comprised only 4% of the community across sulfate-bearing sediments from multiple cores and did not change in abundance in sediments from the methanogenic zone at the site with the lowest sedimentation rate. Microbial communities were significantly structured by sediment age and the availability of sulfate as an electron acceptor in pore waters. However, microbial communities demonstrated no partitioning based on the sediment type they inhabited. These results indicate that microbial communities in the SCS are structured by the availability of electron donors and acceptors rather than sedimentological characteristics.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

Directory of Open Access Journals (Sweden)

A. Zuend

2010-08-01

Full Text Available Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008. This model allows the reliable computation of the liquid-liquid coexistence curve (binodal, corresponding tie-lines, the limit of stability/metastability (spinodal, and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six

A phase-field model for non-equilibrium solidification of intermetallics

International Nuclear Information System (INIS)

Assadi, H.

2007-01-01

Intermetallics may exhibit unique solidification behaviour-including slow growth kinetics, anomalous partitioning and formation of unusual growth morphologies-because of departure from local equilibrium. A phase-field model is developed and used to illustrate these non-equilibrium effects in solidification of a prototype B2 intermetallic phase. The model takes sublattice compositions as primary field variables, from which chemical long-range order is derived. The diffusive reactions between the two sublattices, and those between each sublattice and the liquid phase are taken as 'internal' kinetic processes, which take place within control volumes of the system. The model can thus capture solute and disorder trapping effects, which are consistent-over a wide range of the solid/liquid interface thickness-with the predictions of the sharp-interface theory of solute and disorder trapping. The present model can also take account of solid-state ordering and thus illustrate the effects of chemical ordering on microstructure formation and crystal growth kinetics

Comparison of modeling approaches for carbon partitioning: Impact on estimates of global net primary production and equilibrium biomass of woody vegetation from MODIS GPP

Science.gov (United States)

Takeshi Ise; Creighton M. Litton; Christian P. Giardina; Akihiko Ito

2010-01-01

Partitioning of gross primary production (GPP) to aboveground versus belowground, to growth versus respiration, and to short versus long�]lived tissues exerts a strong influence on ecosystem structure and function, with potentially large implications for the global carbon budget. A recent meta-analysis of forest ecosystems suggests that carbon partitioning...

Toxicity of sediments potentially contaminated by coal mining and natural gas extraction to unionid mussels and commonly tested benthic invertebrates

Science.gov (United States)

Wang, Ning; Ingersoll, Christopher G.; Kunz, James L.; Brumbaugh, William G.; Kane, Cindy M.; Evans, R. Brian; Alexander, Steven; Walker, Craig; Bakaletz, Steve

2013-01-01

Sediment toxicity tests were conducted to assess potential effects of contaminants associated with coal mining or natural gas extraction activities in the upper Tennessee River basin and eastern Cumberland River basin in the United States. Test species included two unionid mussels (rainbow mussel, Villosa iris, and wavy-rayed lampmussel, Lampsilis fasciola, 28-d exposures), and the commonly tested amphipod, Hyalella azteca (28-d exposure) and midge, Chironomus dilutus (10-d exposure). Sediments were collected from seven test sites with mussel communities classified as impacted and in proximity to coal mining or gas extraction activities, and from five reference sites with mussel communities classified as not impacted and no or limited coal mining or gas extraction activities. Additional samples were collected from six test sites potentially with high concentrations of polycyclic aromatic hydrocarbons (PAHs) and from a test site contaminated by a coal ash spill. Mean survival, length, or biomass of one or more test species was reduced in 10 of 14 test samples (71%) from impacted areas relative to the response of organisms in the five reference samples. A higher proportion of samples was classified as toxic to mussels (63% for rainbow mussels, 50% for wavy-rayed lampmussels) compared with amphipods (38%) or midge (38%). Concentrations of total recoverable metals and total PAHs in sediments did not exceed effects-based probable effect concentrations (PECs). However, the survival, length, or biomasses of the mussels were reduced significantly with increasing PEC quotients for metals and for total PAHs, or with increasing sum equilibrium-partitioning sediment benchmark toxic units for PAHs. The growth of the rainbow mussel also significantly decreased with increasing concentrations of a major anion (chloride) and major cations (calcium and magnesium) in sediment pore water. Results of the present study indicated that (1) the findings from laboratory tests were generally

Distribution of polycyclic aromatic hydrocarbons in water and surface sediments from Daya Bay, China

International Nuclear Information System (INIS)

Zhou, J.L.; Maskaoui, K.

2003-01-01

Findings indicate an urgent need to establish a monitoring program for persistent organic pollutants in water and sediment. - Marine culture is thriving in China and represents a major component of the regional economy in coastal zones, yet the environmental quality of many of those areas has never been studied. This paper attempts to investigate the quality status of Daya Bay, a key aquaculture area in China. The levels of 16 polycyclic aromatic hydrocarbons (PAHs) were determined in water and sediment samples of the bay. The total concentrations of 16 PAHs varied from 4228 to 29325 ng l -1 in water, and from 115 to 1134 ng g -1 dry weight in sediments. In comparison to many other marine systems studied, the PAH levels in Daya Bay waters were relatively high, and at six sites they were sufficiently high (>10 μg l -1 ) to cause acute toxicity. The PAH composition pattern in sediments suggest dominance by medium to high molecular weight compounds, and the ratio of certain related PAHs indicate important pyrolytic and petrogenic sources. Further analysis showed that the distribution coefficient (K D ) increased with the particular organic carbon content of sediments, consistent with the PAH partition theory. The organic carbon normalised distribution coefficient (K oc ) also increased with the compounds' octanol/water partition coefficient (K ow ), confirming the potential applicability of the linear free energy relationships in the modelling and prediction of PAH behaviour in marine environments

Uranium isotopes in waters and bottom sediments of rivers and lakes in Poland

International Nuclear Information System (INIS)

Pietrzak-Flis, Z.; Kaminska, I.; Chrzanowski, E.

2004-01-01

Activity concentrations of 238 U, 234 U and 235 U were determined in waters and bottom sediments in two main rivers in Poland (the Vistula and Odra rivers) with their tributaries, in four coastal rivers and six lakes. Concentration of 238 U and 233 U were compared with the concentrations of 226 Ra determined in another study. As compared with concentrations in coastal rivers and in lakes, enhanced concentrations of the radionuclides were observed in water and bottom sediments in the upper and middle courses of Vistula river, whereas in the Odra river the enhanced concentrations were present only in the bottom sediments. The enhanced concentrations in the Vistula river result from the discharge of coal mine waters from the Upper Silesian Coal Basin, and they indicate that the discharge was continued. The enhanced concentration in Odra river observed only in bottom sediments indicate that the discharge occurred in the past. The 234 U/ 238 U ratio for the bottom sediments was close to unity, indicating that these isotopes were close to equilibrium, whereas for water the average ratio was form 1.2 for lakes to 1.5 for the Vistula river, demonstrating the lack of equilibrium. (author)

Safety-Critical Partitioned Software Architecture: A Partitioned Software Architecture for Robotic

Science.gov (United States)

Horvath, Greg; Chung, Seung H.; Cilloniz-Bicchi, Ferner

2011-01-01

The flight software on virtually every mission currently managed by JPL has several major flaws that make it vulnerable to potentially fatal software defects. Many of these problems can be addressed by recently developed partitioned operating systems (OS). JPL has avoided adopting a partitioned operating system on its flight missions, primarily because doing so would require significant changes in flight software design, and the risks associated with changes of that magnitude cannot be accepted by an active flight project. The choice of a partitioned OS can have a dramatic effect on the overall system and software architecture, allowing for realization of benefits far beyond the concerns typically associated with the choice of OS. Specifically, we believe that a partitioned operating system, when coupled with an appropriate architecture, can provide a strong infrastructure for developing systems for which reusability, modifiability, testability, and reliability are essential qualities. By adopting a partitioned OS, projects can gain benefits throughout the entire development lifecycle, from requirements and design, all the way to implementation, testing, and operations.

Comments on equilibrium, transient equilibrium, and secular equilibrium in serial radioactive decay

International Nuclear Information System (INIS)

Prince, J.R.

1979-01-01

Equations describing serial radioactive decay are reviewed along with published descriptions or transient and secular equilibrium. It is shown that terms describing equilibrium are not used in the same way by various authors. Specific definitions are proposed; they suggest that secular equilibrium is a subset of transient equilibrium

Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

Science.gov (United States)

Román, Iván P; Mastromichali, Anna; Tyrovola, Konstantina; Canals, Antonio; Psillakis, Elefteria

2014-02-21

Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption. Copyright © 2014 Elsevier B.V. All rights reserved.

Remobilization of polycyclic aromatic hydrocarbons and organic matter in seawater during sediment resuspension experiments from a polluted coastal environment: Insights from Toulon Bay (France).

Science.gov (United States)

Guigue, Catherine; Tedetti, Marc; Dang, Duc Huy; Mullot, Jean-Ulrich; Garnier, Cédric; Goutx, Madeleine

2017-10-01

Polycyclic aromatic hydrocarbons (PAHs) and organic matter contents were measured in seawater during resuspension experiments using sediments collected from Toulon Bay (Northwestern Mediterranean Sea, France). The studied sediments were very highly contaminated in PAHs, especially in 4-ring compounds emitted from combustion processes. The sediments used for resuspension experiments were collected at 0-2 cm (diagenetically new organic matter, OM) and 30-32 cm depths (diagenetically transformed OM). They were both mostly composed of fine particles (seawater up to 10-, 1.3-, 4.4- and 5.7-fold, respectively. The remobilization in seawater was higher for 4-6 ring PAHs, especially benzo(g,h,i)perylene, whose concentration exceeded the threshold values of the European Water Framework Directive. This noted the potential harmful effects of sediment resuspension on marine biota. From these sediment resuspension experiments, we determined OC-normalized partition coefficients of PAHs between sediment and water (K oc ) and found that during such events, the transfer of PAHs from sediment particles to seawater was lower than that predicted from octanol-water partition coefficients (K ow ) (i.e., measured K oc  > K oc predicted from K ow ). The results confirmed the sequestration role of sedimentary OC quality and grain size on PAHs; the OM diagenetic state seemed to impact the partition process but in a relatively minor way. Furthermore, differences were observed between 2-4 ring and 5-6 ring PAHs, with the latter displaying a relatively higher mobility towards seawater. These differences may be explained by the distribution of these two PAH pools within different OM moieties, such as humic substances and black carbon. Copyright © 2017 Elsevier Ltd. All rights reserved.

Controls on sediment cover in bedrock-alluvial channels of the Henry Mountains, Utah

Science.gov (United States)

Hodge, R. A.; Yager, E.; Johnson, J. P.; Tranmer, A.

2017-12-01

The location and extent of sediment cover in bedrock-alluvial channels influences sediment transport rates, channel incision and instream ecology. However, factors affecting sediment cover and how it responds to changes in relative sediment supply have rarely been quantitatively evaluated in field settings. Using field surveys and SFM analysis of channel reach topography, we quantified sediment cover and channel properties including slope, width, grain size distributions, and bedrock and alluvial roughness in North Wash and Chelada Creek in the Henry Mountains, Utah. Along reaches where upstream sediment supply does not appear to be restricted, we find that the fraction of local bedrock exposure increases as a function of local relative transport capacity . In a downstream section of Chelada Creek, decadal-scale sediment supply has been restricted by an upstream culvert that has caused a backwater effect and corresponding upstream deposition. In this section, alluvial cover is uncorrelated with local stream power. To test the impact of relative sediment supply on sediment cover, a 1D sediment transport model was used to predict the equilibrium sediment cover in Chelada Creek under varying flow and sediment supply conditions. Sediment transport in each model section was predicted using the partial cover model of Johnson (2015), which accounts for differences in bedrock and alluvial roughness on critical shear stress and flow resistance. Model runs in which sediment supply was approximately equal to mean transport capacity produced a pattern of sediment cover which best matched the field observations upstream of the culvert. However, runs where sediment supply was under-capacity produced the pattern most similar to field observations downstream of the culvert, consistent with our field-based interpretations. Model results were insensitive to initial sediment cover, and equilibrium was relatively quickly reached, suggesting that the channel is responsive to changes in

Isotherm, kinetic, and thermodynamic study of ciprofloxacin sorption on sediments.

Science.gov (United States)

Mutavdžić Pavlović, Dragana; Ćurković, Lidija; Grčić, Ivana; Šimić, Iva; Župan, Josip

2017-04-01

In this study, equilibrium isotherms, kinetics and thermodynamics of ciprofloxacin on seven sediments in a batch sorption process were examined. The effects of contact time, initial ciprofloxacin concentration, temperature and ionic strength on the sorption process were studied. The K d parameter from linear sorption model was determined by linear regression analysis, while the Freundlich and Dubinin-Radushkevich (D-R) sorption models were applied to describe the equilibrium isotherms by linear and nonlinear methods. The estimated K d values varied from 171 to 37,347 mL/g. The obtained values of E (free energy estimated from D-R isotherm model) were between 3.51 and 8.64 kJ/mol, which indicated a physical nature of ciprofloxacin sorption on studied sediments. According to obtained n values as measure of intensity of sorption estimate from Freundlich isotherm model (from 0.69 to 1.442), ciprofloxacin sorption on sediments can be categorized from poor to moderately difficult sorption characteristics. Kinetics data were best fitted by the pseudo-second-order model (R 2  > 0.999). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°) and entropy (ΔS°) were calculated to estimate the nature of ciprofloxacin sorption. Results suggested that sorption on sediments was a spontaneous exothermic process.

Control of Delta Avulsion by Downstream Sediment Sinks

Science.gov (United States)

Salter, Gerard; Paola, Chris; Voller, Vaughan R.

2018-01-01

Understanding how fluxes are partitioned at delta bifurcations is critical for predicting patterns of land loss and gain in deltas worldwide. Although the dynamics of river deltas are influenced from both upstream and downstream, previous studies of bifurcations have focused on upstream controls. Using a quasi-1-D bifurcation model, we show that flow switching in bifurcations is strongly influenced by downstream sediment sinks. We find that coupling between upstream and downstream feedbacks can lead to oscillations in water and sediment flux partitioning. The frequency and initial rate of growth/decay of the oscillations depend on both upstream and downstream conditions, with dimensionless bifurcate length and bypass fraction emerging as key downstream parameters. With a strong offshore sink, causing bypass in the bifurcate branches, we find that bifurcation dynamics become "frozen"; that is, the bifurcation settles on a permanent discharge ratio. In contrast, under depositional conditions, we identify three dynamical regimes: symmetric; soft avulsion, where both branches remain open but the dominant branch switches; and full avulsion. Finally, we show that differential subsidence alters these regimes, with the difference in average sediment supply to each branch exactly compensating for the difference in accommodation generation. Additionally, the model predicts that bifurcations with shorter branches are less asymmetric than bifurcations with longer branches, all else equal, providing a possible explanation for the difference between backwater length distributaries, which tend to be avulsive, and relatively stable mouth-bar-scale networks. We conclude that bifurcations are sensitive both quantitatively and qualitatively to downstream sinks.

Polymers as reference partitioning phase: polymer calibration for an analytically operational approach to quantify multimedia phase partitioning

DEFF Research Database (Denmark)

Gilbert, Dorothea; Witt, Gesine; Smedes, Foppe

2016-01-01

Polymers are increasingly applied for the enrichment of hydrophobic organic chemicals (HOCs) from various types of samples and media in many analytical partitioning-based measuring techniques. We propose using polymers as a reference partitioning phase and introduce polymer-polymer partitioning......-air) and multimedia partition coefficients (lipid-water, air-water) were calculated by applying the new concept of a polymer as reference partitioning phase and by using polymer-polymer partition coefficients as conversion factors. The present study encourages the use of polymer-polymer partition coefficients...

Concentrations of some elements in the coastal sea sediments. Bays with marinas

International Nuclear Information System (INIS)

Obhodas, J.; Kutle, A.; Valkovic, V.

2006-01-01

Surface sediments and sediment cores from two bays in the Adriatic sea (Punat Bay and Soline Bay, Croatia) have been analyzed for a number of elements, in particular: Ti, V, Mn, Fe, Cu, Zn, As and Pb, by using XRF. Maps of elemental distribution in surface sediments show increased concentrations for some elements present in antifouling paints (Cu, Zn, Pb) near the service areas in the villages or marinas. Core profiles for these elements were used to evaluate the environmental impact of newly constructed marinas. Source partition indicates the influence of other sources located in near by villages. The critical factor in these considerations was shown to be water exchange with the open sea. (author)

The relative importance of the adsorption and partitioning mechanisms in hydrophilic interaction liquid chromatography.

Science.gov (United States)

Gritti, Fabrice; Höltzel, Alexandra; Tallarek, Ulrich; Guiochon, Georges

2015-01-09

We propose an original model of effective diffusion along packed beds of mesoporous particles for HILIC developed by combining Torquatos model for heterogeneous beds (external eluent+particles), Landauers model for porous particles (solid skeleton+internal eluent), and the time-averaged model for the internal eluent (bulk phase+diffuse water (W) layer+rigid W layer). The new model allows to determine the analyte concentration in rigid and diffuse W layer from the experimentally determined retention factor and intra-particle diffusivity and thus to distinguish the retentive contributions from adsorption and partitioning. We apply the model to investigate the separation of toluene (TO, as a non-retained compound), nortriptyline (NT), cytosine (CYT), and niacin (NA) on an organic ethyl/inorganic silica hybrid adsorbent. Elution conditions are varied through the choice of a third solvent (W, ethanol, tetrahydrofuran (THF), acetonitrile (ACN), or n-hexane) in a mobile phase (MP) of ACN/aqueous acetate buffer (pH 5)/third solvent (90/5/5, v/v/v). Whereas NA and CYT retention factors increase monotonously from W to n-hexane as third solvent, NT retention reaches its maximum with polar aprotic third solvents. The involved equilibrium constants for adsorption and partitioning, however, do not follow the same trends as the overall retention factors. NT retention is dominated by partitioning and NA retention by adsorption, while CYT retention is controlled by adsorption rather than partitioning. Our results reveal that the relative importance of adsorption and partitioning mechanisms depends in a complex way from analyte properties and experimental parameters and cannot be predicted generally. Copyright © 2014 Elsevier B.V. All rights reserved.

Predicting long-term and short-term tidal flat morphodynamics using a dynamic equilibrium theory

NARCIS (Netherlands)

Hu, Z.; Wang, Z.B.; Zitman, T.J.; Stive, M.J.F.; Bouma, T.J.

2015-01-01

Dynamic equilibrium theory is a fruitful concept, which we use to systematically explain the tidal flat morphodynamic response to tidal currents, wind waves, sediment supply, and other sedimentological drivers. This theory stems from a simple analytical model that derives the tide- or wave-dominated

Partitioning of fluorotelomer alcohols to octanol and different sources of dissolved organic carbon.

Science.gov (United States)

Carmosini, Nadia; Lee, Linda S

2008-09-01

Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their equilibrium partitioning behavior. Experimentally determined partition coefficients for FTOHs between soil/water and air/water have been reported, but direct measurements of partition coefficients for dissolved organic carbon (DOC)/water (K(doc)) and octanol/ water(K(ow)) have been lacking. Here we measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water using enhanced solubility or dialysis bag techniques, and also quantified K(ow) values for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log K(doc) values for 8:2 FTOH using the enhanced solubility technique with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00-3.97 with the lowest values obtained for the biosolids and an average across all other DOC sources (biosolid DOC excluded) of 3.54 +/- 0.29. For 6:2 FTOH and Aldrich humic acid, a log K(doc) value of 1.96 +/- 0.45 was measured using the dialysis technique. These average values are approximately 1 to 2 log units lower than previously indirectly estimated K(doc) values. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log K(ow) values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) were in good agreement with previously reported estimates. Using relationships between experimentally measured partition coefficients and C-atom chain length, we estimated K(doc) and K(ow) values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally.

Soils and organic sediments

International Nuclear Information System (INIS)

Head, M.J.

1999-01-01

The organic component of soils is basically made up of substances of an individual nature (fats, waxes, resins, proteins, tannic substances, and many others), and humic substances (Kononova, 1966). These are complex polymers formed from breakdown products of the chemical and biological degradation of plant and animal residues. They are dark coloured, acidic, predominantly aromatic compounds ranging in molecular weight from less than one thousand to tens of thousands (Schnitzer, 1977). They can be partitioned into three main fractions:(i) Humic acid, which is soluble in dilute alkaline solution, but can be precipitated by acidification of the alkaline extract.(ii) Fulvic acid, which is soluble in alkaline solution, but is also soluble on acidification.(iii) Humin that cannot be extracted from the soil or sediment by dilute acid or alkaline solutions. It has mostly been assumed that the humic and fulvic acid components of the soil are part of the mobile, or 'active' component, and the humin component is part of the 'passive' component. Other types of organic sediments are likely to contain chemical breakdown products of plant material, plant fragments and material brought in from outside sources. The outside material can be contemporaneous with sediment deposition, can be older material, or younger material incorporated into the sediment long after deposition. Recognition of 'foreign' material is essential for dating, but is not an easy task. Examples of separation techniques for humic and non humic components are evaluated for their efficiency

Inference of directional selection and mutation parameters assuming equilibrium.

Science.gov (United States)

Vogl, Claus; Bergman, Juraj

2015-12-01

In a classical study, Wright (1931) proposed a model for the evolution of a biallelic locus under the influence of mutation, directional selection and drift. He derived the equilibrium distribution of the allelic proportion conditional on the scaled mutation rate, the mutation bias and the scaled strength of directional selection. The equilibrium distribution can be used for inference of these parameters with genome-wide datasets of "site frequency spectra" (SFS). Assuming that the scaled mutation rate is low, Wright's model can be approximated by a boundary-mutation model, where mutations are introduced into the population exclusively from sites fixed for the preferred or unpreferred allelic states. With the boundary-mutation model, inference can be partitioned: (i) the shape of the SFS distribution within the polymorphic region is determined by random drift and directional selection, but not by the mutation parameters, such that inference of the selection parameter relies exclusively on the polymorphic sites in the SFS; (ii) the mutation parameters can be inferred from the amount of polymorphic and monomorphic preferred and unpreferred alleles, conditional on the selection parameter. Herein, we derive maximum likelihood estimators for the mutation and selection parameters in equilibrium and apply the method to simulated SFS data as well as empirical data from a Madagascar population of Drosophila simulans. Copyright © 2015 Elsevier Inc. All rights reserved.

Polyacrylate–water partitioning of biocidal compounds: Enhancing the understanding of biocide partitioning between render and water

DEFF Research Database (Denmark)

Bollmann, Ulla E.; Ou, Yi; Mayer, Philipp

2014-01-01

-N-octylisothiazolinone). The correlation of the polyacrylate-water partition constants with the octanol-water partition constants is significant, but the polyacrylate-water partition constants were predominantly below octanol-water partition constants (Kow). The comparison with render-water distribution constants showed that estimating...

Transport of perfluoroalkyl acids in a water-saturated sediment column investigated under near-natural conditions

International Nuclear Information System (INIS)

Vierke, Lena; Möller, Axel; Klitzke, Sondra

2014-01-01

The aim of this study was to gain an understanding of the transport of C 4–10 perfluoroalkyl carboxylic acids (PFCAs) and C 4,6,8 perfluoroalkyl sulfonic acids (PFSAs) in a water-saturated sediment column representing a riverbank filtration scenario under near-natural conditions. Short-chain PFCAs and PFSAs with up to six C-atoms showed complete tracer-like breakthrough. Longer chain ones were retarded due to sorption to the sediment or due to other processes in the aqueous phase. The study reports the first column derived sediment–water partition coefficients ranging from 0.01 cm 3 g −1 to 0.41 cm 3 g −1 for C 4,6 PFSAs and from 0.0 cm 3 g −1 to 6.5 cm 3 g −1 for C 4,5,6,8,9 PFCAs. The results clearly indicate that short-chain PFCAs and PFSAs may pose a problem if contaminated surface waters are used for drinking water production via riverbank filtration. Highlights: • Transport of per- and polyfluorinated compounds in a riverbank filtration scenario. • Investigations under near-natural conditions with a water-saturated sediment column. • Processes in water and sediment control the transport of analytes. • Short chain PFCAs and PFSAs are not retarded in the water-saturated sediment column. • First column derived sediment–water partition coefficients. -- Quantification of breakthrough of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) under conditions simulating a riverbank filtration scenario

Determination of sedimentation rate in Thane creek using 210Pb dating

International Nuclear Information System (INIS)

Sahu, S.K.; Bhangare, R.C.; Ajmal, P.Y; Tiwari, M.; Pandit, G.G.; Puranik, V.D.

2012-01-01

Sediments are good representatives of the geochemical history of a particular area. They can be regarded as good archives of environmental processes and their effects. Therefore, the study of sediments in coastal areas has great importance for the understanding of the interaction between human activities and marine systems. The sedimentation process can be correlated with time by assessing decays of radionuclides like 210 Pb, 137 Cs and 14 C in different layers of it. 210 Pb and its environmental cycle have been commonly used as environmental tracer in many environmental studies. For assessment of chronological history of pollution in the Mumbai region, sediment samples were collected from Thane creek and sedimentation rates were estimated by measurement of 210 Po activity which is in equilibrium with 210 Pb

Polydimethylsiloxane-air partition ratios for semi-volatile organic compounds by GC-based measurement and COSMO-RS estimation: Rapid measurements and accurate modelling.

Science.gov (United States)

Okeme, Joseph O; Parnis, J Mark; Poole, Justen; Diamond, Miriam L; Jantunen, Liisa M

2016-08-01

Polydimethylsiloxane (PDMS) shows promise for use as a passive air sampler (PAS) for semi-volatile organic compounds (SVOCs). To use PDMS as a PAS, knowledge of its chemical-specific partitioning behaviour and time to equilibrium is needed. Here we report on the effectiveness of two approaches for estimating the partitioning properties of polydimethylsiloxane (PDMS), values of PDMS-to-air partition ratios or coefficients (KPDMS-Air), and time to equilibrium of a range of SVOCs. Measured values of KPDMS-Air, Exp' at 25 °C obtained using the gas chromatography retention method (GC-RT) were compared with estimates from a poly-parameter free energy relationship (pp-FLER) and a COSMO-RS oligomer-based model. Target SVOCs included novel flame retardants (NFRs), polybrominated diphenyl ethers (PBDEs), polycyclic aromatic hydrocarbons (PAHs), organophosphate flame retardants (OPFRs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). Significant positive relationships were found between log KPDMS-Air, Exp' and estimates made using the pp-FLER model (log KPDMS-Air, pp-LFER) and the COSMOtherm program (log KPDMS-Air, COSMOtherm). The discrepancy and bias between measured and predicted values were much higher for COSMO-RS than the pp-LFER model, indicating the anticipated better performance of the pp-LFER model than COSMO-RS. Calculations made using measured KPDMS-Air, Exp' values show that a PDMS PAS of 0.1 cm thickness will reach 25% of its equilibrium capacity in ∼1 day for alpha-hexachlorocyclohexane (α-HCH) to ∼ 500 years for tris (4-tert-butylphenyl) phosphate (TTBPP), which brackets the volatility range of all compounds tested. The results presented show the utility of GC-RT method for rapid and precise measurements of KPDMS-Air. Copyright © 2016. Published by Elsevier Ltd.

Quasi-equilibrium analysis of the ion-pair mediated membrane transport of low-permeability drugs.

Science.gov (United States)

Miller, Jonathan M; Dahan, Arik; Gupta, Deepak; Varghese, Sheeba; Amidon, Gordon L

2009-07-01

The aim of this research was to gain a mechanistic understanding of ion-pair mediated membrane transport of low-permeability drugs. Quasi-equilibrium mass transport analyses were developed to describe the ion-pair mediated octanol-buffer partitioning and hydrophobic membrane permeation of the model basic drug phenformin. Three lipophilic counterions were employed: p-toluenesulfonic acid, 2-naphthalenesulfonic acid, and 1-hydroxy-2-naphthoic acid (HNAP). Association constants and intrinsic octanol-buffer partition coefficients (Log P(AB)) of the ion-pairs were obtained by fitting a transport model to double reciprocal plots of apparent octanol-buffer distribution coefficients versus counterion concentration. All three counterions enhanced the lipophilicity of phenformin, with HNAP providing the greatest increase in Log P(AB), 3.7 units over phenformin alone. HNAP also enhanced the apparent membrane permeability of phenformin, 27-fold in the PAMPA model, and 4.9-fold across Caco-2 cell monolayers. As predicted from a quasi-equilibrium analysis of ion-pair mediated membrane transport, an order of magnitude increase in phenformin flux was observed per log increase in counterion concentration, such that log-log plots of phenformin flux versus HNAP concentration gave linear relationships. These results provide increased understanding of the underlying mechanisms of ion-pair mediated membrane transport, emphasizing the potential of this approach to enable oral delivery of low-permeability drugs.

Carbon 14, carbon 13 and oxygen 18 in carbonate sediments from lake Titicaca. Preliminary estimates of sedimentation rate and paleoclimatological attempt

International Nuclear Information System (INIS)

Fontes, J.-C.; Boulange, Bruno; Rodrigo, L.-A.

1981-01-01

Stable isotope and radiocarbon measurements in carbonates from Titicaca lake indicate equilibrium with lake water and atmospheric CO 2 . Average sedimentation rate is close to 0,5 mm.yr -1 for the last millenium which was marked by large fluctuations of the hydrologic balance and lake level [fr

Carbon 14, carbon 13 and oxygen 18 in carbonate sediments from Lake Titicaca. Preliminary estimates of sedimentation rate and paleoclimatological attempt

Energy Technology Data Exchange (ETDEWEB)

Fontes, J.C. (Paris-11 Univ., 91 - Orsay (France)); Boulange, B. (Orstom, 75 - Paris (France)); Rodrigo, L.A. (Universidad Mayor de San Andres, La Paz (Bolivia). Lab. de Fisica Cosmica de Chacaltaya)

1981-07-06

Stable isotope and radiocarbon measurements in carbonates from Lake Titicaca indicate equilibrium with lake water and atmospheric CO/sub 2/. Average sedimentation rate is close to 0,5 mm.yr/sup -1/ for the last millenium which was marked by large fluctuations of the hydrologic balance and lake level.

Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

International Nuclear Information System (INIS)

Ackerman, J.P.; Johnson, T.R.

1993-01-01

The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing

Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

Energy Technology Data Exchange (ETDEWEB)

Ackerman, J.P.; Johnson, T.R.

1993-10-01

The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing.

Investigations of Cu, Pb and Zn partitioning by sequential extraction in harbour sediments after electrodialytic remediation

DEFF Research Database (Denmark)

Kirkelund, Gunvor Marie; Ottosen, Lisbeth M.; Villumsen, Arne

2010-01-01

remediation time. A three step sequential extraction scheme (BCR), with an extra residual step, was used to evaluate the heavy metal distribution in the sediments before and after electrodialytic remediation. Cu was mainly associated with the oxidisable phase of the sediment, both before and after remediation...

Sorption kinetics of Cs and Sr in sediments of a Savannah River Site reservoir

International Nuclear Information System (INIS)

Stephens, J.A.

1997-07-01

Laboratory measurements of the sorption and desorption of 134 Cs and 85 Sr to sediments were conducted. These sediments were sampled from the profundal zone of Par Pond at the Savannah River Site, Aiken, South Carolina. The isotopes 134 Cs and 85 Sr were used to trace the sorption properties of the main contaminants found in the reservoir which are 137 Cs and 90 Sr respectively. The sorption behavior of these two elements was studied using spiked sediment/water slurries of a known mass to volume ratio. The results reveal that Sr undergoes significant reversible sorption while a fraction of Cs irreversibly sorbs to the sediment. The calculated distribution coefficient Kd at equilibrium was (3 ± 0.6) x 10 3 for 134 Cs after 60 d and (1 ± 0.2) x 10 3 for 85 Sr after 7 d at pH ∼ 6 and slurry ratio of 1:1000 g/ml. The K d for 134 Cs ranged from 2 x 10 2 to 3 x 10 4 depending on pH and conductivity. The 85 Sr reached equilibrium in a few days, while 134 Cs reached an apparent equilibrium in 1--2 months. The K d for 134 Cs was a function of the slurry ratio, pH, conductivity, and contact time. These factors were interrelated since the sediments released ions to the slurry mixture which decreased the pH and increased the conductivity. A sorption isotherm measured for 134 Cs was linear at water concentrations from 60 mBq/ml to 20 Bq/ml. A kinetic model was proposed to describe the basic sorption of 134 Cs to Par Pond sediments under homogeneous laboratory conditions

The complex formation-partition and partition-association models of solvent extraction of ions

International Nuclear Information System (INIS)

Siekierski, S.

1976-01-01

Two models of the extraction process have been proposed. In the first model it is assumed that the partitioning neutral species is at first formed in the aqueous phase and then transferred into the organic phase. The second model is based on the assumption that equivalent amounts of cations are at first transferred from the aqueous into the organic phase and then associated to form a neutral molecule. The role of the solubility parameter in extraction and the relation between the solubility of liquid organic substances in water and the partition of complexes have been discussed. The extraction of simple complexes and complexes with organic ligands has been discussed using the first model. Partition coefficients have been calculated theoretically and compared with experimental values in some very simple cases. The extraction of ion pairs has been discussed using the partition-association model and the concept of single-ion partition coefficients. (author)

Influence of contact time and sediment composition on the bioavailability of Cd in sediments

International Nuclear Information System (INIS)

Zhong Huan; Kraemer, Lisa; Evans, Douglas

2013-01-01

Stable isotope 111 Cd was spiked into sediments of different organic content levels for 3 days to 2 months. Bioavailability of spiked Cd to deposit-feeders, assessed by in vitro Cd solubilization, generally decreased with contact time but became comparable with that of background Cd after 2 months. This could be explained by the gradual transfer of Cd from the more mobile geochemical phase (carbonate associated phase) to more refractory phases (Fe–Mn oxide associated phase, and organic associated phase) within 2 months. The sedimentary organic content had a weak effect on Cd solubilization, while the distribution of Cd in carbonate or Fe–Mn oxide associated phase could have a larger influence on the solubilization of sedimentary Cd and its change with contact time. The observations in this study emphasize the need to consider Cd sequestration over time in sediments of various compositions, which would be useful in risk assessment of contaminated sediments. Highlights: ► Cd may reach equilibrium in sediments after 2 months of aging. ► Sediment composition could affect change of Cd bioavailability with contact time. ► Sedimentary organic content has a weak effect on Cd bioavailability. ► Cd associated with carbonates is more bioavailable than Cd with Fe/Mn oxides. ► Change in Cd solid speciation explains decrease of Cd bioavailability over time. - Transfer of Cd from carbonate phase to Fe–Mn oxide phase in sediments was important in affecting the decrease of Cd bioavailability over time.

A study of lead and cadmium speciation in some estuarine and coastal sediments

Digital Repository Service at National Institute of Oceanography (India)

Chakraborty, P.; Babu, P.V.R.; Sarma, V.V.

., Campbell, M., Weir, E., 2002, Identifying and managing adverse environmental health effects: 3. Lead exposure. CMAJ 166, 1287–1292. Stohs, S.J., Bagchi, D., 1995, Oxidative mechanisms in the toxicity of metal ions. Free Radical Biology and Medicine, 18... the kinetic speciation of Pb and Cd in the coastal and estuarine sediments of Bay of Bengal. Consider sediments samples of n different components, in which each component, M-Sediment i , exists in equilibrium with its dissociation products: the free metal...

COMPUTING VERTICES OF INTEGER PARTITION POLYTOPES

Directory of Open Access Journals (Sweden)

A. S. Vroublevski

2015-01-01

Full Text Available The paper describes a method of generating vertices of the polytopes of integer partitions that was used by the authors to calculate all vertices and support vertices of the partition polytopes for all n ≤ 105 and all knapsack partitions of n ≤ 165. The method avoids generating all partitions of n. The vertices are determined with the help of sufficient and necessary conditions; in the hard cases, the well-known program Polymake is used. Some computational aspects are exposed in more detail. These are the algorithm for checking the criterion that characterizes partitions that are convex combinations of two other partitions; the way of using two combinatorial operations that transform the known vertices to the new ones; and employing the Polymake to recognize a limited number (for small n of partitions that need three or more other partitions for being convexly expressed. We discuss the computational results on the numbers of vertices and support vertices of the partition polytopes and some appealing problems these results give rise to.

Sorption Characteristics of Sediments in the Upper Mississippi River System Above Lake Pepin

National Research Council Canada - National Science Library

James, W

1999-01-01

This technical note examines equilibrium phosphorus processes and sorption characteristics for sediments collected from the Minnesota River, immediately upstream from its confluence with the Upper Mississippi River (UMR...

Geochemical partitioning of Cu and Ni in mangrove sediments: Relationships with their bioavailability

Digital Repository Service at National Institute of Oceanography (India)

Chakraborty, P.; Ramteke, D.; Chakraborty, S.

Sequential extraction study was performed to determine the concentrations of non-residual metal-complexes in the mangrove sediments from the Divar Island, (west coast of India). Accumulation of metal in the mangrove roots (from the same location...

The partitioning of copper among selected phases of geologic media of two porphyry copper districts, Puerto Rico

Science.gov (United States)

Learned, R.E.; Chao, T.T.; Sanzolone, R.F.

1981-01-01

In experiments designed to determine the manner in which copper is partitioned among selected phases that constitute geologic media, we have applied the five-step sequential extraction procedure of Chao and Theobald to the analysis of drill core, soils, and stream sediments of the Rio Vivi and Rio Tanama porphyry copper districts of Puerto Rico. The extraction procedure affords a convenient means of determining the trace-metal content of the following fractions: (1) Mn oxides and "reactive" Fe oxides; (2) "amorphous" Fe oxides; (3) "crystalline" Fe oxides; (4) sulfides and magnetite; and (5) silicates. An additional extraction between steps (1) and (2) was performed to determine organic-related copper in stream sediments. The experimental results indicate that apportionment of copper among phases constituting geologic media is a function of geochemical environment. Distinctive partitioning patterns were derived from the analysis of drill core from each of three geochemical zones: (a) the supergene zone of oxidation; (b) the supergene zone of enrichment; and (c) the hypogene zone; and similarly, from the analysis of; (d) soils on a weakly leached capping; (e) soils on a strongly leached capping; and (f) active stream sediment. The experimental results also show that geochemical contrasts (anomaly-to-background ratios) vary widely among the five fractions of each sampling medium investigated, and that at least one fraction of each medium provides substantially stronger contrast than does the bulk medium. Fraction (1) provides optimal contrast for stream sediments of the district; fraction (2) provides optimal contrast for soils on a weakly leached capping; fraction (3) provides optimal contrast for soils on a strongly leached capping. Selective extraction procedures appear to have important applications to the orientation and interpretive stages of geochemical exploration. Further investigation and testing of a similar nature are recommended. ?? 1981.

Study of the behaviour of radioactive cobalt in the coastal environment

International Nuclear Information System (INIS)

Hansen, A.M.

1988-05-01

Mineral surfaces play an important role in regulating the concentrations of dissolved radionuclides and other trace elements in natural water systems. In bulk sediments, the different minerals present may exhibit completely different uptake mechanisms, and compete simultaneously for the same radionuclide. This study examines the adsorption behaviour of radiocobalt in two natural sediments collected in the coastal area adjacent to the Laguna Verde Nuclear Power Plant Site in Vera Cruz, Mexico. These sediment samples provided a complex substrate for trace metal removal, as shown by their different physical, chemical and mineralogical properties. Radiocobalt partitioning between these sediments and solution was determined using an isotope dilution technique, with Co-57 as the tracer. The uptake experiments were done under controlled conditions to determine the effects of pH, ionic strength, sediment binding site concentration, and mineral composition on Co adsorption. The experimental work included both time-dependent and equilibrium studies of Co partitioning. The time-dependent studies revealed two different rates (and hence processes) responsible for the removal of Co onto the sediments: a relatively fast initial reaction (complete within one week) which appears to be due to uptake on non-carbonate surface (perhaps oxide surfaces), and a slower rate of uptake (reaching equilibrium within 60 d or more) due to the formation of solid solutions of Co on calcite surfaces. The sorption of Co decreased as the ionic strength increased. In seawater, it appears that Mg ions suppress radiocobalt sorption (particularly during the fast uptake step), perhaps by decreasing the number of available binding sites on the sediments. The results of these uptake studies were modeled successfully using the triple layer-surface complexation model, which treats surface functional groups on the adsorbent as ligands capable of forming surface complexes with solution species. Refs, figs and

Assessment of heavy metals pollution in bottom sediments of the Arabian Gulf after the Gulf War oil spill 1991

International Nuclear Information System (INIS)

Nasr, S.M.; Ahmed, M.H.; El-Raey, M.; Frihy, O.E.; Abdel Motti, A.

1999-01-01

The major objective of this study was to carry out a sequential geochemical extraction scheme for the partitioning of Fe, Mn, Co, Cu, Zn, Ni, Cr and Pb in the bottom sediments of the Arabian Gulf to detect any potential pollution impact on the gulf sediments following the 1991 gulf war oil spill, and to differentiate between anthropogenic inputs and natural background of heavy metals

Partitioning of etofenprox under simulated California rice-growing conditions.

Science.gov (United States)

Vasquez, Martice E; Gunasekara, Amrith S; Cahill, Thomas M; Tjeerdema, Ronald S

2010-01-01

The pyrethroid insecticide etofenprox is of current interest to rice farmers in the Sacramento Valley owing to its effectiveness against the rice water weevil, Lissorhoptrus oryzophilus Kuschel. This study aimed to describe the partitioning of etofenprox under simulated rice field conditions by determining its Henry's law constant (H) (an estimate of volatilization) and organic carbon-normalized soil-water distribution coefficient (K(oc)) at representative field temperatures. A comparison of etofenprox and lambda-cyhalothrin is presented using a level-1 fugacity model. Experimental determination of H revealed that etofenprox partitioned onto the apparatus walls and did not significantly volatilize; the maximum value of H was estimated to be 6.81 x 10(-1) Pa m(3) mol(-1) at 25 degrees C, based on its air and water method detection limits. Calculated values for H ranged from 5.6 x 10(-3) Pa m(3) mol(-1) at 5 degrees C to 2.9 x 10(-1) Pa m(3) mol(-1) at 40 degrees C, based on estimated solubility and vapor pressure values at various temperatures. Log K(oc) values (at 25 degrees C) were experimentally determined to be 6.0 and 6.4 for Princeton and Richvale rice field soils, respectively, and were very similar to the values for other pyrethroids. Finally, temperature appears to have little influence on etofenprox sorption, as the log K(oc) for the Princeton soil at 35 degrees C was 6.1. High sorption coefficients and relatively insignificant desorption and volatilization of etofenprox suggest that its insolubility drives it to partition from water by sorbing to soils with high affinity. Offsite movement is unlikely unless transported in a bound state on suspended sediments.

Mercury partition in the interface between a contaminated lagoon and the ocean: The role of particulate load and composition

International Nuclear Information System (INIS)

Pato, P.; Otero, M.; Valega, M.; Lopes, C.B.; Pereira, M.E.; Duarte, A.C.

2010-01-01

After having estimated the patterns of flow to the ocean and found some seasonal and tidal differences, mainly with regard to the relative importance of dissolved and particulate fractions, mercury partitioning at the interface between a contaminated lagoon and the Atlantic Ocean was investigated during four tidal cycles in contrasting season and tidal regimes. Mercury was found to be located predominantely in the particulate fraction throughout the year, contributing to its retention within the system. Seasonal conditions, variations in marine and fluvial signals and processes affecting bed sediment resuspension influenced the character and concentration of suspended particulate matter in the water column. Variation in the nature, levels and partitioning of organic carbon in the particulate fraction affected levels of particulate mercury as well as mercury partitioning. These results highlight the dominant role of suspended particulate matter in the distribution of anthropogenic mercury and reinforce the importance of competitive behavior related to organic carbon in mercury scavenging.

Effects of sulfur on lead partitioning during sludge incineration based on experiments and thermodynamic calculations.

Science.gov (United States)

Liu, Jing-yong; Huang, Shu-jie; Sun, Shui-yu; Ning, Xun-an; He, Rui-zhe; Li, Xiao-ming; Chen, Tao; Luo, Guang-qian; Xie, Wu-ming; Wang, Yu-Jie; Zhuo, Zhong-xu; Fu, Jie-wen

2015-04-01

Experiments in a tubular furnace reactor and thermodynamic equilibrium calculations were conducted to investigate the impact of sulfur compounds on the migration of lead (Pb) during sludge incineration. Representative samples of typical sludge with and without the addition of sulfur compounds were combusted at 850 °C, and the partitioning of Pb in the solid phase (bottom ash) and gas phase (fly ash and flue gas) was quantified. The results indicate that three types of sulfur compounds (S, Na2S and Na2SO4) added to the sludge could facilitate the volatilization of Pb in the gas phase (fly ash and flue gas) into metal sulfates displacing its sulfides and some of its oxides. The effect of promoting Pb volatilization by adding Na2SO4 and Na2S was superior to that of the addition of S. In bottom ash, different metallic sulfides were found in the forms of lead sulfide, aluminosilicate minerals, and polymetallic-sulfides, which were minimally volatilized. The chemical equilibrium calculations indicated that sulfur stabilizes Pb in the form of PbSO4(s) at low temperatures (incineration process mainly depended on the gas phase reaction, the surface reaction, the volatilization of products, and the concentration of Si, Ca and Al-containing compounds in the sludge. These findings provide useful information for understanding the partitioning behavior of Pb, facilitating the development of strategies to control the volatilization of Pb during sludge incineration. Copyright © 2014 Elsevier Ltd. All rights reserved.

Equilibrium sampling of environmental pollutants in fish: comparison with lipid-normalized concentrations and homogenization effects on chemical activity.

Science.gov (United States)

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha; McLachlan, Michael S

2011-07-01

Equilibrium sampling of organic pollutants into the silicone polydimethylsiloxane (PDMS) has recently been applied in biological tissues including fish. Pollutant concentrations in PDMS can then be multiplied with lipid/PDMS distribution coefficients (D(Lipid,PDMS) ) to obtain concentrations in fish lipids. In the present study, PDMS thin films were used for equilibrium sampling of polychlorinated biphenyls (PCBs) in intact tissue of two eels and one salmon. A classical exhaustive extraction technique to determine lipid-normalized PCB concentrations, which assigns the body burden of the chemical to the lipid fraction of the fish, was additionally applied. Lipid-based PCB concentrations obtained by equilibrium sampling were 85 to 106% (Norwegian Atlantic salmon), 108 to 128% (Baltic Sea eel), and 51 to 83% (Finnish lake eel) of those determined using total extraction. This supports the validity of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher in the homogenates (statistically significant in 18 of 21 cases, p equilibrium sampling and partition coefficients determined using tissue homogenates. Copyright © 2011 SETAC.

Space-partition method for the variance-based sensitivity analysis: Optimal partition scheme and comparative study

International Nuclear Information System (INIS)

Zhai, Qingqing; Yang, Jun; Zhao, Yu

2014-01-01

Variance-based sensitivity analysis has been widely studied and asserted itself among practitioners. Monte Carlo simulation methods are well developed in the calculation of variance-based sensitivity indices but they do not make full use of each model run. Recently, several works mentioned a scatter-plot partitioning method to estimate the variance-based sensitivity indices from given data, where a single bunch of samples is sufficient to estimate all the sensitivity indices. This paper focuses on the space-partition method in the estimation of variance-based sensitivity indices, and its convergence and other performances are investigated. Since the method heavily depends on the partition scheme, the influence of the partition scheme is discussed and the optimal partition scheme is proposed based on the minimized estimator's variance. A decomposition and integration procedure is proposed to improve the estimation quality for higher order sensitivity indices. The proposed space-partition method is compared with the more traditional method and test cases show that it outperforms the traditional one

Experimental determination of the partitioning coefficient of β-pinene oxidation products in SOAs.

Science.gov (United States)

Hohaus, Thorsten; Gensch, Iulia; Kimmel, Joel; Worsnop, Douglas R; Kiendler-Scharr, Astrid

2015-06-14

The composition of secondary organic aerosols (SOAs) formed by β-pinene ozonolysis was experimentally investigated in the Juelich aerosol chamber. Partitioning of oxidation products between gas and particles was measured through concurrent concentration measurements in both phases. Partitioning coefficients (Kp) of 2.23 × 10(-5) ± 3.20 × 10(-6) m(3) μg(-1) for nopinone, 4.86 × 10(-4) ± 1.80 × 10(-4) m(3) μg(-1) for apoverbenone, 6.84 × 10(-4) ± 1.52 × 10(-4) m(3) μg(-1) for oxonopinone and 2.00 × 10(-3) ± 1.13 × 10(-3) m(3) μg(-1) for hydroxynopinone were derived, showing higher values for more oxygenated species. The observed Kp values were compared with values predicted using two different semi-empirical approaches. Both methods led to an underestimation of the partitioning coefficients with systematic differences between the methods. Assuming that the deviation between the experiment and the model is due to non-ideality of the mixed solution in particles, activity coefficients of 4.82 × 10(-2) for nopinone, 2.17 × 10(-3) for apoverbenone, 3.09 × 10(-1) for oxonopinone and 7.74 × 10(-1) for hydroxynopinone would result using the vapour pressure estimation technique that leads to higher Kp. We discuss that such large non-ideality for nopinone could arise due to particle phase processes lowering the effective nopinone vapour pressure such as diol- or dimer formation. The observed high partitioning coefficients compared to modelled results imply an underestimation of SOA mass by applying equilibrium conditions.

Sediment–water distribution of contaminants of emerging concern in a mixed use watershed

Energy Technology Data Exchange (ETDEWEB)

Fairbairn, David J., E-mail: david.fairbairn@state.mn.us [University of Minnesota, Water Resources Center, 1985 Buford Ave., St Paul, MN 55108 (United States); Karpuzcu, M. Ekrem [University of Minnesota, Water Resources Center, 1985 Buford Ave., St Paul, MN 55108 (United States); Arnold, William A. [University of Minnesota, Civil, Environmental, and Geo-Engineering, 500 Pillsbury Drive SE, Minneapolis, MN 55455 (United States); Barber, Brian L. [University of Minnesota, Department of Soil, Water, and Climate, 1902 Dudley Ave, Saint Paul, MN 55108 (United States); Kaufenberg, Elizabeth F. [University of Minnesota, Water Resources Center, 1985 Buford Ave., St Paul, MN 55108 (United States); Koskinen, William C. [United States Department of Agriculture, Agricultural Research Service, 1991 Upper Buford Circle, University of Minnesota, Saint Paul, MN 55108 (United States); Novak, Paige J. [University of Minnesota, Civil, Environmental, and Geo-Engineering, 500 Pillsbury Drive SE, Minneapolis, MN 55455 (United States); Rice, Pamela J. [United States Department of Agriculture, Agricultural Research Service, 1991 Upper Buford Circle, University of Minnesota, Saint Paul, MN 55108 (United States); Swackhamer, Deborah L. [University of Minnesota, Water Resources Center, 1985 Buford Ave., St Paul, MN 55108 (United States)

2015-02-01

This study evaluated the occurrence and distribution of 15 contaminants of emerging concern (CECs) in stream water and sediments in the Zumbro River watershed in Minnesota and compared these with sub-watershed land uses. Sixty pairs of sediment and water samples were collected across all seasons from four stream sites for over two years and analyzed for selected personal care products, pesticides, human and veterinary medications, and phytoestrogens. Spatial and temporal analyses indicate that pharmaceuticals and personal care products (urban/residential CECs) are significantly elevated in water and/or sediment at sites with greater population density (> 100 people/km{sup 2}) and percentage of developed land use (> 8% of subwatershed area) than those with less population density and land area under development. Significant spatial variations of agricultural pesticides in water and sediment were detectable, even though all sites had a high percentage of agricultural land use. Seasonality in CEC concentration was observed in water but not in sediment, although sediment concentrations of three CECs did vary between years. Average measured non-equilibrium distribution coefficients exceeded equilibrium hydrophobic partitioning-based predictions for 5 of the 7 detected CECs by at least an order of magnitude. Agreement of measured and predicted distribution coefficients improved with increasing hydrophobicity and in-stream persistence. The more polar and degradable CECs showed greater variability in measured distributions across different sampling events. Our results confirm that CECs are present in urban and agricultural stream sediments, including those CECs that would typically be thought of as non-sorptive based on their log K{sub ow} values. These results and the observed patterns of sediment and water distributions augment existing information to improve prediction of CEC fate and transport, leading to more accurate assessments of exposure and risk to surface water

The prediction of blood-tissue partitions, water-skin partitions and skin permeation for agrochemicals.

Science.gov (United States)

Abraham, Michael H; Gola, Joelle M R; Ibrahim, Adam; Acree, William E; Liu, Xiangli

2014-07-01

There is considerable interest in the blood-tissue distribution of agrochemicals, and a number of researchers have developed experimental methods for in vitro distribution. These methods involve the determination of saline-blood and saline-tissue partitions; not only are they indirect, but they do not yield the required in vivo distribution. The authors set out equations for gas-tissue and blood-tissue distribution, for partition from water into skin and for permeation from water through human skin. Together with Abraham descriptors for the agrochemicals, these equations can be used to predict values for all of these processes. The present predictions compare favourably with experimental in vivo blood-tissue distribution where available. The predictions require no more than simple arithmetic. The present method represents a much easier and much more economic way of estimating blood-tissue partitions than the method that uses saline-blood and saline-tissue partitions. It has the added advantages of yielding the required in vivo partitions and being easily extended to the prediction of partition of agrochemicals from water into skin and permeation from water through skin. © 2013 Society of Chemical Industry.

Application of a surface complexation model to the interactions of Pu and Am with Esk Estuary sediments

International Nuclear Information System (INIS)

Turner, D.R.; Knox, S.; Titley, J.G.; Hamilton-Taylor, J.; Kelly, M.; Williams, G.

1990-10-01

Previous work has shown that Pu is remobilised from Esk sediments at low salinities of overlying water. A constant capacitance surface complexation model has been developed in order to understand and model the chemical processes occurring. The model is based on detailed chemical characterisation of sediment samples from the estuary. The following measurements were carried out to provide input parameters for the model: specific surface area; total surface sites (tritium exchange); proton and major ion exchange (potentiometric titration); and actinide (Pu and Am) partition coefficient as a function of pH and salinity at sediment and actinide concentrations typical of the Esk. (author)

Slow sedimentation and deformability of charged lipid vesicles.

Directory of Open Access Journals (Sweden)

Iván Rey Suárez

Full Text Available The study of vesicles in suspension is important to understand the complicated dynamics exhibited by cells in in vivo and in vitro. We developed a computer simulation based on the boundary-integral method to model the three dimensional gravity-driven sedimentation of charged vesicles towards a flat surface. The membrane mechanical behavior was modeled using the Helfrich Hamiltonian and near incompressibility of the membrane was enforced via a model which accounts for the thermal fluctuations of the membrane. The simulations were verified and compared to experimental data obtained using suspended vesicles labelled with a fluorescent probe, which allows visualization using fluorescence microscopy and confers the membrane with a negative surface charge. The electrostatic interaction between the vesicle and the surface was modeled using the linear Derjaguin approximation for a low ionic concentration solution. The sedimentation rate as a function of the distance of the vesicle to the surface was determined both experimentally and from the computer simulations. The gap between the vesicle and the surface, as well as the shape of the vesicle at equilibrium were also studied. It was determined that inclusion of the electrostatic interaction is fundamental to accurately predict the sedimentation rate as the vesicle approaches the surface and the size of the gap at equilibrium, we also observed that the presence of charge in the membrane increases its rigidity.

Equilibrium Droplets on Deformable Substrates: Equilibrium Conditions.

Science.gov (United States)

Koursari, Nektaria; Ahmed, Gulraiz; Starov, Victor M

2018-05-15

Equilibrium conditions of droplets on deformable substrates are investigated, and it is proven using Jacobi's sufficient condition that the obtained solutions really provide equilibrium profiles of both the droplet and the deformed support. At the equilibrium, the excess free energy of the system should have a minimum value, which means that both necessary and sufficient conditions of the minimum should be fulfilled. Only in this case, the obtained profiles provide the minimum of the excess free energy. The necessary condition of the equilibrium means that the first variation of the excess free energy should vanish, and the second variation should be positive. Unfortunately, the mentioned two conditions are not the proof that the obtained profiles correspond to the minimum of the excess free energy and they could not be. It is necessary to check whether the sufficient condition of the equilibrium (Jacobi's condition) is satisfied. To the best of our knowledge Jacobi's condition has never been verified for any already published equilibrium profiles of both the droplet and the deformable substrate. A simple model of the equilibrium droplet on the deformable substrate is considered, and it is shown that the deduced profiles of the equilibrium droplet and deformable substrate satisfy the Jacobi's condition, that is, really provide the minimum to the excess free energy of the system. To simplify calculations, a simplified linear disjoining/conjoining pressure isotherm is adopted for the calculations. It is shown that both necessary and sufficient conditions for equilibrium are satisfied. For the first time, validity of the Jacobi's condition is verified. The latter proves that the developed model really provides (i) the minimum of the excess free energy of the system droplet/deformable substrate and (ii) equilibrium profiles of both the droplet and the deformable substrate.

Sensitivity and spin-up times of cohesive sediment transport models used to simulate bathymetric change: Chapter 31

Science.gov (United States)

Schoellhamer, D.H.; Ganju, N.K.; Mineart, P.R.; Lionberger, M.A.; Kusuda, T.; Yamanishi, H.; Spearman, J.; Gailani, J. Z.

2008-01-01

Bathymetric change in tidal environments is modulated by watershed sediment yield, hydrodynamic processes, benthic composition, and anthropogenic activities. These multiple forcings combine to complicate simple prediction of bathymetric change; therefore, numerical models are necessary to simulate sediment transport. Errors arise from these simulations, due to inaccurate initial conditions and model parameters. We investigated the response of bathymetric change to initial conditions and model parameters with a simplified zero-dimensional cohesive sediment transport model, a two-dimensional hydrodynamic/sediment transport model, and a tidally averaged box model. The zero-dimensional model consists of a well-mixed control volume subjected to a semidiurnal tide, with a cohesive sediment bed. Typical cohesive sediment parameters were utilized for both the bed and suspended sediment. The model was run until equilibrium in terms of bathymetric change was reached, where equilibrium is defined as less than the rate of sea level rise in San Francisco Bay (2.17 mm/year). Using this state as the initial condition, model parameters were perturbed 10% to favor deposition, and the model was resumed. Perturbed parameters included, but were not limited to, maximum tidal current, erosion rate constant, and critical shear stress for erosion. Bathymetric change was most sensitive to maximum tidal current, with a 10% perturbation resulting in an additional 1.4 m of deposition over 10 years. Re-establishing equilibrium in this model required 14 years. The next most sensitive parameter was the critical shear stress for erosion; when increased 10%, an additional 0.56 m of sediment was deposited and 13 years were required to re-establish equilibrium. The two-dimensional hydrodynamic/sediment transport model was calibrated to suspended-sediment concentration, and despite robust solution of hydrodynamic conditions it was unable to accurately hindcast bathymetric change. The tidally averaged

Does bioleaching represent a biotechnological strategy for remediation of contaminated sediments?

Energy Technology Data Exchange (ETDEWEB)

Fonti, Viviana, E-mail: v.fonti@univpm.it; Dell' Anno, Antonio; Beolchini, Francesca

2016-09-01

Bioleaching is a consolidated biotechnology in the mining industry and in bio-hydrometallurgy, where microorganisms mediate the solubilisation of metals and semi-metals from mineral ores and concentrates. Bioleaching also has the potential for ex-situ/on-site remediation of aquatic sediments that are contaminated with metals, which represent a key environmental issue of global concern. By eliminating or reducing (semi-)metal contamination of aquatic sediments, bioleaching may represent an environmentally friendly and low-cost strategy for management of contaminated dredged sediments. Nevertheless, the efficiency of bioleaching in this context is greatly influenced by several abiotic and biotic factors. These factors need to be carefully taken into account before selecting bioleaching as a suitable remediation strategy. Here we review the application of bioleaching for sediment bioremediation, and provide a critical view of the main factors that affect its performance. We also discuss future research needs to improve bioleaching strategies for contaminated aquatic sediments, in view of large-scale applications. - Highlights: • Bioleaching may represent a sustainable strategy for contaminated dredged sediments • The performance is greatly influenced by several abiotic and biotic factors • Geochemical characteristics and metal partitioning have a key role • Sulphide minerals in the sediment are a favorable element • Microorganisms other than Fe/S oxidisers may open new perspectives.

Does bioleaching represent a biotechnological strategy for remediation of contaminated sediments?

International Nuclear Information System (INIS)

Fonti, Viviana; Dell'Anno, Antonio; Beolchini, Francesca

2016-01-01

Bioleaching is a consolidated biotechnology in the mining industry and in bio-hydrometallurgy, where microorganisms mediate the solubilisation of metals and semi-metals from mineral ores and concentrates. Bioleaching also has the potential for ex-situ/on-site remediation of aquatic sediments that are contaminated with metals, which represent a key environmental issue of global concern. By eliminating or reducing (semi-)metal contamination of aquatic sediments, bioleaching may represent an environmentally friendly and low-cost strategy for management of contaminated dredged sediments. Nevertheless, the efficiency of bioleaching in this context is greatly influenced by several abiotic and biotic factors. These factors need to be carefully taken into account before selecting bioleaching as a suitable remediation strategy. Here we review the application of bioleaching for sediment bioremediation, and provide a critical view of the main factors that affect its performance. We also discuss future research needs to improve bioleaching strategies for contaminated aquatic sediments, in view of large-scale applications. - Highlights: • Bioleaching may represent a sustainable strategy for contaminated dredged sediments • The performance is greatly influenced by several abiotic and biotic factors • Geochemical characteristics and metal partitioning have a key role • Sulphide minerals in the sediment are a favorable element • Microorganisms other than Fe/S oxidisers may open new perspectives

Evaluation of scission and crosslinking yields in γ-irradiated poly(acrylic acid) and poly(methacrylic acid) from weight- and Ζ-average molecular weights determined by sedimentation equilibrium

International Nuclear Information System (INIS)

Hill, D.J.T.; O'Donnell, J.H.; Winzor, C.L.; Winzor, D.J.

1990-01-01

Weight- and Ζ-average molecular weights, M-bar W (D) and M-bar Ζ (D), of poly(methacrylic acid) (PMMA) and poly(acrylic acid) (PAA) have been determined by sedimentation equilibrium in the ultracentrifuge after various doses D of γ-radiation in vacuum. Relationships between [M i (0)/M i (D)-1]/D and D (i=w or Ζ), derived recently by O'Donnell and coworkers, have been used to determine radiation chemical yields for scission and crosslinking of G(S)=6.0, G(X)=0 for PMAA and G(S)=0, G(X)=0.44 for PAA. Allowance was necessary for the effects of COOH decomposition on the average values of the molecular weight and partial specific volume for irradiated PAA. (author)

Quantifying the Effects of Near-Bed Concentration on the Sediment Flux after the Operation of the Three Gorges Dam, Yangtze River

Directory of Open Access Journals (Sweden)

Li He

2017-12-01

Full Text Available The regime of sediment transport in the Jingjiang Reach has significantly changed from quasi-equilibrium to sub-saturation since the impoundment of the Three Gorges Dam (TGD, and vertical profiles of suspended sediment concentration (SSC have changed accordingly. Vertical profiles of SSC data measured at three hydrological stations in the Jingjiang Reach (Zhicheng, Shaishi, and Jianli, before and after the impoundment of TGD, were collected and analyzed. Analytic results indicate a remarkably large concentration in the near-bed zone (within 10% of water depth from the river-bed in a sub-saturated channel. The maximum measured concentration was up to 15 times the vertical average concentration, while the ratio in quasi-equilibrium channel was less than four times that. Concentrations normalized with reference concentration at the same height, and may decrease with increasing values of suspension index (settling velocity over shear velocity. In addition, concentration near the water surface may be larger than concentration in the near-bed region when the suspension index is smaller than 0.01. Sediment flux transported in the near-bed zone may be up to 35% of the total sediment flux in unsaturated flows. The relationship between deviations of estimating sediment flux when ignoring the near-bed concentration and discharge in flood season and non-flood season are different in unsaturated and quasi-equilibrium channels. Analysis indicates that, in the quasi-equilibrium channel, more attention should be paid to near-bed concentration during non-flood season, the same as measurements during flood season with larger discharge.

Partitioning in P-T concept

International Nuclear Information System (INIS)

Zhang Peilu; Qi Zhanshun; Zhu Zhixuan

2000-01-01

Comparison of dry- and water-method for partitioning fission products and minor actinides from the spent fuels, and description of advance of dry-method were done. Partitioning process, some typical concept and some results of dry-method were described. The problems fond in dry-method up to now were pointed out. The partitioning study program was suggested

Distribution and ecological relevance of fine sediments in organic-enriched lagoons: The case study of the Cabras lagoon (Sardinia, Italy)

Energy Technology Data Exchange (ETDEWEB)

Magni, P. [CNR-IAMC, National Research Council - Institute for Coastal Marine Environment Localita Sa Mardini, Torregrande, 09072 Oristano (Italy); International Marine Centre, Localita Sa Mardini, Torregrande, 09072 Oristano (Italy)], E-mail: paolo.magni@iamc.cnr.it; De Falco, G. [CNR-IAMC, National Research Council - Institute for Coastal Marine Environment Localita Sa Mardini, Torregrande, 09072 Oristano (Italy); International Marine Centre, Localita Sa Mardini, Torregrande, 09072 Oristano (Italy); Como, S. [International Marine Centre, Localita Sa Mardini, Torregrande, 09072 Oristano (Italy); Casu, D. [Dip. di Botanica ed Ecologia vegetale, Universita di Sassari, 07100 Sassari (Italy); Floris, A. [Dip. di Zoologia e Genetica evoluzionistica, Universita di Sassari, 07100 Sassari (Italy); Petrov, A.N. [Institute of Biology of the Southern Seas NASU, 99011 Sevastopol (Ukraine); Castelli, A. [Dip. di Biologia, Universita di Pisa, 56126 Pisa (Italy); Perilli, A. [CNR-IAMC, National Research Council - Institute for Coastal Marine Environment Localita Sa Mardini, Torregrande, 09072 Oristano (Italy); International Marine Centre, Localita Sa Mardini, Torregrande, 09072 Oristano (Italy)

2008-03-15

In organic-enriched sedimentary systems, like many Mediterranean coastal lagoons, a detailed analysis of sediment grain size composition and partitioning within the muds is crucial to investigate sedimentological trends related to both hydrodynamic energy and basin morphology. In these systems, sediment dynamics are particularly important because the partitioning and transport of fine sediments can strongly influence the redistribution and accumulation of large amounts of organic matter, and consequently the distribution of benthic assemblages and the trophic status and functioning of a lagoon. Nevertheless, studies on benthic-sediment relationships have been based mainly on a rather coarse analysis of sediment grain size features. In muddy systems, however, this approach may impede a proper evaluation of the relationships and effects of the distribution of fine sediment and organic matter on the biotic benthic components. Here we show that the distribution of sedimentary organic matter (OM) and total organic carbon (TOC) in the Cabras lagoon (Sardinia, Italy) can be explained (i.e., predicted) as a function of a nonlinear increase in the amount of the cohesive fraction of sediments ({<=}8 {mu}m grain size particles) and that this fraction strongly influences the structure, composition and distribution of macrobenthic assemblages. Even in such a homogeneously muddy system, characterized by 'naturally' occurring impoverished communities, impaired benthic assemblages were found at {<=}8 {mu}m, OM, TOC contents of about 77%, 11% and 3.5%, respectively. A review of studies conducted in Mediterranean coastal lagoons highlighted a lack of direct integrated analysis of sediment features and the biotic components. We suggest that, especially in organic-enriched coastal lagoons, monitoring programs should primarily investigate and consider the cohesive fraction of sediments in order to allow a better assessment of benthic-sediment relationships and ecological

Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

International Nuclear Information System (INIS)

Marx, D.

1959-11-01

We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

Force-Field Functor Theory: Classical Force-Fields which Reproduce Equilibrium Quantum Distributions

Directory of Open Access Journals (Sweden)

Ryan eBabbush

2013-10-01

Full Text Available Feynman and Hibbs were the first to variationally determine an effective potential whose associated classical canonical ensemble approximates the exact quantum partition function. We examine the existence of a map between the local potential and an effective classical potential which matches the exact quantum equilibrium density and partition function. The usefulness of such a mapping rests in its ability to readily improve Born-Oppenheimer potentials for use with classical sampling. We show that such a map is unique and must exist. To explore the feasibility of using this result to improve classical molecular mechanics, we numerically produce a map from a library of randomly generated one-dimensional potential/effective potential pairs then evaluate its performance on independent test problems. We also apply the map to simulate liquid para-hydrogen, finding that the resulting radial pair distribution functions agree well with path integral Monte Carlo simulations. The surprising accessibility and transferability of the technique suggest a quantitative route to adapting Born-Oppenheimer potentials, with a motivation similar in spirit to the powerful ideas and approximations of density functional theory.

Thermodynamic chemical energy transfer mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium chemical reactions

International Nuclear Information System (INIS)

Roh, Heui-Seol

2015-01-01

Chemical energy transfer mechanisms at finite temperature are explored by a chemical energy transfer theory which is capable of investigating various chemical mechanisms of non-equilibrium, quasi-equilibrium, and equilibrium. Gibbs energy fluxes are obtained as a function of chemical potential, time, and displacement. Diffusion, convection, internal convection, and internal equilibrium chemical energy fluxes are demonstrated. The theory reveals that there are chemical energy flux gaps and broken discrete symmetries at the activation chemical potential, time, and displacement. The statistical, thermodynamic theory is the unification of diffusion and internal convection chemical reactions which reduces to the non-equilibrium generalization beyond the quasi-equilibrium theories of migration and diffusion processes. The relationship between kinetic theories of chemical and electrochemical reactions is also explored. The theory is applied to explore non-equilibrium chemical reactions as an illustration. Three variable separation constants indicate particle number constants and play key roles in describing the distinct chemical reaction mechanisms. The kinetics of chemical energy transfer accounts for the four control mechanisms of chemical reactions such as activation, concentration, transition, and film chemical reactions. - Highlights: • Chemical energy transfer theory is proposed for non-, quasi-, and equilibrium. • Gibbs energy fluxes are expressed by chemical potential, time, and displacement. • Relationship between chemical and electrochemical reactions is discussed. • Theory is applied to explore nonequilibrium energy transfer in chemical reactions. • Kinetics of non-equilibrium chemical reactions shows the four control mechanisms

A field studies and modeling approach to develop organochlorine pesticide and PCB total maximum daily load calculations: Case study for Echo Park Lake, Los Angeles, CA

Energy Technology Data Exchange (ETDEWEB)

Vasquez, V.R., E-mail: vrvasquez@ucla.edu [Environmental Science and Engineering Program, University of California, Los Angeles, Los Angeles, CA 90095-1496 (United States); Curren, J., E-mail: janecurren@yahoo.com [Environmental Science and Engineering Program, University of California, Los Angeles, Los Angeles, CA 90095-1496 (United States); Lau, S.-L., E-mail: simlin@ucla.edu [Department of Civil and Environmental Engineering, University of California, Los Angeles, Los Angeles, CA 90095-1496 (United States); Stenstrom, M.K., E-mail: stenstro@seas.ucla.edu [Department of Civil and Environmental Engineering, University of California, Los Angeles, Los Angeles, CA 90095-1496 (United States); Suffet, I.H., E-mail: msuffet@ucla.edu [Environmental Science and Engineering Program, University of California, Los Angeles, Los Angeles, CA 90095-1496 (United States)

2011-09-01

Echo Park Lake is a small lake in Los Angeles, CA listed on the USA Clean Water Act Section 303(d) list of impaired water bodies for elevated levels of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in fish tissue. A lake water and sediment sampling program was completed to support the development of total maximum daily loads (TMDL) to address the lake impairment. The field data indicated quantifiable levels of OCPs and PCBs in the sediments, but lake water data were all below detection levels. The field sediment data obtained may explain the contaminant levels in fish tissue using appropriate sediment-water partitioning coefficients and bioaccumulation factors. A partition-equilibrium fugacity model of the whole lake system was used to interpret the field data and indicated that half of the total mass of the pollutants in the system are in the sediments and the other half is in soil; therefore, soil erosion could be a significant pollutant transport mode into the lake. Modeling also indicated that developing and quantifying the TMDL depends significantly on the analytical detection level for the pollutants in field samples and on the choice of octanol-water partitioning coefficient and bioaccumulation factors for the model. - Research highlights: {yields} Fugacity model using new OCP and PCB field data supports lake TMDL calculations. {yields} OCP and PCB levels in lake sediment were found above levels for impairment. {yields} Relationship between sediment data and available fish tissue data evaluated. {yields} Model provides approximation of contaminant sources and sinks for a lake system. {yields} Model results were sensitive to analytical detection and quantification levels.

Entropy production in a fluid-solid system far from thermodynamic equilibrium.

Science.gov (United States)

Chung, Bong Jae; Ortega, Blas; Vaidya, Ashwin

2017-11-24

The terminal orientation of a rigid body in a moving fluid is an example of a dissipative system, out of thermodynamic equilibrium and therefore a perfect testing ground for the validity of the maximum entropy production principle (MaxEP). Thus far, dynamical equations alone have been employed in studying the equilibrium states in fluid-solid interactions, but these are far too complex and become analytically intractable when inertial effects come into play. At that stage, our only recourse is to rely on numerical techniques which can be computationally expensive. In our past work, we have shown that the MaxEP is a reliable tool to help predict orientational equilibrium states of highly symmetric bodies such as cylinders, spheroids and toroidal bodies. The MaxEP correctly helps choose the stable equilibrium in these cases when the system is slightly out of thermodynamic equilibrium. In the current paper, we expand our analysis to examine i) bodies with fewer symmetries than previously reported, for instance, a half-ellipse and ii) when the system is far from thermodynamic equilibrium. Using two-dimensional numerical studies at Reynolds numbers ranging between 0 and 14, we examine the validity of the MaxEP. Our analysis of flow past a half-ellipse shows that overall the MaxEP is a good predictor of the equilibrium states but, in the special case of the half-ellipse with aspect ratio much greater than unity, the MaxEP is replaced by the Min-MaxEP, at higher Reynolds numbers when inertial effects come into play. Experiments in sedimentation tanks and with hinged bodies in a flow tank confirm these calculations.

Does equilibrium passive sampling reflect actual in situ bioaccumulation of PAHs and petroleum hydrocarbon mixtures in aquatic worms?

NARCIS (Netherlands)

Muijs, B.|info:eu-repo/dai/nl/194995526; Jonker, M.T.O.|info:eu-repo/dai/nl/175518793

2012-01-01

Over the past couple of years, several analytical methods have been developed for assessing the bioavailability of environmental contaminants in sediments and soils. Comparison studies suggest that equilibrium passive sampling methods generally provide the better estimates of internal concentrations

Partitioning planning studies: Preliminary evaluation of metal and radionuclide partitioning the high-temperature thermal treatment systems

International Nuclear Information System (INIS)

Liekhus, K.; Grandy, J.; Chambers, A.

1997-03-01

A preliminary study of toxic metals and radionuclide partitioning during high-temperature processing of mixed waste has been conducted during Fiscal Year 1996 within the Environmental Management Technology Evaluation Project. The study included: (a) identification of relevant partitioning mechanisms that cause feed material to be distributed between the solid, molten, and gas phases within a thermal treatment system; (b) evaluations of existing test data from applicable demonstration test programs as a means to identify and understand elemental and species partitioning; and, (c) evaluation of theoretical or empirical partitioning models for use in predicting elemental or species partitioning in a thermal treatment system. This preliminary study was conducted to identify the need for and the viability of developing the tools capable of describing and predicting toxic metals and radionuclide partitioning in the most applicable mixed waste thermal treatment processes. This document presents the results and recommendations resulting from this study that may serve as an impetus for developing and implementing these predictive tools

Partitioning planning studies: Preliminary evaluation of metal and radionuclide partitioning the high-temperature thermal treatment systems

Energy Technology Data Exchange (ETDEWEB)

Liekhus, K.; Grandy, J.; Chambers, A. [and others

1997-03-01

A preliminary study of toxic metals and radionuclide partitioning during high-temperature processing of mixed waste has been conducted during Fiscal Year 1996 within the Environmental Management Technology Evaluation Project. The study included: (a) identification of relevant partitioning mechanisms that cause feed material to be distributed between the solid, molten, and gas phases within a thermal treatment system; (b) evaluations of existing test data from applicable demonstration test programs as a means to identify and understand elemental and species partitioning; and, (c) evaluation of theoretical or empirical partitioning models for use in predicting elemental or species partitioning in a thermal treatment system. This preliminary study was conducted to identify the need for and the viability of developing the tools capable of describing and predicting toxic metals and radionuclide partitioning in the most applicable mixed waste thermal treatment processes. This document presents the results and recommendations resulting from this study that may serve as an impetus for developing and implementing these predictive tools.

Analysis of Heavy Metals in Surface Sediments from Agh Gel Wetland, Iran

Directory of Open Access Journals (Sweden)

Soheil Sobhanardakani

2016-06-01

Full Text Available Background: Soil and sediment serve as major reservoir for contaminants as they possess ability to bind various chemicals together. In this study the concentrations of heavy metals Cd, Cr and Cu were analyzed in surface sediments of Agh Gel Wetland in west of Iran. Methods: The sediment samples were taken from 10 stations. The samples were subjected to bulk digestion and chemical partitioning and Cd, Cr and Cu concentrations of the sediments were determined by ICP-OES. Geo-accumulation index (I-geo, Contamination factor (CF and Pollution load index (PLI were used to evaluate the magnitude of contaminants in the sediment profile. Results: The mean sediment concentrations (mg kg-1 dry weight ranged within 0.20-0.29 (Cd, 58-71 (Cr and 23-36 (Cu. According to the I-geo values, the sediments' qualities are classified as unpolluted to moderately polluted category. According to the CF values, the sediments' qualities are classified as low to moderate contamination. Furthermore, the PLI values indicated that there were no metal pollution exists for all sampling stations. Conclusion: The Agh Gel Wetland is potential to be threatened by chemical pollutants such as agricultural effluent. So to preserve the environment of the Agh Gel Wetland from deterioration, periodically monitoring of the water and sediment qualities is recommended.

Energy Harvesting, Electrode Processes and the Partitioning and Speciation of Solid Phase Iron and Sulfur in Marine Sediments

National Research Council Canada - National Science Library

Reimers, Clare

2003-01-01

.... Sediment, pore water and electrode surface analyses indicated that electricity product ion is coupled to the oxidation of dissolved and solid-phase forms of reduced sulfur supplied from the sediments...

Improved models for the prediction of activity coefficients in nearly athermal mixtures .2. A theoretically-based G(E)-model based on the van der Waals partition function

DEFF Research Database (Denmark)

Kontogeorgis, Georgios; Georgios, Nikolopoulos; Fredenslund, Aage

1997-01-01

of the generalized van der Waals partition function and attempts to account for all non-energetic effects of solutions of both short- and long-chain alkanes, including alkane polymers. Both the free-volume effects and the density-dependent rotational degrees of freedom are considered. The resulting G(E)-model which......, despite its derivation from a partition function resembles the Flory-Huggins formula, is suitable for vapor-liquid and solid-liquid equilibrium calculations for nearly athermal polymer solutions as well as for alkane systems. We show that using plausible assumptions for the free-volume and the external...

Equilibrium relations and bipolar cognitive mapping for online analytical processing with applications in international relations and strategic decision support.

Science.gov (United States)

Zhang, Wen-Ran

2003-01-01

Bipolar logic, bipolar sets, and equilibrium relations are proposed for bipolar cognitive mapping and visualization in online analytical processing (OLAP) and online analytical mining (OLAM). As cognitive models, cognitive maps (CMs) hold great potential for clustering and visualization. Due to the lack of a formal mathematical basis, however, CM-based OLAP and OLAM have not gained popularity. Compared with existing approaches, bipolar cognitive mapping has a number of advantages. First, bipolar CMs are formal logical models as well as cognitive models. Second, equilibrium relations (with polarized reflexivity, symmetry, and transitivity), as bipolar generalizations and fusions of equivalence relations, provide a theoretical basis for bipolar visualization and coordination. Third, an equilibrium relation or CM induces bipolar partitions that distinguish disjoint coalition subsets not involved in any conflict, disjoint coalition subsets involved in a conflict, disjoint conflict subsets, and disjoint harmony subsets. Finally, equilibrium energy analysis leads to harmony and stability measures for strategic decision and multiagent coordination. Thus, this work bridges a gap for CM-based clustering and visualization in OLAP and OLAM. Basic ideas are illustrated with example CMs in international relations.

The Euler–Riemann gases, and partition identities

International Nuclear Information System (INIS)

Chair, Noureddine

2013-01-01

The Euler theorem in partition theory and its generalization are derived from a non-interacting quantum field theory in which each bosonic mode with a given frequency is equivalent to a sum of bosonic mode whose frequency is twice (s-times) as much, and a fermionic (parafermionic) mode with the same frequency. Explicit formulas for the graded parafermionic partition functions are obtained, and the inverse of the graded partition function (IGPPF), turns out to be bosonic (fermionic) partition function depending on the parity of the order s of the parafermions. It is also shown that these partition functions are generating functions of partitions of integers with restrictions, the Euler generating function is identified with the inverse of the graded parafermionic partition function of order 2. As a result we obtain new sequences of partitions of integers with given restrictions. If the parity of the order s is even, then mixing a system of parafermions with a system whose partition function is (IGPPF), results in a system of fermions and bosons. On the other hand, if the parity of s is odd, then, the system we obtain is still a mixture of fermions and bosons but the corresponding Fock space of states is truncated. It turns out that these partition functions are given in terms of the Jacobi theta function θ 4 , and generate sequences in partition theory. Our partition functions coincide with the overpartitions of Corteel and Lovejoy, and jagged partitions in conformal field theory. Also, the partition functions obtained are related to the Ramond characters of the superconformal minimal models, and in the counting of the Moore–Read edge spectra that appear in the fractional quantum Hall effect. The different partition functions for the Riemann gas that are the counter parts of the Euler gas are obtained by a simple change of variables. In particular the counter part of the Jacobi theta function is (ζ(2t))/(ζ(t) 2 ) . Finally, we propose two formulas which brings

Hawk: A Runtime System for Partitioned Objects

NARCIS (Netherlands)

Ben Hassen, S.; Bal, H.E.; Tanenbaum, A.S.

1997-01-01

Hawk is a language-independent runtime system for writing data-parallel programs using partitioned objects. A partitioned object is a multidimensional array of elements that can be partitioned and distributed by the programmer. The Hawk runtime system uses the user-defined partitioning of objects

[On the partition of acupuncture academic schools].

Science.gov (United States)

Yang, Pengyan; Luo, Xi; Xia, Youbing

2016-05-01

Nowadays extensive attention has been paid on the research of acupuncture academic schools, however, a widely accepted method of partition of acupuncture academic schools is still in need. In this paper, the methods of partition of acupuncture academic schools in the history have been arranged, and three typical methods of"partition of five schools" "partition of eighteen schools" and "two-stage based partition" are summarized. After adeep analysis on the disadvantages and advantages of these three methods, a new method of partition of acupuncture academic schools that is called "three-stage based partition" is proposed. In this method, after the overall acupuncture academic schools are divided into an ancient stage, a modern stage and a contemporary stage, each schoolis divided into its sub-school category. It is believed that this method of partition can remedy the weaknesses ofcurrent methods, but also explore a new model of inheritance and development under a different aspect through thedifferentiation and interaction of acupuncture academic schools at three stages.

Remediation of organochlorine pesticides contaminated lake sediment using activated carbon and carbon nanotubes.

Science.gov (United States)

Hua, Shan; Gong, Ji-Lai; Zeng, Guang-Ming; Yao, Fu-Bing; Guo, Min; Ou, Xiao-Ming

2017-06-01

Organochlorine pesticides (OCPs) in sediment were a potential damage for humans and ecosystems. The aim of this work was to determine the effectiveness of carbon materials remedy hexachlorocyclohexane (HCH) and dichlorodiphenyltrichloroethanes (DDTs) in sediment. Two different carbon materials including activated carbon (AC) and multi-walled carbon nanotubes (MWCNTs) were used in the present research. Sediment treated with 2 wt% AC and MWCNTs after 150 d contact showed 97%, and 75% reduction for HCH, and 93% and 59% decrease for DDTs in aqueous equilibrium concentration, respectively. Similarly, the reduction efficiencies of DDT and HCH uptake by semipermeable membrane devices (SPMDs) treated with AC (MWCNTs) were 97% (75%) and 92% (63%), respectively under the identical conditions. Furthermore, for 2 wt% AC (MWCNTs) system, a reduction of XAD beads uptake up to 87% (52%) and 73% (67%) was obtained in HCH and DDT flux to overlying water in quiescent system. Adding MWCNTs to contaminated sediment did not significantly decrease aqueous equilibrium concentration and DDTs and HCH availability in SPMDs compared to AC treatment. A series of results indicated that AC had significantly higher remediation efficiency towards HCH and DDTs in sediment than MWCNTs. Additionally, the removal efficiencies of two organic pollutants improved with increasing material doses and contact times. The greater effectiveness of AC was attributed to its greater specific surface area, which was favorable for binding contaminants. These results highlighted the potential for using AC as in-situ sorbent amendments for sediment remediation. Copyright © 2017 Elsevier Ltd. All rights reserved.

Trace-element speciation and partitioning in environmental geochemistry and health

Energy Technology Data Exchange (ETDEWEB)

Farmer, J.G.; Gibson, M.J.; Lovell, M.A.

1983-09-01

Establishment of the chemical form and associations of trace elements is important in the scientifc and medical fields related to environmental geochemistry and health. Fundamental understanding of trace-element behavior, the realistic formulation of historical perspectives of trace-element contamination, an assessment of environmental transformation processes and a thorough appraisal of environment-related ill health and disease all depend on knowledge of the chemical speciation and partitioning of trace elements. These topics and the development of analytical speciation techniques and procedures are discussed with reference to trace-element studies in the Department of Forensic Medicine and Science, University of Glasgow, on lacustrine sediments and water, the atmosphere, soil and street dirt of an urban environment, and human biological fluids. 206 references, 4 figures.

Analysis of load balance in hybrid partitioning | Talib | Botswana ...

African Journals Online (AJOL)

In information retrieval systems, there are three types of index partitioning schemes - term partitioning, document partitioning, and hybrid partitioning. The hybrid-partitioning scheme combines both term and document partitioning schemes. Term partitioning provides high concurrency, which means that queries can be ...

Sediment transport through self-adjusting, bedrock-walled waterfall plunge pools

Science.gov (United States)

Scheingross, Joel S.; Lamb, Michael P.

2016-05-01

Many waterfalls have deep plunge pools that are often partially or fully filled with sediment. Sediment fill may control plunge-pool bedrock erosion rates, partially determine habitat availability for aquatic organisms, and affect sediment routing and debris flow initiation. Currently, there exists no mechanistic model to describe sediment transport through waterfall plunge pools. Here we develop an analytical model to predict steady-state plunge-pool depth and sediment-transport capacity by combining existing jet theory with sediment transport mechanics. Our model predicts plunge-pool sediment-transport capacity increases with increasing river discharge, flow velocity, and waterfall drop height and decreases with increasing plunge-pool depth, radius, and grain size. We tested the model using flume experiments under varying waterfall and plunge-pool geometries, flow hydraulics, and sediment size. The model and experiments show that through morphodynamic feedbacks, plunge pools aggrade to reach shallower equilibrium pool depths in response to increases in imposed sediment supply. Our theory for steady-state pool depth matches the experiments with an R2 value of 0.8, with discrepancies likely due to model simplifications of the hydraulics and sediment transport. Analysis of 75 waterfalls suggests that the water depths in natural plunge pools are strongly influenced by upstream sediment supply, and our model provides a mass-conserving framework to predict sediment and water storage in waterfall plunge pools for sediment routing, habitat assessment, and bedrock erosion modeling.

Characterization of phosphorus sorption on the sediments of Yangtze River Estuary and its adjacent areas

International Nuclear Information System (INIS)

Cao, Xiaoyan; Liu, Xiaoyue; Zhu, Jiamei; Wang, Lisha; Liu, Sumei; Yang, Guipeng

2017-01-01

This paper studied the kinetics, isotherm and thermodynamics of phosphorus sorption onto the sediments of the Yangtze River estuary and its adjacent waters, as well as the sediments' compositions and physicochemical properties. The process could be described well by a two-compartment first order equation. The sorbed phosphorus mainly consisted of Ex-P and Fe-P, with Ex-P being the dominant. The equilibrium isotherms could be fitted well with a modified Langmuir equation. The calculations of the thermodynamic parameters indicated that the process was spontaneous and exothermic. The CEC and the fractions of clay, calcite and organic matter were correlated with the sorption parameters, while the surface proton charge of the sediments was significantly negatively correlated with them. Considering the kinetics and phosphorus forms changes during the process, the sorption in our study could be considered that the physical process plays an important role. - Highlights: • The kinetic curves and phosphorus fractions changes during sorption were studied. • The sorbed phosphorus mainly consisted of Ex − P and Fe-P, with Ex − P being dominant. • The equilibrium isotherms and thermodynamic parameters were investigated. • Sediment composition and surface characteristics influenced phosphorus sorption parameters.

Three-Dimensional Sediment Dynamics in Well-Mixed Estuaries : Importance of the Internally Generated Overtide, Spatial Settling Lag, and Gravitational Circulation

NARCIS (Netherlands)

Wei, X.; Kumar, M.; Schuttelaars, H.M.

2018-01-01

To investigate the dominant sediment transport and trapping mechanisms, a semi-analytical three-dimensional model is developed resolving the dynamic effects of salt intrusion on sediment in well-mixed estuaries in morphodynamic equilibrium. As a study case, a schematized estuary with a converging

Distribution, speciation, environmental risk, and source identification of heavy metals in surface sediments from the karst aquatic environment of the Lijiang River, Southwest China.

Science.gov (United States)

Xu, Daoquan; Wang, Yinghui; Zhang, Ruijie; Guo, Jing; Zhang, Wei; Yu, Kefu

2016-05-01

The distribution and speciation of several heavy metals, i.e., As, Cd, Cr, Cu, Hg, Pb, and Zn, in surface sediments from the karst aquatic environment of the Lijiang River, Southwest China, were studied comparatively. The mean contents of Cd, Cu, Hg, Pb, and Zn were 1.72, 38.07, 0.18, 51.54, and 142.16 mg/kg, respectively, which were about 1.5-6 times higher than their corresponding regional sediment background values. Metal speciation obtained by the optimized BCR protocol highlighted the bioavailable threats of Cd, Cu, and Zn, which were highly associated with the exchangeable fraction (the labile phase). Hierarchical cluster analysis indicated that in sediments, As and Cr were mainly derived from natural and industrial sources, whereas fertilizer application might lead to the elevated level of Cd. Besides, Cu, Hg, Pb, and Zn were related to traffic activities. The effects-based sediment quality guidelines (SQGs) showed that Hg, Pb, and Zn could pose occasional adverse effects on sediment-dwelling organisms. However, based on the potential ecological risk assessment (PER) and risk assessment code (RAC), Cd was the most outstanding pollutant and posed the highest ecological hazard and bioavailable risk among the selected metals. Moreover, the metal partitioning between water and sediments was quantified through the calculation of the pseudo-partitioning coefficient (K P), and result implied that the sediments in this karst aquatic environment cannot be used as stable repositories for the metal pollutants.

Partitioning sparse rectangular matrices for parallel processing

Energy Technology Data Exchange (ETDEWEB)

Kolda, T.G.

1998-05-01

The authors are interested in partitioning sparse rectangular matrices for parallel processing. The partitioning problem has been well-studied in the square symmetric case, but the rectangular problem has received very little attention. They will formalize the rectangular matrix partitioning problem and discuss several methods for solving it. They will extend the spectral partitioning method for symmetric matrices to the rectangular case and compare this method to three new methods -- the alternating partitioning method and two hybrid methods. The hybrid methods will be shown to be best.

A brief history of partitions of numbers, partition functions and their modern applications

Science.gov (United States)

Debnath, Lokenath

2016-04-01

'Number rules the universe.' The Pythagoras 'If you wish to forsee the future of mathematics our course is to study the history and present conditions of the science.' Henri Poincaré 'The primary source (Urqell) of all mathematics are integers.' Hermann Minkowski This paper is written to commemorate the centennial anniversary of the Mathematical Association of America. It deals with a short history of different kinds of natural numbers including triangular, square, pentagonal, hexagonal and k-gonal numbers, and their simple properties and their geometrical representations. Included are Euclid's and Pythagorean's main contributions to elementary number theory with the main contents of the Euclid Elements of the 13-volume masterpiece of mathematical work. This is followed by Euler's new discovery of the additive number theory based on partitions of numbers. Special attention is given to many examples, Euler's theorems on partitions of numbers with geometrical representations of Ferrers' graphs, Young's diagrams, Lagrange's four-square theorem and the celebrated Waring problem. Included are Euler's generating functions for the partitions of numbers, Euler's pentagonal number theorem, Gauss' triangular and square number theorems and the Jacobi triple product identity. Applications of the theory of partitions of numbers to different statistics such as the Bose- Einstein, Fermi- Dirac, Gentile, and Maxwell- Boltzmann statistics are briefly discussed. Special attention is given to pedagogical information through historical approach to number theory so that students and teachers at the school, college and university levels can become familiar with the basic concepts of partitions of numbers, partition functions and their modern applications, and can pursue advanced study and research in analytical and computational number theory.

Radiocaesium, plutonium and americium partitioning and solid speciation in sized, inter-tidal sediments from Strangford Lough

International Nuclear Information System (INIS)

Ledgerwood, F.K.; Larmour, R.A.; Mitchell, P.I.; Leon Vintro, L.; Ryan, R.W.

1999-01-01

Fine-grained surface (0-2 cm) sediment was collected at an inter-tidal site (Mahee Island) in Strangford Lough, on the NE coast of Ireland in September 1997. The sediment was wet-sieved into standard sized fractions using Endecott test sieves and the fractions assayed for 137 Cs, 239,240 Pu and 241 Am content. Sub-samples of each fraction were measured with a Malvern 2600 laser diffraction analyser, which confirmed that >90% of the particles in each fraction was in the defined size range

Hydrologic controls on equilibrium soil depths

Science.gov (United States)

Nicótina, L.; Tarboton, D. G.; Tesfa, T. K.; Rinaldo, A.

2011-04-01

This paper deals with modeling the mutual feedbacks between runoff production and geomorphological processes and attributes that lead to patterns of equilibrium soil depth. Our primary goal is an attempt to describe spatial patterns of soil depth resulting from long-term interactions between hydrologic forcings and soil production, erosion, and sediment transport processes under the framework of landscape dynamic equilibrium. Another goal is to set the premises for exploiting the role of soil depths in shaping the hydrologic response of a catchment. The relevance of the study stems from the massive improvement in hydrologic predictions for ungauged basins that would be achieved by using directly soil depths derived from geomorphic features remotely measured and objectively manipulated. Hydrological processes are here described by explicitly accounting for local soil depths and detailed catchment topography. Geomorphological processes are described by means of well-studied geomorphic transport laws. The modeling approach is applied to the semiarid Dry Creek Experimental Watershed, located near Boise, Idaho. Modeled soil depths are compared with field data obtained from an extensive survey of the catchment. Our results show the ability of the model to describe properly the mean soil depth and the broad features of the distribution of measured data. However, local comparisons show significant scatter whose origins are discussed.

Hazard evaluation of ten organophosphorous insecticides against the midge, Chironomus riparius via QSAR

Science.gov (United States)

Landrum, Peter F.; Fisher, Susan W.; Hwang, Haejo; Hickey, James P.

1999-01-01

Toxicities of ten organophosphorus (OP) insecticides were measured against midge larvae (Chironomus riparius) under varying temperature (11, 18, and 25°C) and pH (6, 7, and 8) conditions and with and without sediment. Toxicity usually increased with increasing temperature and was greater in the absence of sediment. No trend was found with varying pH. A series of unidimensional parameters and multidimensional models were used to describe the changes in toxicity. Log Kow was able to explain about 40–60% of the variability in response data for aqueous exposures while molecular volume and aqueous solubility were less predictive. Likewise, the linear solvation energy relationship (LSER) model only explained 40–70% of the response variability, suggesting that factors other than solubility were most important for producing the observed response. Molecular connectivity was the most useful for describing the variability in the response. In the absence of sediment, 1χv and 3κ were best able to describe the variation in response among all compounds at each pH (70–90%). In the presence of sediment, even molecular connectivity could not describe the variability until the partitioning potential to sediment was accounted for by assuming equilibrium partitioning. After correcting for partitioning, the same molecular connectivity terms as in the aqueous exposures described most of the variability, 61–87%, except for the 11°C data where correlations were not significant. Molecular connectivity was a better tool than LSER or the unidimensional variables to explain the steric fitness of OP insecticides which was crucial to the toxicity.

Application of Radiotracer Methodology for Understanding the Influence of Geochemical Fractionation on Metal Bioavailability in Estuarine Sediments

Energy Technology Data Exchange (ETDEWEB)

Fisher, N. S.; Baumann, Z. [School of Marine and Atmospheric Sciences, Stony Brook University, Stony Brook, NY (United States)

2013-07-15

To evaluate the extent to which contaminated sediments could introduce metals into marine food chains, gamma emitting radioisotopes of arsenic, cadmium and chromium were used to study their geochemical fractionation in estuarine sediments and bioavailability to deposit feeding polychaetes. Radioisotopes were added to sediments directly or via planktonic debris and were then fractionated with a sequential extraction scheme after aging for up to 90 days. The assimilation of ingested metals was positively related to their partitioning in the two most readily extractable (labile) sediment fractions and negatively related to refractory organic fractions, oxides, and pyrite. In comparison to uptake from ingested sediment, metal uptake from pore water was negligible. A metal bioaccumulation model, modified to consider their geochemical fractionation, was found to quantitatively predict metal concentrations in benthic polychaetes better than total metal concentrations in sediment. Metals need to desorb from ingested particles into gut fluid within the polychaete gut before they can be assimilated. (author)

New Linear Partitioning Models Based on Experimental Water: Supercritical CO2 Partitioning Data of Selected Organic Compounds.

Science.gov (United States)

Burant, Aniela; Thompson, Christopher; Lowry, Gregory V; Karamalidis, Athanasios K

2016-05-17

Partitioning coefficients of organic compounds between water and supercritical CO2 (sc-CO2) are necessary to assess the risk of migration of these chemicals from subsurface CO2 storage sites. Despite the large number of potential organic contaminants, the current data set of published water-sc-CO2 partitioning coefficients is very limited. Here, the partitioning coefficients of thiophene, pyrrole, and anisole were measured in situ over a range of temperatures and pressures using a novel pressurized batch-reactor system with dual spectroscopic detectors: a near-infrared spectrometer for measuring the organic analyte in the CO2 phase and a UV detector for quantifying the analyte in the aqueous phase. Our measured partitioning coefficients followed expected trends based on volatility and aqueous solubility. The partitioning coefficients and literature data were then used to update a published poly parameter linear free-energy relationship and to develop five new linear free-energy relationships for predicting water-sc-CO2 partitioning coefficients. A total of four of the models targeted a single class of organic compounds. Unlike models that utilize Abraham solvation parameters, the new relationships use vapor pressure and aqueous solubility of the organic compound at 25 °C and CO2 density to predict partitioning coefficients over a range of temperature and pressure conditions. The compound class models provide better estimates of partitioning behavior for compounds in that class than does the model built for the entire data set.

High-temperature partition functions, specific heats and spectral radiative properties of diatomic molecules with an improved calculation of energy levels

Science.gov (United States)

Qin, Z.; Zhao, J. M.; Liu, L. H.

2018-05-01

The level energies of diatomic molecules calculated by the frequently used Dunham expansion will become less accurate for high-lying vibrational and rotational levels. In this paper, the potential curves for the lower-lying electronic states with accurate spectroscopic constants are reconstructed using the Rydberg-Klein-Rees (RKR) method, which are extrapolated to the dissociation limits by fitting of the theoretical potentials, and the rest of the potential curves are obtained from the ab-initio results in the literature. Solving the rotational dependence of the radial Schrödinger equation over the obtained potential curves, we determine the rovibrational level energies, which are then used to calculate the equilibrium and non-equilibrium thermodynamic properties of N2, N2+, NO, O2, CN, C2, CO and CO+. The partition functions and the specific heats are systematically validated by available data in the literature. Finally, we calculate the radiative source strengths of diatomic molecules in thermodynamic equilibrium, which agree well with the available values in the literature. The spectral radiative intensities for some diatomic molecules in thermodynamic non-equilibrium are calculated and validated by available experimental data.

Sorption of trace cesium on 21 Hanford Site sediment types

International Nuclear Information System (INIS)

Routson, R.C.; Barney, G.S.; Smith, R.M.; Delegard, C.A.

1980-03-01

Sorption of trace cesium (Cs) was measured on 21 Hanford Site sediment types. A Box-Behnken statistical design was used to develop empirical-statistical equations predicting 137 Cs sorption as a function of the equilibrium concentrations of macroions Na + , K + , and Ca +2 in solution over the concentration ranges of 3.0 to 0.001M, 0.2 to 0.002M, and 0.2 to 0.002M, respectively. These equations are required to estimate trace Cs transport from Hanford ground disposal sites. Average Cs sorption equations for the 21 sediments will be presented and discussed

Distribution, sources and composition of antibiotics in sediment, overlying water and pore water from Taihu Lake, China

Energy Technology Data Exchange (ETDEWEB)

Xu, Jian [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Laboratory of Riverine Ecological Conservation and Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Yuan, E-mail: zhangyuan@craes.org.cn [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Laboratory of Riverine Ecological Conservation and Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhou, Changbo [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Guo, Changsheng; Wang, Dingming [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Laboratory of Riverine Ecological Conservation and Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Du, Ping [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Luo, Yi [College of Environmental Sciences and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Nankai University, Tianjin 300071 (China); Wan, Jun; Meng, Wei [State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Laboratory of Riverine Ecological Conservation and Technology, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China)

2014-11-01

The occurrence of 15 antibiotics classified as sulphonamides, fluoroquinolones, macrolides, tetracyclines and trimethoprim in sediment, overlying water, and pore water matrices in Taihu Lake, China was studied. The total concentrations were from 4.1 μg/kg to 731 μg/kg, from 127 ng/L to 1210 ng/L, and from 1.5 ng/L to 216 ng/L in sediment, overlying water and pore water, respectively. Antibiotics in different locations originated from various sources, depending on human, agricultural and aquacultural activities. Composition analysis indicated that human-derived and animal-derived drugs significantly contributed to the total contamination of antibiotics in the lake, indicating the high complexity of contamination sources in Taihu Lake Basin. The in situ sediment–pore water partitioning coefficients were generally greater than sediment–overlying water partitioning coefficients, suggesting continuous inputs into the lake water. This study shows that antibiotics are ubiquitous in all compartments in Taihu Lake, and their potential hazards to the aquatic ecosystem need further investigation. - Highlights: • Antibiotics are ubiquitous in sediment, overlying water and pore water in Taihu Lake. • Antibiotics in Taihu Lake originated from human and nonhuman activities. • Ksp is higher than Ksw, indicating the continuous antibiotics input to lake water.

Distribution, sources and composition of antibiotics in sediment, overlying water and pore water from Taihu Lake, China

International Nuclear Information System (INIS)

Xu, Jian; Zhang, Yuan; Zhou, Changbo; Guo, Changsheng; Wang, Dingming; Du, Ping; Luo, Yi; Wan, Jun; Meng, Wei

2014-01-01

The occurrence of 15 antibiotics classified as sulphonamides, fluoroquinolones, macrolides, tetracyclines and trimethoprim in sediment, overlying water, and pore water matrices in Taihu Lake, China was studied. The total concentrations were from 4.1 μg/kg to 731 μg/kg, from 127 ng/L to 1210 ng/L, and from 1.5 ng/L to 216 ng/L in sediment, overlying water and pore water, respectively. Antibiotics in different locations originated from various sources, depending on human, agricultural and aquacultural activities. Composition analysis indicated that human-derived and animal-derived drugs significantly contributed to the total contamination of antibiotics in the lake, indicating the high complexity of contamination sources in Taihu Lake Basin. The in situ sediment–pore water partitioning coefficients were generally greater than sediment–overlying water partitioning coefficients, suggesting continuous inputs into the lake water. This study shows that antibiotics are ubiquitous in all compartments in Taihu Lake, and their potential hazards to the aquatic ecosystem need further investigation. - Highlights: • Antibiotics are ubiquitous in sediment, overlying water and pore water in Taihu Lake. • Antibiotics in Taihu Lake originated from human and nonhuman activities. • Ksp is higher than Ksw, indicating the continuous antibiotics input to lake water

Equilibrium and non-equilibrium phenomena in arcs and torches

NARCIS (Netherlands)

Mullen, van der J.J.A.M.

2000-01-01

A general treatment of non-equilibrium plasma aspects is obtained by relating transport fluxes to equilibrium restoring processes in so-called disturbed Bilateral Relations. The (non) equilibrium stage of a small microwave induced plasma serves as case study.

Development of partitioning method : cold experiment with partitioning test facility in NUCEF (I)

International Nuclear Information System (INIS)

Yamaguchi, Isoo; Morita, Yasuji; Kondo, Yasuo

1996-03-01

A test facility in which about 1.85 x 10 14 Bq of high-level liquid waste can be treated has been completed in 1994 at Nuclear Fuel Cycle Safety Engineering Research Facility (NUCEF) for research and development of Partitioning Method. The outline of the partitioning test facility and support equipments for it which were design terms, constructions, arrangements, functions and inspections were given in JAERI-Tech 94-030. The present report describes the results of the water transfer test and partitioning tests, which are methods of precipitation by denitration, oxalate precipitation, solvent extraction, and adsorption with inorganic ion exchanger, using nitric acid to master operation method of the test facility. As often as issues related to equipments occurred during the tests, they were improved. As to issues related to processes such as being stopped up of columns, their measures of solution were found by testing in laboratories. They were reflected in operation of the Partitioning Test Facility. Their particulars and improving points were described in this report. (author)

Retardation of volatile organic compounds in ground water in low organic carbon sediments

International Nuclear Information System (INIS)

Hoffman, F.

1995-04-01

It is postulated that adsorption onto aquifer matrix surfaces is only one of the processes that retard contaminants in ground water in unconsolidated sediments; others include hydrodynamic dispersion, abiotic/biotic degradation, matrix diffusion, partitioning to organic carbon, diffusion into and retention in dead-end pores, etc. This work aims at these processes in defining the K d of VOCs in sediments with low organic carbon content. Experiments performed include an initial column experiment for VOC (TCE and perchloroethylene(PCE)) retardation tests on geological materials, PCE and TCE data from LLNL sediments, and a preliminary multilayer sampler experiment. The VOC K d s in low organic carbon permeable aquifer materials are dependent on the VOC composition and independent of aquifer grain size, indicating that sorption was not operative and that the primary retarding factors are diffusion controlled. The program of future experiments is described

A critical compilation and review of default soil solid/liquid partition coefficients, Kd, for use in environmental assessments

International Nuclear Information System (INIS)

Thibault, D.H.; Sheppard, M.I.; Smith, P.A.

1990-03-01

Environmental assessments of the Canadian concept for disposal of nuclear fuel waste in plutonic rock formations require analyses of the migration of nuclides from the disposal vault to the biosphere. Analyses of nuclide migration via groundwater through the geosphere, unconsolidated overburden and soil use models requiring solid/liquid partition coefficients (K d ) to describe the interaction of the nuclides with the solid materials. This report presents element-specific soil solid/liquid partition coefficients based on a detailed survey of the literature. Values for clays, silt, sand and organic soils are summarized. Partition coefficients for the following elements are presented: americium, antimony, arsenic, barium, boron, cadmium, calcium, carbon, cerium, cesium, chromium, cobalt, copper, curium, europium, iodine, iron, lead, lithium, manganese, molybdenum, neptunium, nickel, niobium, palladium, phosphorus, plutonium, polonium, radium, ruthenium, samarium, selenium, silver, strontium, technetium, tellurium, terbium, thorium, tin, tritium, uranium, zinc, and zirconium. The values compiled in this study are compared with earlier K d value compendiums and are the values recommended for the use in the soil, deep sediment and overburden models for the Environmental Impact Statement on the concept for disposal of Canada's nuclear fuel waste

Application of annular centrifugal contactors in the hot test of the improved total partitioning process for high level liquid waste.

Science.gov (United States)

Duan, Wuhua; Chen, Jing; Wang, Jianchen; Wang, Shuwei; Feng, Xiaogui; Wang, Xinghai; Li, Shaowei; Xu, Chao

2014-08-15

High level liquid waste (HLLW) produced from the reprocessing of the spent nuclear fuel still contains moderate amounts of uranium, transuranium (TRU) actinides, (90)Sr, (137)Cs, etc., and thus constitutes a permanent hazard to the environment. The partitioning and transmutation (P&T) strategy has increasingly attracted interest for the safe treatment and disposal of HLLW, in which the partitioning of HLLW is one of the critical technical issues. An improved total partitioning process, including a TRPO (tri-alkylphosphine oxide) process for the removal of actinides, a CESE (crown ether strontium extraction) process for the removal of Sr, and a CECE (calixcrown ether cesium extraction) process for the removal of Cs, has been developed to treat Chinese HLLW. A 160-hour hot test of the improved total partitioning process was carried out using 72-stage 10-mm-dia annular centrifugal contactors (ACCs) and genuine HLLW. The hot test results showed that the average DFs of total α activity, Sr and Cs were 3.57 × 10(3), 2.25 × 10(4) and 1.68 × 10(4) after the hot test reached equilibrium, respectively. During the hot test, 72-stage 10-mm-dia ACCs worked stable, continuously with no stage failing or interruption of the operation. Copyright © 2014 Elsevier B.V. All rights reserved.

Geochemistry of bed and suspended sediment in the Mississippi river system: provenance versus weathering and winnowing.

Science.gov (United States)

Piper, D Z; Ludington, Steve; Duval, J S; Taylor, H E

2006-06-01

Stream-bed sediment for the size fraction less than 150 microm, examined in 14,000 samples collected mostly from minor tributaries to the major rivers throughout the Mississippi River drainage system, is composed of 5 mineral fractions identified by factor analysis-Al-silicate minerals, quartz, calcite and dolomite, heavy minerals, and an Fe-Mn fraction. The Al-silicate fraction parallels its distribution in the regolith, emphasizing the local sediment source as a primary control to its distribution. Quartz and the heavy-mineral fraction, and associated trace elements, exhibit a complementary distribution to that of the Al-silicate fraction, with a level of enrichment in the bed sediment that is achieved through winnowing and sorting. The carbonate fraction has a distribution suggesting its dissolution during transport. Trace elements partitioned onto the Fe-Mn, possibly amorphous oxyhydride, fraction are introduced to the streams, in part, through human activity. Except for the heavy-mineral fraction, these fractions are identified in suspended sediment from the Mississippi River itself. Although comparison of the tributary bed sediment with the riverine suspended sediment is problematic, the geochemistry of the suspended sediment seems to corroborate the interpretation of the geochemistry of the bed sediment.

Re-dissolution of caesium and plutonium from Irish Sea sediments: a comparison between different modelling approaches

International Nuclear Information System (INIS)

Iosjpe, M.A.; Perianez, R.B.

2004-01-01

Recently, there has been experimental evidence of re-dissolution of plutonium and caesium taking place from contaminated Irish Sea sediments. Thus, sediments are behaving as a long-term source of waste radionuclides to the water column. The objective of this work consists of studying such re-dissolution process by means of mathematical modelling. In particular, two models with different conceptual and numerical approaches will be used. The first is a box model for long-term dispersion from Sellafield to the Arctic marine environment in which water fluxes between boxes are obtained from basic oceanographic information. Water sediment interactions of radionuclides are described through sedimentation and remobilization processes on the basis of the sediment equilibrium distribution coefficient. The second model is a high resolution 3D model in which advective transport is obtained from the calculated current fields. Thus, tidal mixing is explicitly computed. Exchanges of radionuclides between the liquid and solid phases are described in terms of kinetic transfer coefficients. As a consequence, the model has a general applicability and can be used in situations out from equilibrium conditions. Both models have been used to simulate the dispersion of instantaneous releases from Sellafield and to simulate the process of re-dissolution of radionuclides from contaminated sediments. Results from both models are comparable, being differences in activity levels in water and sediments smaller than should be expected from the different modelling approaches. Some general conclusions on the applicability of each modelling approach and on how they can be combined to improve predictions can also be extracted from this work. (author)

Betweenness-based algorithm for a partition scale-free graph

International Nuclear Information System (INIS)

Zhang Bai-Da; Wu Jun-Jie; Zhou Jing; Tang Yu-Hua

2011-01-01

Many real-world networks are found to be scale-free. However, graph partition technology, as a technology capable of parallel computing, performs poorly when scale-free graphs are provided. The reason for this is that traditional partitioning algorithms are designed for random networks and regular networks, rather than for scale-free networks. Multilevel graph-partitioning algorithms are currently considered to be the state of the art and are used extensively. In this paper, we analyse the reasons why traditional multilevel graph-partitioning algorithms perform poorly and present a new multilevel graph-partitioning paradigm, top down partitioning, which derives its name from the comparison with the traditional bottom—up partitioning. A new multilevel partitioning algorithm, named betweenness-based partitioning algorithm, is also presented as an implementation of top—down partitioning paradigm. An experimental evaluation of seven different real-world scale-free networks shows that the betweenness-based partitioning algorithm significantly outperforms the existing state-of-the-art approaches. (interdisciplinary physics and related areas of science and technology)

Understanding thermodynamics of drug partitioning in micelles and delivery to proteins: Studies with naproxen, diclofenac sodium, tetradecyltrimethylammonium bromide, and bovine serum albumin

International Nuclear Information System (INIS)

Talele, Paurnima; Choudhary, Sinjan; Kishore, Nand

2016-01-01

Highlights: • Interactions of non-steroidal anti-inflammatory drugs studied with TTAB micelles, monomers. • Thermodynamics of drug-surfactant interactions and partitioning in micelles addressed. • Mechanism of drug partitioning addressed based on energetics of interactions. • Partitioning in micelles depends on functional groups on drugs. • Such studies are needed for target oriented synthesis and efficient drug delivery. - Abstract: The use of surfactants in drug delivery has offered several advantages. Quantitative knowledge of the interactions of drugs with micellar systems is essential for deriving guidelines to design efficient drug delivery systems. In this work we have quantitatively addressed the mechanism of interaction of naproxen and diclofenac sodium with the micelles and monomers of tetradecyltrimethylammonium bromide (TTAB) based on thermodynamic studies by using isothermal titration calorimetry. The mechanism of interaction of the drugs with TTAB is based on identification of the nature of interactions of the former with the surfactant micelles and monomers. The values of partitioning constant (which is same as equilibrium constant for the reaction of drugs with the surfactant micelles), enthalpy, entropy and stoichiometry of partitioning have been determined and discussed in terms of possible intermolecular interactions. Further, the interaction of the drug naproxen with bovine serum albumin, when delivered from the micellar media has also been addressed in terms of binding constant, enthalpy and entropy of binding. The results are important in developing improved strategies for effective drug delivery systems.

Sediment control - an appropriate solution for small irrigation channels

International Nuclear Information System (INIS)

Shoag, M.A.

2002-01-01

Sediment control is one of the key factors considered prior to the design of an irrigation channel. When the channel takes off from its headworks, its slope is usually smaller than that of the parent stream to obtain required head. If the sediment load is heavy then the channel can not maintain equilibrium since the high influx can not be transported fully due to its small gradient. This results in the deposition of part incoming sediment in the channel itself. A typical irrigation intake suitable for small schemes, which consists of a simple settling basin with double orifice: one at the inlet from the river and the other at the outlet to the canal. The basin is provided with a side spill weir near its downstream end, to discharge flows in excess of the maximum canal capacity. This paper deals with the experimental study of such an arrangement. Different flows were run covering a range of levels in the river, from minimum to flood flows to check the hydraulic performance of the layout and in particular to study its effectiveness in settling sediment at low flows and avoiding excessive sediment input to the canal during flood. (author)

Plane partition vesicles

International Nuclear Information System (INIS)

Rensburg, E J Janse van; Ma, J

2006-01-01

We examine partitions and their natural three-dimensional generalizations, plane partitions, as models of vesicles undergoing an inflation-deflation transition. The phase diagrams of these models include a critical point corresponding to an inflation-deflation transition, and exhibits multicritical scaling in the vicinity of a multicritical point located elsewhere on the critical curve. We determine the locations of the multicritical points by analysing the generating functions using analytic and numerical means. In addition, we determine the numerical values of the multicritical scaling exponents associated with the multicritical scaling regimes in these models

The importance of applying an appropriate data partitioning

CERN Document Server

Dimitrov, Gancho; The ATLAS collaboration

2015-01-01

In this presentation are described specific technical solutions put in place in various database applications of the ATLAS experiment at LHC where we make use of several partitioning techniques available in Oracle 11g. With the broadly used range partitioning and its option of automatic interval partitioning we add our own logic in PLSQL procedures and scheduler jobs to sustain data sliding windows in order to enforce various data retention policies. We also make use of the new Oracle 11g reference partitioning in the ATLAS Nightly Build System to achieve uniform data segmentation. However the most challenging was to segment the data of the new ATLAS Distributed Data Management system, which resulted in tens of thousands list type partitions and sub-partitions. Partition and sub-partition management, index strategy, statistics gathering and queries execution plan stability are important factors when choosing an appropriate physical model for the application data management. The so-far accumulated knowledge wi...

Effects of Flaming Gorge Dam hydropower operations on sediment transport in the Browns Park reach of the Green River, Utah and Colorado

International Nuclear Information System (INIS)

Williams, G.P.; Tomasko, D.; Cho, H.E.; Yin, S.C.L.

1995-05-01

Three methods for comparing sediment transport were applied to four proposed hydropower operational scenarios under study for Flaming Gorge Dam on the Green River in Utah. These methods were effective discharge, equilibrium potential, and cumulative sediment load with flow exceedance plots. Sediment loads transported by the Green River in the Browns Park reach were calculated with the Engelund-Hansen equation for three historical water years and four hydropower operational scenarios. A model based on the Engelund-Hansen equation was developed using site-specific information and validated by comparing predictions for a moderate water year with measured historical values. The three methods were used to assess the impacts of hydropower operational scenarios on sediment resources. The cumulative sediment load method provided the most useful information for impact evaluation. Effective discharge was not a useful tool because of the limited number of discrete flows associated with synthetic hydrographs for the hydropower operational scenarios. The equilibrium potential method was relatively insensitive to the variations in operating conditions, rendering it comparatively ineffective for impact evaluation

Perfluoroalkyl and polyfluoroalkyl substances in sediments from South Bohai coastal watersheds, China

International Nuclear Information System (INIS)

Zhu, Zhaoyun; Wang, Tieyu; Wang, Pei; Lu, Yonglong; Giesy, John P.

2014-01-01

Highlights: • Relatively high concentrations of PFAS, especially PFOA, were found in the Xiaoqing River sediment. • PFOA and PFBS were the dominant PFAS in the sediments from coastal and riverine area, respectively. • Concentrations of PFNA, PFDA and PFHxS in sediment were significantly correlated with concentrations of organic carbon. • Risks posed by PFOA and PFOS to benthic organisms from concentrations of PFAS in sediments were small. - Abstract: This study investigated the concentrations and distribution of Perfluoroalkyl and polyfluoroalkyl substances (PFAS) in sediments of 12 rivers from South Bohai coastal watersheds. The highest concentrations of ΣPFAS (31.920 ng g −1 dw) and PFOA (29.021 ng g −1 dw) were found in sediments from the Xiaoqing River, which was indicative of local point sources in this region. As for other rivers, concentrations of ΣPFAS ranged from 0.218 to 1.583 ng g −1 dw were found in the coastal sediments and from 0.167 to 1.953 ng g −1 dw in the riverine sediments. Predominant PFAS from coastal and riverine areas were PFOA and PFBS, with percentages of 30% and 35%, respectively. Partitioning analysis showed the concentrations of PFNA, PFDA and PFHxS were significantly correlated with organic carbon. The results of a preliminary environmental hazard assessment showed that PFOS posed the highest hazard in the Mi River, while PFOA posed a relative higher hazard in the Xiaoqing River

Excitation energy partition in deeply inelastic collisions between 40Ar and Ag at 27 MeV per nucleon

International Nuclear Information System (INIS)

Borderie, B.; Rivet, M.F.; Cabot, C.; Fuchs, H.; Gardes, D.; Hanappe, F.; Jouan, D.; Montoya, M.

1991-01-01

The dynamics of the two partners produced in dissipative collisions has been experimentally studied for the system 40 Ar+Ag at 27 MeV per nucleon. Primary masses of the fragments can then be calculated; the excitation energy partition between the two fragments is derived from the number of particles evaporated by each fragment. We found that this division evolves from equipartition to a repartition close to thermal equilibrium in the excitation energy range 300-350 MeV or interaction times 5-10x10 -22 s. (orig.)

226Ra chronology of a coastal marine sediment

International Nuclear Information System (INIS)

Koide, M.; Bruland, K.; Goldberg, E.D.

1976-01-01

Unsupported 226 Ra (tsub (1/2) = 1620 years) in marine sediments can provide a basis for measuring rates of accumulation of the order of centimeters per thousand years. The excess radium apparently enters the sediments incorporated in phytoplankton. The sensitivity of the method depends upon the initial value of the unsupported 226 Ra and of the value of 230 Th, a parent of 226 Ra, in the sedimentary components. 226 Ra dating was applied to a sediment taken from the slope of the San Clemente Basin in the Southern California coastal region. Rates of sedimentation over two half-lives of the nuclide were found to be either 5.2 or 5.3 cm/1000 years depending upon which of two models for the geochronology is used. One model assumes that the 230 Th brings to the deposit an amount of 226 Ra in equilibrium with it. The other is based upon the growth of the 226 Ra from the 230 Th in the sedimentary components. 238+239 Pu and 210 Pb levels in the upper strata indicated sedimentation rates of the order of 100-500 cm/1000 years, i.e. much faster accumulations. It is suggested that these derived rates are spurious and reflect bioturbative activities of surface-living organisms. (Auth.)

Mercury contaminated sediment sites—An evaluation of remedial options

Energy Technology Data Exchange (ETDEWEB)

Randall, Paul M., E-mail: randall.paul@epa.gov [U.S. Environmental Protection Agency, Office of Research and Development, National Risk Management Research Laboratory, 26 West Martin Luther King Drive, Cincinnati, OH 45268 (United States); Chattopadhyay, Sandip, E-mail: Sandip.Chattopadhyay@tetratech.com [Tetra Tech, Inc., 250 West Court Street, Suite 200W, Cincinnati, OH 45202 (United States)

2013-08-15

Mercury (Hg) is a naturally-occurring element that is ubiquitous in the aquatic environment. Though efforts have been made in recent years to decrease Hg emissions, historically-emitted Hg can be retained in the sediments of aquatic bodies where they may be slowly converted to methylmercury (MeHg). Consequently, Hg in historically-contaminated sediments can result in high levels of significant exposure for aquatic species, wildlife and human populations consuming fish. Even if source control of contaminated wastewater is achievable, it may take a very long time, perhaps decades, for Hg-contaminated aquatic systems to reach relatively safe Hg levels in both water and surface sediment naturally. It may take even longer if Hg is present at higher concentration levels in deep sediment. Hg contaminated sediment results from previous releases or ongoing contributions from sources that are difficult to identify. Due to human activities or physical, chemical, or biological processes (e.g. hydrodynamic flows, bioturbation, molecular diffusion, and chemical transformation), the buried Hg can be remobilized into the overlying water. Hg speciation in the water column and sediments critically affect the reactivity (i.e. conversion of inorganic Hg(II) to MeHg), transport, and its exposure to living organisms. Also, geochemical conditions affect the activity of methylating bacteria and its availability for methylation. This review paper discusses remedial considerations (e.g. key chemical factors in fate and transport of Hg, source characterization and control, environmental management procedures, remediation options, modeling tools) and includes practical case studies for cleaning up Hg-contaminated sediment sites. -- Highlights: ► Managing mercury-contaminated sediment sites are challenging to remediate. ► Remediation technologies are making a difference in managing these sites. ► Partitioning plays a dominant role in the distribution of mercury species. ► Mathematical

Present status of partitioning developments

International Nuclear Information System (INIS)

Nakamura, Haruto; Kubota, Masumitsu; Tachimori, Shoichi

1978-09-01

Evolution and development of the concept of partitioning of high-level liquid wastes (HLLW) in nuclear fuel reprocessing are reviewed historically from the early phase of separating useful radioisotopes from HLLW to the recent phase of eliminating hazardous nuclides such as transuranium elements for safe waste disposal. Since the criteria in determining the nuclides for elimination and the respective decontamination factors are important in the strategy of partitioning, current views on the criteria are summarized. As elimination of the transuranium is most significant in the partitioning, various methods available of separating them from fission products are evaluated. (auth.)

Classification algorithms using adaptive partitioning

KAUST Repository

Binev, Peter; Cohen, Albert; Dahmen, Wolfgang; DeVore, Ronald

2014-01-01

© 2014 Institute of Mathematical Statistics. Algorithms for binary classification based on adaptive tree partitioning are formulated and analyzed for both their risk performance and their friendliness to numerical implementation. The algorithms can be viewed as generating a set approximation to the Bayes set and thus fall into the general category of set estimators. In contrast with the most studied tree-based algorithms, which utilize piecewise constant approximation on the generated partition [IEEE Trans. Inform. Theory 52 (2006) 1335.1353; Mach. Learn. 66 (2007) 209.242], we consider decorated trees, which allow us to derive higher order methods. Convergence rates for these methods are derived in terms the parameter - of margin conditions and a rate s of best approximation of the Bayes set by decorated adaptive partitions. They can also be expressed in terms of the Besov smoothness β of the regression function that governs its approximability by piecewise polynomials on adaptive partition. The execution of the algorithms does not require knowledge of the smoothness or margin conditions. Besov smoothness conditions are weaker than the commonly used Holder conditions, which govern approximation by nonadaptive partitions, and therefore for a given regression function can result in a higher rate of convergence. This in turn mitigates the compatibility conflict between smoothness and margin parameters.

Classification algorithms using adaptive partitioning

KAUST Repository

Binev, Peter

2014-12-01

© 2014 Institute of Mathematical Statistics. Algorithms for binary classification based on adaptive tree partitioning are formulated and analyzed for both their risk performance and their friendliness to numerical implementation. The algorithms can be viewed as generating a set approximation to the Bayes set and thus fall into the general category of set estimators. In contrast with the most studied tree-based algorithms, which utilize piecewise constant approximation on the generated partition [IEEE Trans. Inform. Theory 52 (2006) 1335.1353; Mach. Learn. 66 (2007) 209.242], we consider decorated trees, which allow us to derive higher order methods. Convergence rates for these methods are derived in terms the parameter - of margin conditions and a rate s of best approximation of the Bayes set by decorated adaptive partitions. They can also be expressed in terms of the Besov smoothness β of the regression function that governs its approximability by piecewise polynomials on adaptive partition. The execution of the algorithms does not require knowledge of the smoothness or margin conditions. Besov smoothness conditions are weaker than the commonly used Holder conditions, which govern approximation by nonadaptive partitions, and therefore for a given regression function can result in a higher rate of convergence. This in turn mitigates the compatibility conflict between smoothness and margin parameters.

Maximum Recoverable Gas from Hydrate Bearing Sediments by Depressurization

KAUST Repository

Terzariol, Marco

2017-11-13

The estimation of gas production rates from hydrate bearing sediments requires complex numerical simulations. This manuscript presents a set of simple and robust analytical solutions to estimate the maximum depressurization-driven recoverable gas. These limiting-equilibrium solutions are established when the dissociation front reaches steady state conditions and ceases to expand further. Analytical solutions show the relevance of (1) relative permeabilities between the hydrate free sediment, the hydrate bearing sediment, and the aquitard layers, and (2) the extent of depressurization in terms of the fluid pressures at the well, at the phase boundary, and in the far field. Close form solutions for the size of the produced zone allow for expeditious financial analyses; results highlight the need for innovative production strategies in order to make hydrate accumulations an economically-viable energy resource. Horizontal directional drilling and multi-wellpoint seafloor dewatering installations may lead to advantageous production strategies in shallow seafloor reservoirs.

The Benefits of Adaptive Partitioning for Parallel AMR Applications

Energy Technology Data Exchange (ETDEWEB)

Steensland, Johan [Sandia National Lab. (SNL-CA), Livermore, CA (United States). Advanced Software Research and Development

2008-07-01

Parallel adaptive mesh refinement methods potentially lead to realistic modeling of complex three-dimensional physical phenomena. However, the dynamics inherent in these methods present significant challenges in data partitioning and load balancing. Significant human resources, including time, effort, experience, and knowledge, are required for determining the optimal partitioning technique for each new simulation. In reality, scientists resort to using the on-board partitioner of the computational framework, or to using the partitioning industry standard, ParMetis. Adaptive partitioning refers to repeatedly selecting, configuring and invoking the optimal partitioning technique at run-time, based on the current state of the computer and application. In theory, adaptive partitioning automatically delivers superior performance and eliminates the need for repeatedly spending valuable human resources for determining the optimal static partitioning technique. In practice, however, enabling frameworks are non-existent due to the inherent significant inter-disciplinary research challenges. This paper presents a study of a simple implementation of adaptive partitioning and discusses implied potential benefits from the perspective of common groups of users within computational science. The study is based on a large set of data derived from experiments including six real-life, multi-time-step adaptive applications from various scientific domains, five complementing and fundamentally different partitioning techniques, a large set of parameters corresponding to a wide spectrum of computing environments, and a flexible cost function that considers the relative impact of multiple partitioning metrics and diverse partitioning objectives. The results show that even a simple implementation of adaptive partitioning can automatically generate results statistically equivalent to the best static partitioning. Thus, it is possible to effectively eliminate the problem of determining the

The distribution and adsorption behavior of aliphatic amines in marine and lacustrine sediments

Science.gov (United States)

Wang, Xu-chen; Lee, Cindy

1990-10-01

The methylated amines—monomethyl-, dimethyl-, and trimethyl amine (MMA, DMA, TMA)—are commonly found in aquatic environments, apparently as a result of decomposition processes. Adsorption of these amines to clay minerals and organic matter significantly influences their distribution in sediments. Laboratory measurements using 14C-radiolabelled amines and application of a linear partitioning model resulted in calculated adsorption coefficients of 2.4-4.7 (MMA), 3.3 (DMA), and 3.3-4.1 (TMA). Further studies showed that adsorption of amines is influenced by salinity of the porewaters, and clay mineral and organic matter content of the sediment solid phase. Concentrations of monomethyl- and dimethyl amine were measured in the porewaters and the solid phase of sediment samples collected from Flax Pond and Lake Ronkonkoma (NY), Long Island Sound, and the coastal Peru upwelling area. These two amines were present in all sediments investigated. A clear seasonal increase in the solid-phase concentration of MMA and DMA in Flax Pond sediments was likely related to the annual senescence of salt marsh grasses, either directly as a source of these compounds or indirectly by providing additional exchange capacity to the sediments. The distribution of amines in the solid and dissolved phases observed in all sediments investigated suggests that the distribution of these compounds results from a balance among production, decomposition, and adsorption processes.

Non-equilibrium synthesis of alloys using lasers

International Nuclear Information System (INIS)

Mazumder, J.; Choi, J.; Ribaudo, C.; Wang, A.; Kar, A.

1993-01-01

This paper discusses microstructure and properties of alloys, produced by laser alloying and cladding technique, for various applications. These include Fe-Cr-W-C alloys for wear resistance, Ni-Cr-Al-Hf alloys for high temperature oxidation resistance and Mg-Al alloys for corrosion resistance. Also a mathematical model will be presented for the prediction of the composition of the metastable phases produced by laser synthesis. Microstructure was characterized using various electron optical techniques such as Transmission Electron Microscopy (TEM), Scanning Electron Microscopy (SEM), Auger Electron Spectroscopy (AES) and Energy Dispersive X-Ray Analysis (EDAX). Wear properties were characterized by a line contact Block on Cylinder method. High temperature oxidation properties were characterized by using Perkin-Elmer Thermo-Gravimetric Analyzer (TGA) where dynamic weight change were monitored at 1,200 C. Corrosion properties were evaluated by a potentio-dynamic method using a computer controlled Potentiostat manufactured by EG ampersand G. A non-equilibrium M 6 C type carbide was found to be responsible for the improved wear resistance. Increased solid-solubility of Hf was found to be a major factor in improving the high temperature oxidation resistance of the Ni-Cr-Al-Hf alloys. Micro-Crystalline phases were observed in Mg-Al alloys. The rapid solidification was modeled using heat transfer in the liquid pool and the solid substrate and mass transfer in the liquid pool. Non-equilibrium partition coefficient was introduced through the boundary condition at the liquid-solid interface. A good correlation was observed between the prediction and the experimental data. 54 refs

Effects of nutrient loading on the carbon balance of coastal wetland sediments

Science.gov (United States)

Morris, J.T.; Bradley, P.M.

1999-01-01

Results of a 12-yr study in an oligotrophic South Carolina salt marsh demonstrate that soil respiration increased by 795 g C m-2 yr-1 and that carbon inventories decreased in sediments fertilized with nitrogen and phosphorus. Fertilized plots became net sources of carbon to the atmosphere, and sediment respiration continues in these plots at an accelerated pace. After 12 yr of treatment, soil macroorganic matter in the top 5 cm of sediment was 475 g C m-2 lower in fertilized plots than in controls, which is equivalent to a constant loss rate of 40 g C m-2 yr-1. It is not known whether soil carbon in fertilized plots has reached a new equilibrium or continues to decline. The increase in soil respiration in the fertilized plots was far greater than the loss of sediment organic matter, which indicates that the increase in soil respiration was largely due to an increase in primary production. Sediment respiration in laboratory incubations also demonstrated positive effects of nutrients. Thus, the results indicate that increased nutrient loading of oligotrophic wetlands can lead to an increased rate of sediment carbon turnover and a net loss of carbon from sediments.

Trace metal distribution in sediments of the Pearl River Estuary and the surrounding coastal area, South China

International Nuclear Information System (INIS)

Ip, Carman C.M.; Li Xiangdong; Zhang Gan; Wai, Onyx W.H.; Li, Y.-S.

2007-01-01

Surface sediments and sediment cores collected at the Pearl River Estuary (PRE) and its surrounding coastal area were analysed for total metal concentrations, chemical partitioning, and Pb isotopic compositions. The distribution of Cu, Cr, Pb, and Zn demonstrated a typical diffusion pattern from the land to the direction of the sea. Two hotspots of trace metal contamination were located at the mixed zone between freshwater and marine waters. The enrichment of metals in the sediments could be attributed to the deposition of the dissolved and particulate trace metals in the water column at the estuarine area. The similar Pb isotopic signatures of the sediments at the PRE and its surrounding coastal area offered strong evidence that the PRE was a major source of trace metals to the adjacent coastal area. Slightly lower 206 Pb/ 207 Pb ratios in the coastal sediments may indicate other inputs of Pb in addition to the PRE sources, including the inputs from Hong Kong and other parts of the region. - The distribution of trace metals in sediments reflected contaminant sources, physical and chemical deposition processes

Modeling sediment transport with an integrated view of the biofilm effects

Science.gov (United States)

Fang, H. W.; Lai, H. J.; Cheng, W.; Huang, L.; He, G. J.

2017-09-01

Most natural sediment is invariably covered by biofilms in reservoirs and lakes, which have significant influence on bed form dynamics and sediment transport, and also play a crucial role in natural river evolution, pollutant transport, and habitat changes. However, most models for sediment transport are based on experiments using clean sediments without biological materials. In this study, a three-dimensional mathematical model of hydrodynamics and sediment transport is presented with a comprehensive consideration of the biofilm effects. The changes of the bed resistance mainly due to the different bed form dynamics of the biofilm-coated sediment (biosediment), which affect the hydrodynamic characteristics, are considered. Moreover, the variations of parameters related to sediment transport after the biofilm growth are integrated, including the significant changes of the incipient velocity, settling velocity, reference concentration, and equilibrium bed load transport rate. The proposed model is applied to evaluate the effects of biofilms on the hydrodynamic characteristics and sediment transport in laboratory experiments. Results indicate that the mean velocity increases after the biofilm growth, and the turbulence intensity near the river bed decreases under the same flow condition. Meanwhile, biofilm inhibits sediment from moving independently. Thus, the moderate erosion is observed for biosediment resulting in smaller suspended sediment concentrations. The proposed model can reasonably reflect these sediment transport characteristics with biofilms, and the approach to integration of the biological impact could also be used in other modeling of sediment transport, which can be further applied to provide references for the integrated management of natural aqueous systems.

Gas/aerosol Partitioning Parameterisation For Global Modelling: A Physical Interpretation of The Relationship Between Activity Coefficients and Relative Humidity

Science.gov (United States)

Metzger, S.; Dentener, F. J.; Lelieveld, J.; Pandis, S. N.

A computationally efficient model (EQSAM) to calculate gas/aerosol partitioning ofsemi-volatile inorganic aerosol components has been developed for use in global- atmospheric chemistry and climate models; presented at the EGS 2001.We introduce and discuss here the physics behind the parameterisation, upon whichthe EQuilib- rium Simplified Aerosol Model EQSAM is based. The parameterisation,which ap- proximates the activity coefficient calculation sufficiently accurately forglobal mod- elling, is based on a method that directly relates aerosol activitycoefficients to the ambient relative humidity, assuming chemical equilibrium.It therefore provides an interesting alternative for the computationally expensiveiterative activity coefficient calculation methods presently used in thermodynamicgas/aerosol equilibrium mod- els (EQMs). The parameterisation can be used,however, also in dynamical models that calculate mass transfer between theliquid/solid aerosol phases and the gas/phase explicitly; dynamical models oftenincorporate an EQM to calculate the aerosol com- position. The gain of theparameterisation is that the entire system of the gas/aerosol equilibrium partitioningcan be solved non-iteratively, a substantial advantage in global modelling.Since we have already demonstrated at the EGS 2001 that EQSAM yields similarresults as current state-of-the-art equilibrium models, we focus here on a dis- cussionof our physical interpretation of the parameterisation; the identification of theparameters needed is crucial. Given the lag of reliable data, the best way tothor- oughly validate the parameterisation for global modelling applications is theimple- mentation in current state-of-the-art gas/aerosol partitioning routines, whichare embe- ded in e.g. a global atmospheric chemistry transport model, by comparingthe results of the parameterisation against the ones based on the widely used activitycoefficient calculation methods (i.e. Bromley, Kussik-Meissner or Pitzer). Then

Gentile statistics and restricted partitions

Indian Academy of Sciences (India)

The partition function of Gentile statistics also has the property that it nicely interpolates between the ... We now construct the partition function for such a system which also incorporates the property of interpolation ... As in [4], we however keep s arbitrary even though for s > 2 there are no quadratic. Hamiltonian systems.

Characteristics of phosphorus adsorption by sediment mineral matrices with different particle sizes

Directory of Open Access Journals (Sweden)

Yang Xiao

2013-07-01

Full Text Available The particle size of sediment is one of the main factors that influence the phosphorus physical adsorption on sediment. In order to eliminate the effect of other components of sediment on the phosphorus physical adsorption the sediment mineral matrices were obtained by removing inorganic matter metal oxides, and organic matter from natural sediments, which were collected from the Nantong reach of the Yangtze River. The results show that an exponential relationship exists between the median particle size (D50 and specific surface area (Sg of the sediment mineral matrices, and the fine sediment mineral matrix sample has a larger specific surface area and pore volume than the coarse sediment particles. The kinetic equations were used to describe the phosphorus adsorption process of the sediment mineral matrices, including the Elovich equation, quasi-first-order adsorption kinetic equation, and quasi-second-order adsorption kinetic equation. The results show that the quasi-second-order adsorption kinetic equation has the best fitting effect. Using the mass conservation and Langmuir adsorption kinetic equations, a formula was deduced to calculate the equilibrium adsorption capacity of the sediment mineral matrices. The results of this study show that the phosphorus adsorption capacity decreases with the increase of D50, indicating that the specific surface area and pore volume are the main factors in determining the phosphorus adsorption capacity of the sediment mineral matrices. This study will help understand the important role of sediment in the transformation of phosphorus in aquatic environments.

The importance of having an appropriate data segmentation (partitioning)

CERN Document Server

Dimitrov, Gancho; The ATLAS collaboration

2014-01-01

In this presentation will be shown real life examples from database applications in the ATLAS experiment @ LHC where we make use of many Oracle partitioning techniques available in Oracle 11g. With the broadly used range partitioning and its option of automatic interval partitioning we add our own logic in PLSQL for sustaining data sliding windows in order to enforce various data retention policies. We also make use of the reference partitioning in some use cases, however the most challenging was to segment the data of a large bookkeeping system which resulted in tens of thousands list partitions and list sub-partitions. Partition and sub-partition management, index strategy, statistics gathering and queries execution plan stability are important factors when choosing an appropriate for the use case data management model. The gained experience with all of those will be shared with the audience.

Equilibrium and pre-equilibrium emissions in proton-induced ...

Indian Academy of Sciences (India)

necessary for the domain of fission-reactor technology for the calculation of nuclear transmutation ... tions occur in three stages: INC, pre-equilibrium and equilibrium (or compound. 344. Pramana ... In the evaporation phase of the reaction, the.

Generating Milton Babbitt's all-partition arrays

OpenAIRE

Bemman, Brian; Meredith, David

2016-01-01

In most of Milton Babbitt's (1916–2011) works written since the early 1960s, both the pitch and rhythmic content is organized according to a highly constrained structure known as the all-partition array. The all-partition array provides a framework that ensures that as many different forms of a tone row as possible (generated by any combination of transposition, inversion or reversal) are expressed 'horizontally' and that each integer partition of 12 whose cardinality is no greater than the n...

Lift of dilogarithm to partition identities

International Nuclear Information System (INIS)

Terhoeven, M.

1992-11-01

For the whole set of dilogarithm identities found recently using the thermodynamic Bethe-Ansatz for the ADET series of purely elastic scattering theories we give partition identities which involve characters of those conformal field theories which correspond to the UV-limits of the scattering theories. These partition identities in turn allow to derive the dilogarithm identities using modular invariance and a saddle point approximation. We conjecture on possible generalizations of this correspondance, namely, a lift from dilogarithm to partition identities. (orig.)

Shape characteristics of equilibrium and non-equilibrium fractal clusters.

Science.gov (United States)

Mansfield, Marc L; Douglas, Jack F

2013-07-28

It is often difficult in practice to discriminate between equilibrium and non-equilibrium nanoparticle or colloidal-particle clusters that form through aggregation in gas or solution phases. Scattering studies often permit the determination of an apparent fractal dimension, but both equilibrium and non-equilibrium clusters in three dimensions frequently have fractal dimensions near 2, so that it is often not possible to discriminate on the basis of this geometrical property. A survey of the anisotropy of a wide variety of polymeric structures (linear and ring random and self-avoiding random walks, percolation clusters, lattice animals, diffusion-limited aggregates, and Eden clusters) based on the principal components of both the radius of gyration and electric polarizability tensor indicates, perhaps counter-intuitively, that self-similar equilibrium clusters tend to be intrinsically anisotropic at all sizes, while non-equilibrium processes such as diffusion-limited aggregation or Eden growth tend to be isotropic in the large-mass limit, providing a potential means of discriminating these clusters experimentally if anisotropy could be determined along with the fractal dimension. Equilibrium polymer structures, such as flexible polymer chains, are normally self-similar due to the existence of only a single relevant length scale, and are thus anisotropic at all length scales, while non-equilibrium polymer structures that grow irreversibly in time eventually become isotropic if there is no difference in the average growth rates in different directions. There is apparently no proof of these general trends and little theoretical insight into what controls the universal anisotropy in equilibrium polymer structures of various kinds. This is an obvious topic of theoretical investigation, as well as a matter of practical interest. To address this general problem, we consider two experimentally accessible ratios, one between the hydrodynamic and gyration radii, the other

Occurence of antibiotic compounds found in the water column and bottom sediments from a stream receiving two waste water treatment plant effluents in northern New Jersey, 2008

Science.gov (United States)

Gibs, Jacob; Heckathorn, Heather A.; Meyer, Michael T.; Klapinski, Frank R.; Alebus, Marzooq; Lippincott, Robert

2013-01-01

An urban watershed in northern New Jersey was studied to determine the presence of four classes of antibiotic compounds (macrolides, fluoroquinolones, sulfonamides, and tetracyclines) and six degradates in the water column and bottom sediments upstream and downstream from the discharges of two wastewater treatment plants (WWTPs) and a drinking-water intake (DWI). Many antibiotic compounds in the four classes not removed by conventional WWTPs enter receiving waters and partition to stream sediments. Samples were collected at nine sampling locations on 2 days in September 2008. Two of the nine sampling locations were background sites upstream from two WWTP discharges on Hohokus Brook. Another background site was located upstream from a DWI on the Saddle River above the confluence with Hohokus Brook. Because there is a weir downstream of the confluence of Hohokus Brook and Saddle River, the DWI receives water from Hohokus Brook at low stream flows. Eight antibiotic compounds (azithromycin (maximum concentration 0.24 μg/L), ciprofloxacin (0.08 μg/L), enrofloxacin (0.015 μg/L), erythromycin (0.024 μg/L), ofloxacin (0.92 μg/L), sulfamethazine (0.018 μg/L), sulfamethoxazole (0.25 μg/L), and trimethoprim (0.14 μg/L)) and a degradate (erythromycin-H2O (0.84 μg/L)) were detected in the water samples from the sites downstream from the WWTP discharges. The concentrations of six of the eight detected compounds and the detected degradate compound decreased with increasing distance downstream from the WWTP discharges. Azithromycin, ciprofloxacin, ofloxacin, and trimethoprim were detected in stream-bottom sediments. The concentrations of three of the four compounds detected in sediments were highest at a sampling site located downstream from the WWTP discharges. Trimethoprim was detected in the sediments from a background site. Pseudo-partition coefficients normalized for streambed sediment organic carbon concentration were calculated for azithromycin, ciprofloxacin, and

210Pb and Mass Flux Imbalance Between the Settling Particulates and Sediments at a Sediment Trap

Science.gov (United States)

Wu, C.; Chung, Y.; Hung, G.

2005-05-01

In order to evaluate the mass balance problems between the settling particulates and the underlying sediments, sediment traps were deployed at M1 site (21o32¡¦N, 119o28¡¦E; 2948m) where a box core was taken recently. The sediment trap results were previously published (Chung et al., 2004: Continental Shelf Research). We report here the 210Pb profile measured on this box core by determining its daughter, 210Po, with alpha spectrometry, assuming the paired nuclides are in radioactive equilibrium. The box core (33 cm long, taken in June, 2004) was analyzed for the distributions of its water content, loss on ignition (LOI), and 210Pb. The water content decreases with depth and averages about 55 percent; the LOI as a measure of the total organic matter (TOM) is fairly constant at about 12 percent. The 210Pb profile shows a general exponential decrease with depth, yielding a maximum sedimentation rate of 0.26cm/y, applying a constant flux and constant sedimentation rate model. This rate translates to a mass flux of 0.31g/cm2/y or about 8.5g/m2/d with a dry bulk density of 1.2g/cm3. Based on the excess 210Pb inventory integrated over the core length, the 210Pb flux is estimated at about 19.2dpm/cm2/y or 526dpm/cm2/d assuming at steady state. The 210Pb and mass fluxes obtained from the deepest trap at M1 were only 129dpm/m2/d and 0.55g/m2/d, respectively. The large ¡excess¡" of the 210Pb and mass fluxes in the sediments over those measured from the sediment trap (4 times in 210Pb flux and 14 times in mass flux) suggests either the sedimentation rate was overestimated due to neglect of the mixing effect, and/or large additional particulates, as resuspended sediments which contain less 210Pb, have been transported laterally near the bottom from elsewhere.

Data Partitioning Technique for Improved Video Prioritization

Directory of Open Access Journals (Sweden)

Ismail Amin Ali

2017-07-01

Full Text Available A compressed video bitstream can be partitioned according to the coding priority of the data, allowing prioritized wireless communication or selective dropping in a congested channel. Known as data partitioning in the H.264/Advanced Video Coding (AVC codec, this paper introduces a further sub-partition of one of the H.264/AVC codec’s three data-partitions. Results show a 5 dB improvement in Peak Signal-to-Noise Ratio (PSNR through this innovation. In particular, the data partition containing intra-coded residuals is sub-divided into data from: those macroblocks (MBs naturally intra-coded, and those MBs forcibly inserted for non-periodic intra-refresh. Interactive user-to-user video streaming can benefit, as then HTTP adaptive streaming is inappropriate and the High Efficiency Video Coding (HEVC codec is too energy demanding.

Estuarine Sediment Deposition during Wetland Restoration: A GIS and Remote Sensing Modeling Approach

Science.gov (United States)

Newcomer, Michelle; Kuss, Amber; Kentron, Tyler; Remar, Alex; Choksi, Vivek; Skiles, J. W.

2011-01-01

Restoration of the industrial salt flats in the San Francisco Bay, California is an ongoing wetland rehabilitation project. Remote sensing maps of suspended sediment concentration, and other GIS predictor variables were used to model sediment deposition within these recently restored ponds. Suspended sediment concentrations were calibrated to reflectance values from Landsat TM 5 and ASTER using three statistical techniques -- linear regression, multivariate regression, and an Artificial Neural Network (ANN), to map suspended sediment concentrations. Multivariate and ANN regressions using ASTER proved to be the most accurate methods, yielding r2 values of 0.88 and 0.87, respectively. Predictor variables such as sediment grain size and tidal frequency were used in the Marsh Sedimentation (MARSED) model for predicting deposition rates for three years. MARSED results for a fully restored pond show a root mean square deviation (RMSD) of 66.8 mm (<1) between modeled and field observations. This model was further applied to a pond breached in November 2010 and indicated that the recently breached pond will reach equilibrium levels after 60 months of tidal inundation.

EXTENSION OF FORMULAS FOR PARTITION FUNCTIONS

African Journals Online (AJOL)

Ladan et al.

2Department of Mathematics, Ahmadu Bello University, Zaria. ... 2 + 1 + 1. = 1 + 1 + 1 + 1. Partition function ( ). Andrew and Erikson (2004) stated that the ..... Andrews, G.E., 1984, The Theory of Partitions, Cambridge ... Pure Appl. Math.

The distribution dynamics and desorption behaviour of mobile pharmaceuticals and caffeine to combined sewer sediments.

Science.gov (United States)

Hajj-Mohamad, M; Darwano, H; Duy, S Vo; Sauvé, S; Prévost, M; Arp, H P H; Dorner, S

2017-01-01

Pharmaceuticals are discharged to the environment from wastewater resource recovery facilities, sewer overflows, and illicit sewer connections. To understand the fate of pharmaceuticals, there is a need to better understand their sorption dynamics to suspended sediments (SS) and settled sediments (StS) in sewer systems. In this study, such sorption dynamics to both SS and StS were assessed using a batch equilibrium method under both static and dynamic conditions. Experiments were performed with natively occurring and artificially modified concentrations of sewer pharmaceuticals (acetaminophen, theophylline, carbamazepine, and a metabolite of carbamazepine) and caffeine. Differences in apparent distribution coefficients, K d,app , between SS and StS were related to differences in their organic carbon (OC) content, and the practice of artificially modifying the concentration. K d,app values of modified contaminant concentrations and high OC sediments were substantially higher. Pseudo-second order desorption rates for these mobile compounds were also quantified. Successive flushing events to simulate the addition of stormwater to sewer networks revealed that aqueous concentrations would not necessarily decrease, because the added water will rapidly return to equilibrium concentrations with the sediments. Sorption and desorption kinetics must be considered in addition to dilution, to avoid underestimating the influence of dilution on concentrations of pharmaceuticals discharged to the environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

The partition dimension of cycle books graph

Science.gov (United States)

Santoso, Jaya; Darmaji

2018-03-01

Let G be a nontrivial and connected graph with vertex set V(G), edge set E(G) and S ⊆ V(G) with v ∈ V(G), the distance between v and S is d(v,S) = min{d(v,x)|x ∈ S}. For an ordered partition ∏ = {S 1, S 2, S 3,…, Sk } of V(G), the representation of v with respect to ∏ is defined by r(v|∏) = (d(v, S 1), d(v, S 2),…, d(v, Sk )). The partition ∏ is called a resolving partition of G if all representations of vertices are distinct. The partition dimension pd(G) is the smallest integer k such that G has a resolving partition set with k members. In this research, we will determine the partition dimension of Cycle Books {B}{Cr,m}. Cycle books graph {B}{Cr,m} is a graph consisting of m copies cycle Cr with the common path P 2. It is shown that the partition dimension of cycle books graph, pd({B}{C3,m}) is 3 for m = 2, 3, and m for m ≥ 4. pd({B}{C4,m}) is 3 + 2k for m = 3k + 2, 4 + 2(k ‑ 1) for m = 3k + 1, and 3 + 2(k ‑ 1) for m = 3k. pd({B}{C5,m}) is m + 1.

Quantum Dilogarithms and Partition q-Series

Science.gov (United States)

Kato, Akishi; Terashima, Yuji

2015-08-01

In our previous work (Kato and Terashima, Commun Math Phys. arXiv:1403.6569, 2014), we introduced the partition q-series for mutation loop γ—a loop in exchange quiver. In this paper, we show that for a certain class of mutation sequences, called reddening sequences, the graded version of partition q-series essentially coincides with the ordered product of quantum dilogarithm associated with each mutation; the partition q-series provides a state-sum description of combinatorial Donaldson-Thomas invariants introduced by Keller.

Random walk to a nonergodic equilibrium concept

Science.gov (United States)

Bel, G.; Barkai, E.

2006-01-01

Random walk models, such as the trap model, continuous time random walks, and comb models, exhibit weak ergodicity breaking, when the average waiting time is infinite. The open question is, what statistical mechanical theory replaces the canonical Boltzmann-Gibbs theory for such systems? In this paper a nonergodic equilibrium concept is investigated, for a continuous time random walk model in a potential field. In particular we show that in the nonergodic phase the distribution of the occupation time of the particle in a finite region of space approaches U- or W-shaped distributions related to the arcsine law. We show that when conditions of detailed balance are applied, these distributions depend on the partition function of the problem, thus establishing a relation between the nonergodic dynamics and canonical statistical mechanics. In the ergodic phase the distribution function of the occupation times approaches a δ function centered on the value predicted based on standard Boltzmann-Gibbs statistics. The relation of our work to single-molecule experiments is briefly discussed.

A multi-solver quasi-Newton method for the partitioned simulation of fluid-structure interaction

International Nuclear Information System (INIS)

Degroote, J; Annerel, S; Vierendeels, J

2010-01-01

In partitioned fluid-structure interaction simulations, the flow equations and the structural equations are solved separately. Consequently, the stresses and displacements on both sides of the fluid-structure interface are not automatically in equilibrium. Coupling techniques like Aitken relaxation and the Interface Block Quasi-Newton method with approximate Jacobians from Least-Squares models (IBQN-LS) enforce this equilibrium, even with black-box solvers. However, all existing coupling techniques use only one flow solver and one structural solver. To benefit from the large number of multi-core processors in modern clusters, a new Multi-Solver Interface Block Quasi-Newton (MS-IBQN-LS) algorithm has been developed. This algorithm uses more than one flow solver and structural solver, each running in parallel on a number of cores. One-dimensional and three-dimensional numerical experiments demonstrate that the run time of a simulation decreases as the number of solvers increases, albeit at a slower pace. Hence, the presented multi-solver algorithm accelerates fluid-structure interaction calculations by increasing the number of solvers, especially when the run time does not decrease further if more cores are used per solver.

Antibiotics in surface water and sediments from Hanjiang River, Central China: Occurrence, behavior and risk assessment.

Science.gov (United States)

Hu, Ying; Yan, Xue; Shen, Yun; Di, Mingxiao; Wang, Jun

2018-08-15

Thirteen antibiotics including sulfonamides (SAs), tetracyclines (TETs) and fluoroquinolones (FQs) were measured in Hanjiang River (HR) during two periods. The total concentrations of 13 antibiotics in surface water and sediments ranged from 3.1 to 109 ng/l and from 10 to 45 ng/g dry weight, respectively. SAs were dominant in water while the concentrations of TETs were the highest in sediments in two seasons. For their spatial distribution, total concentrations of 13 antibiotics in both matrices were significantly higher in the lower section of HR (p  5.15) due to wastewater release, agricultural activities and water transfer project. Obvious seasonal variations of sulfadiazine, sulfameter, trimethoprim and oxytetracycline in water were observed (p  4.62). Phase partition of antibiotics between water and sediments suggested a greater affinity of TETs and FQs to sediments. In addition, significantly positive relationships were found between SAs (sulfameter, sulfamethoxazole and trimethoprim) and sediment TOC (p Risk assessment indicated that the hazard quotients of antibiotics were higher in the sediment than those in the water. Moreover, antibiotic mixtures posed higher ecological risks to aquatic organisms. Copyright © 2018 Elsevier Inc. All rights reserved.

A statistical mechanical approach to restricted integer partition functions

Science.gov (United States)

Zhou, Chi-Chun; Dai, Wu-Sheng

2018-05-01

The main aim of this paper is twofold: (1) suggesting a statistical mechanical approach to the calculation of the generating function of restricted integer partition functions which count the number of partitions—a way of writing an integer as a sum of other integers under certain restrictions. In this approach, the generating function of restricted integer partition functions is constructed from the canonical partition functions of various quantum gases. (2) Introducing a new type of restricted integer partition functions corresponding to general statistics which is a generalization of Gentile statistics in statistical mechanics; many kinds of restricted integer partition functions are special cases of this restricted integer partition function. Moreover, with statistical mechanics as a bridge, we reveal a mathematical fact: the generating function of restricted integer partition function is just the symmetric function which is a class of functions being invariant under the action of permutation groups. Using this approach, we provide some expressions of restricted integer partition functions as examples.

Treatment characteristics of various sediment components spiked with 2-chlorobiphenyl using reactive activated carbon.

Science.gov (United States)

Choi, Hyeok

2018-04-05

Previously, the concept of reactive activated carbon (RAC), where the porous structure of activated carbon (AC) is impregnated with palladized zerovalent iron, has been proposed to be effective to adsorb and dechlorinate polychlorinated biphenyls (PCBs). To explain the low dechlorination of PCBs bound to actual aquatic sediments under remediation with RAC, this study investigated the role of various solid organic and inorganic sediment components in adsorbing and desorbing PCBs. Detailed fate and transport mechanism of 2-chlorinated biphenyl (2-ClBP) spiked to sediment components, including kaolin, montmorillonite (MMT), coal, graphite, AC, and their mixture, was revealed. Adsorption and holding capability of sediment components toward 2-ClBP strongly influenced amount of spiked 2-ClBP, amount of desorbed 2-ClBP, overall dechlorination of 2-ClBP to biphenyl (BP), and eventual partitioning of 2-ClBP and BP to water, sediment component, and RAC. Order of the amount of spiked 2-ClBP to sediment components after drying, following AC > mixture > coal > graphite > kaolin > MMT, was in agreements (in opposite direction) with order of the amount of desorbed 2-ClBP and order of overall 2-ClBP dechlorination. Substantial role of organic components in aquatic sediments for holding 2-ClBP and thus preventing it from dechlorination on RAC was proven. Copyright © 2017 Elsevier B.V. All rights reserved.

Coastline changes in relation to longshore sediment transport and human impact, along the shoreline of Kato Achaia (NW Peloponnese, Greece

Directory of Open Access Journals (Sweden)

S. POULOS

2001-06-01

Full Text Available Coastal configuration depends upon the equilibrium between available sediment budget and prevailing nearshore wave and current conditions. Human activities often disturb this natural equilibrium by altering the sources of beach material and littoral drift pattern. In the coastal zone of NW Peloponnese, an essentially tideless environment, the oblique approach of wind-induced waves implies an overall longshore drift from east to west. On an annual basis, the potential longshore sediment transport rates at the different sections of the study area (Kato Achaia is estimated to vary between 0.02 10-3 m3/s and 5 103 m3/s and to fluctuate seasonally. The construction of a port and the extraction of aggregates from the R. Peiros have changed significantly the pattern of sediment transport inducing dramatic changes on coastline configuration; thus, the part of the coastline west to the port had retreated as much as 70 m eliminating a touristic beach, while the entrance of the port was silted inhibiting navigation. Coastal engineering measures, such as modification of port-breakwaters and construction of groins have had only minimal contribution in beach recovery. Hence, coastal management plans should consider this dynamic equilibrium and protect the natural coastal system from the arbitrary human activities.

Spatially Partitioned Embedded Runge--Kutta Methods

KAUST Repository

Ketcheson, David I.

2013-10-30

We study spatially partitioned embedded Runge--Kutta (SPERK) schemes for partial differential equations (PDEs), in which each of the component schemes is applied over a different part of the spatial domain. Such methods may be convenient for problems in which the smoothness of the solution or the magnitudes of the PDE coefficients vary strongly in space. We focus on embedded partitioned methods as they offer greater efficiency and avoid the order reduction that may occur in nonembedded schemes. We demonstrate that the lack of conservation in partitioned schemes can lead to nonphysical effects and propose conservative additive schemes based on partitioning the fluxes rather than the ordinary differential equations. A variety of SPERK schemes are presented, including an embedded pair suitable for the time evolution of fifth-order weighted nonoscillatory spatial discretizations. Numerical experiments are provided to support the theory.

Spatially Partitioned Embedded Runge--Kutta Methods

KAUST Repository

Ketcheson, David I.; MacDonald, Colin B.; Ruuth, Steven J.

2013-01-01

We study spatially partitioned embedded Runge--Kutta (SPERK) schemes for partial differential equations (PDEs), in which each of the component schemes is applied over a different part of the spatial domain. Such methods may be convenient for problems in which the smoothness of the solution or the magnitudes of the PDE coefficients vary strongly in space. We focus on embedded partitioned methods as they offer greater efficiency and avoid the order reduction that may occur in nonembedded schemes. We demonstrate that the lack of conservation in partitioned schemes can lead to nonphysical effects and propose conservative additive schemes based on partitioning the fluxes rather than the ordinary differential equations. A variety of SPERK schemes are presented, including an embedded pair suitable for the time evolution of fifth-order weighted nonoscillatory spatial discretizations. Numerical experiments are provided to support the theory.

Microbially assisted recording of the Earth's magnetic field in sediment.

Science.gov (United States)

Zhao, Xiangyu; Egli, Ramon; Gilder, Stuart A; Müller, Sebastian

2016-02-11

Sediments continuously record variations of the Earth's magnetic field and thus provide an important archive for studying the geodynamo. The recording process occurs as magnetic grains partially align with the geomagnetic field during and after sediment deposition, generating a depositional remanent magnetization (DRM) or post-DRM (PDRM). (P)DRM acquisition mechanisms have been investigated for over 50 years, yet many aspects remain unclear. A key issue concerns the controversial role of bioturbation, that is, the mechanical disturbance of sediment by benthic organisms, during PDRM acquisition. A recent theory on bioturbation-driven PDRM appears to solve many inconsistencies between laboratory experiments and palaeomagnetic records, yet it lacks experimental proof. Here we fill this gap by documenting the important role of bioturbation-induced rotational diffusion for (P)DRM acquisition, including the control exerted on the recorded inclination and intensity, as determined by the equilibrium between aligning and perturbing torques acting on magnetic particles.

Simulation of the fate of faecal bacteria in estuarine and coastal waters based on a fractionated sediment transport model

Science.gov (United States)

Yang, Chen; Liu, Ying

2017-08-01

A two-dimensional depth-integrated numerical model is refined in this paper to simulate the hydrodynamics, graded sediment transport process and the fate of faecal bacteria in estuarine and coastal waters. The sediment mixture is divided into several fractions according to the grain size. A bed evolution model is adopted to simulate the processes of the bed elevation change and sediment grain size sorting. The faecal bacteria transport equation includes enhanced source and sink terms to represent bacterial kinetic transformation and disappearance or reappearance due to sediment deposition or re-suspension. A novel partition ratio and dynamic decay rates of faecal bacteria are adopted in the numerical model. The model has been applied to the turbid water environment in the Bristol Channel and Severn estuary, UK. The predictions by the present model are compared with field data and those by non-fractionated model.

Impact of partitioning and transmutation on high-level waste disposal for the fast breeder reactor fuel cycle

International Nuclear Information System (INIS)

Nishihara, Kenji; Oigawa, Hiroyuki; Nakayama, Shinichi; Ono, Kiyoshi; Shiotani, Hiroki

2010-01-01

The impact of partitioning and/or transmutation (PT) technology on high-level waste management was investigated for the equilibrium state of several potential fast breeder reactor (FBR) fuel cycles. Three different fuel cycle scenarios involving PT technology were analyzed: 1) partitioning process only (separation of some fission products), 2) transmutation process only (separation and transmutation of minor actinides), and 3) both partitioning and transmutation processes. The conventional light water reactor (LWR) fuel cycle without PT technology, on which the current repository design is based, was also included for comparison. We focused on the thermal constraints in a geological repository and determined the necessary predisposal storage quantities and time periods (by defining a storage capacity index) for several predefined emplacement configurations through transient thermal analysis. The relation between this storage capacity index and the required repository emplacement area was obtained. We found that the introduction of the FBR fuel cycle without PT can yield a 35% smaller repository per unit electricity generation than the LWR fuel cycle, although the predisposal storage period is prolonged from 50 years for the LWR fuel cycle to 65 years for the FBR fuel cycle without PT. The introduction of the partitioning-only process does not result in a significant reduction of the repository emplacement area from that for the FBR fuel cycle without PT, but the introduction of the transmutation-only process can reduce the emplacement area by a factor of 5 when the storage period is extended from 65 to 95 years. When a coupled partitioning and transmutation system is introduced, the repository emplacement area can be reduced by up to two orders of magnitude by assuming a predisposal storage of 60 years for glass waste and 295 years for calcined waste containing the Sr and Cs fraction. The storage period of 295 years for the calcined waste does not require a large

Salinity impacts on water solubility and n-octanol/water partition coefficients of selected pesticides and oil constituents.

Science.gov (United States)

Saranjampour, Parichehr; Vebrosky, Emily N; Armbrust, Kevin L

2017-09-01

Salinity has been reported to influence the water solubility of organic chemicals entering marine ecosystems. However, limited data are available on salinity impacts for chemicals potentially entering seawater. Impacts on water solubility would correspondingly impact chemical sorption as well as overall bioavailability and exposure estimates used in the regulatory assessment. The pesticides atrazine, fipronil, bifenthrin, and cypermethrin, as well as the crude oil constituent dibenzothiophene together with 3 of its alkyl derivatives, all have different polarities and were selected as model compounds to demonstrate the impact of salinity on their solubility and partitioning behavior. The n-octanol/water partition coefficient (K OW ) was measured in both distilled-deionized water and artificial seawater (3.2%). All compounds had diminished solubility and increased K OW values in artificial seawater compared with distilled-deionized water. A linear correlation curve estimated salinity may increase the log K OW value by 2.6%/1 log unit increase in distilled water (R 2  = 0.97). Salinity appears to generally decrease the water solubility and increase the partitioning potential. Environmental fate estimates based on these parameters indicate elevated chemical sorption to sediment, overall bioavailability, and toxicity in artificial seawater. These dramatic differences suggest that salinity should be taken into account when exposure estimates are made for marine organisms. Environ Toxicol Chem 2017;36:2274-2280. © 2017 SETAC. © 2017 SETAC.

Distribution of radionuclides and elements in Cubatao River sediments

International Nuclear Information System (INIS)

Silva, P.S.C.; Mazzilli, B.P.; Favaro, D.I.T.

2006-01-01

Cubatao River is located in Santos Basin, Sao Paulo State, Brazil. This region is characterized by the occurrence of estuaries and mangrove. Due to its location, near the coastal line, it is also an important industrial area, where phosphate fertilizer plants, petrol refineries, and chemical and steel industries are present. Such human activities contribute to the enhancement of elemental composition in sediments and, in some cases, also increase the radionuclide concentrations, the so called Technologically Enhanced Natural Occurring Radioactive Materials (TENORM). The contamination of land and sediments by TENORM is of major concern. The activity concentration of U and Th series radionuclides was determined in five sediment samples from Cubatao River. The activity concentration ratio was also determined. Equilibrium was observed for the ratio 234 U/ 238 U. The activity ratios of Th/ 238 U, 228 Ra/ 226 Ra and 210 Pb/ 226 Ra were higher than the unity. In the first two cases, the observed values are due to the higher activity of Th in the sediment and in the last case are probably due to the atmospheric deposition of 210 Pb. (author)

Distribution, partitioning and sources of polycyclic aromatic hydrocarbons in Daliao River water system in dry season, China

International Nuclear Information System (INIS)

Guo Wei; He Mengchang; Yang Zhifeng; Lin Chunye; Quan Xiangchun; Men Bing

2009-01-01

Eighteen polycyclic aromatic hydrocarbons (PAHs) were analyzed in 29 surface water, 29 suspended particulate matter (SPM), 28 sediment, and 10 pore water samples from Daliao River water system in dry season. The total PAH concentration ranged from 570.2 to 2318.6 ng L -1 in surface water, from 151.0 to 28483.8 ng L -1 in SPM, from 102.9 to 3419.2 ng g -1 in sediment and from 6.3 to 46.4 μg l -1 in pore water. The concentration of dissolved PAHs was higher than that of particulate PAHs at many sites, but the opposite results were generally observed at the sites of wastewater discharge. The soluble level of PAHs was much higher in the pore water than in the water column. Generally, the water column of the polluted branch streams contained higher content of PAHs than their mainstream. The environmental behaviors and fates of PAHs were examined according to some physicochemical parameters such as pH, organic carbon, SPM content, water content and grain size in sediments. Results showed that organic carbon was the primary factor controlling the distribution of the PAHs in the Daliao River water system. Partitioning of PAHs between sediment solid phase and pore water phase was studied, and the relationship between log K oc and log K ow of PAHs on some sediments and the predicted values was compared. PAHs other than naphthalene and acenaphthylene would be accumulated largely in the sediment of the Dalaio River water system. The sources of PAHs were evaluated employing ratios of specific PAHs compounds and different wastewater discharge sources, indicating that combustion was the main source of PAHs input.

Temporal evolution of cadmium, copper and lead concentration in the Venice Lagoon water in relation with the speciation and dissolved/particulate partition.

Science.gov (United States)

Morabito, Elisa; Radaelli, Marta; Corami, Fabiana; Turetta, Clara; Toscano, Giuseppa; Capodaglio, Gabriele

2018-04-01

In order to study the role of sediment re-suspension and deposition versus the role of organic complexation, we investigated the speciation of cadmium (Cd), copper (Cu) and lead (Pb) in samples collected in the Venice Lagoon during several campaigns from 1992 to 2006. The increment in Cd and Pb concentration in the dissolved phases, observed in the central and northern basins, can be linked to important alterations inside the lagoon caused by industrial and urban factors. The study focuses on metal partition between dissolved and particulate phases. The analyses carried out in different sites illustrate the complex role of organic matter in the sedimentation process. While Cd concentration in sediments can be correlated with organic matter, no such correlation can be established in the case of Pb, whose particulate concentration is related only to the dissolved concentration. In the case of Cu, the role of organic complexation remains unclear. Copyright © 2017 Elsevier Ltd. All rights reserved.

Dynamics of vacuum-sealed, double-leaf partitions

Science.gov (United States)

Kavanaugh, Joshua Stephen

The goal of this research is to investigate the feasibility and potential effectiveness of using vacuum-sealed, double-leaf partitions for applications in noise control. Substantial work has been done previously on double-leaf partitions where the acoustics of the inner chamber and mechanical vibrations of structural supports are passively and actively controlled. The work presented here is unique in that the proposed system aims to eliminate the need for active acoustic control of transmitted acoustic energy by removing all the air between the two panels of the double partition. Therefore, the only remaining energy paths would be along the boundary and at the points where there are intermediate structural supports connecting the two panels. The eventual goal of the research is to develop a high-loss double-leaf partition that simplifies active control by removing the need for control of the air cavity and channeling all the energy into discrete structural paths. The work presented here is a first step towards the goal of designing a high-loss, actively-controlled double-leaf partition with an air-evacuated inner chamber. One experiment is conducted to investigate the effects of various levels of vacuum on the response of a double-leaf partition whose panels are mechanically coupled only at the boundary. Another experiment is conducted which investigates the effect of changing the stiffness of an intermediate support coupling the two panels of a double-leaf partition in which a vacuum has been applied to the inner cavity. The available equipment was able to maintain a 99% vacuum between the panels. Both experiments are accompanied by analytical models used to investigate the importance of various dynamic parameters. Results show that the vacuum-sealed system shows some potential for increased transmission loss, primarily by the changing the natural frequencies of the double-leaf partition.

The relationship of mineral and geochemical composition to artificial radionuclide partitioning in Yenisei river sediments downstream from Krasnoyarsk.

Science.gov (United States)

Bondareva, Lydia

2012-06-01

Discharges from the Mining-and-Chemical Combine (MCC) of Rosatom, downstream from Krasnoyarsk, resulted in radioactive contamination of sediments of the River Yenisei. The concentration of artificial gamma-emitting radionuclides ((137)Cs, (60)Co, (152)Eu, and (241)Am) was determined with the objective to analyze the migration processes leading to the transport of these radionuclides. The content of artificial radionuclides in the surface layers of the study area varied in wide ranges: (137)Cs-318-1,800 Bq/kg, (60)Co-87-720 Bq/kg, (152)Eu-12-287 Bq/kg and (241)Am-6-76 Bq/kg. There was a sequence of migration of radionuclides investigated in the surface layer of sediments that were collected in the near zone of influence of the MCC: (241)Am ≈ (152)Eu > (60)Co > (137)Cs. Radionuclide species have been found to be directly related to sediment structure and composition.

Isospin equilibrium and non-equilibrium in heavy-ion collisions at intermediate energies

International Nuclear Information System (INIS)

Chen Liewen; Ge Lingxiao; Zhang Xiaodong; Zhang Fengshou

1997-01-01

The equilibrium and non-equilibrium of the isospin degree of freedom are studied in terms of an isospin-dependent QMD model, which includes isospin-dependent symmetry energy, Coulomb energy, N-N cross sections and Pauli blocking. It is shown that there exists a transition from the isospin equilibrium to non-equilibrium as the incident energy from below to above a threshold energy in central, asymmetric heavy-ion collisions. Meanwhile, it is found that the phenomenon results from the co-existence and competition of different reaction mechanisms, namely, the isospin degree of freedom reaches an equilibrium if the incomplete fusion (ICF) component is dominant and does not reach equilibrium if the fragmentation component is dominant. Moreover, it is also found that the isospin-dependent N-N cross sections and symmetry energy are crucial for the equilibrium of the isospin degree of freedom in heavy-ion collisions around the Fermi energy. (author)

Polyoxymethylene passive samplers to assess the effectiveness of biochar by reducing the content of freely dissolved fipronil and ethiprole.

Science.gov (United States)

Li, Shasha; Wang, Pingping; Liu, Xingang; Wu, Xiaohu; Dong, Fengshou; Xu, Jun; Zheng, Yongquan

2018-07-15

An equilibrium passive sampler based on polyoxymethylene (POM) was used to determine the freely dissolved concentrations (C free ) of fipronil and ethiprole. The sorption equilibrium times of fipronil and ethiprole in POM were 14.2d and 24.0d, respectively. The POM-water partitioning coefficients (logK POM-water ) were 2.6 for fipronil and 1.4 for ethiprole. The method was further used to evaluate the sorption behavior of biochars which produced by pyrolysis of Magnolia wood (Magnolia denudata) at 300°C, 500°C and 700°C. The amounts of target compounds adsorbed increased with increasing pyrolysis temperature of the biochars. Biochars characterized by a low polarity index had better sorption capacity for the target compounds. The additions of biochars to sediment were effective in reducing C free , and the enhancement was found to be more pronounced with high biochar content. C free in sediment with more organic matter was significantly higher after biochar addition. Increasing the sediment-biochar contact time from 7 to 30d resulted in an increase in sorption of the compounds. We conclude that Magnolia wood biochar effectively reduces the content of freely dissolved fipronil and ethiprole content in sediment. Copyright © 2018. Published by Elsevier B.V.

Partitions in languages and parallel computations

Energy Technology Data Exchange (ETDEWEB)

Burgin, M S; Burgina, E S

1982-05-01

Partitions of entries (linguistic structures) are studied that are intended for parallel data processing. The representations of formal languages with the aid of such structures is examined, and the relationships are considered between partitions of entries and abstract families of languages and automata. 18 references.

Arsenic partitioning among particle-size fractions of mine wastes and stream sediments from cinnabar mining districts.

Science.gov (United States)

Silva, Veronica; Loredo, Jorge; Fernández-Martínez, Rodolfo; Larios, Raquel; Ordóñez, Almudena; Gómez, Belén; Rucandio, Isabel

2014-10-01

Tailings from abandoned mercury mines represent an important pollution source by metals and metalloids. Mercury mining in Asturias (north-western Spain) has been carried out since Roman times until the 1970s. Specific and non-specific arsenic minerals are present in the paragenesis of the Hg ore deposit. As a result of intensive mining operations, waste materials contain high concentrations of As, which can be geochemically dispersed throughout surrounding areas. Arsenic accumulation, mobility and availability in soils and sediments are strongly affected by the association of As with solid phases and granular size composition. The objective of this study was to examine phase associations of As in the fine grain size subsamples of mine wastes (La Soterraña mine site) and stream sediments heavily affected by acid mine drainage (Los Rueldos mine site). An arsenic-selective sequential procedure, which categorizes As content into seven phase associations, was applied. In spite of a higher As accumulation in the finest particle-size subsamples, As fractionation did not seem to depend on grain size since similar distribution profiles were obtained for the studied granulometric fractions. The presence of As was relatively low in the most mobile forms in both sites. As was predominantly linked to short-range ordered Fe oxyhydroxides, coprecipitated with Fe and partially with Al oxyhydroxides and associated with structural material in mine waste samples. As incorporated into short-range ordered Fe oxyhydroxides was the predominant fraction at sediment samples, representing more than 80% of total As.

Partitioning and speciation of trace metal diagenesis in differing depositional environments in the sediments of the Oman margin

Digital Repository Service at National Institute of Oceanography (India)

Alagarsamy, R.; Wolff, G.A.; Chester, R.

, 403 004, India; 2 Oceanography Laboratories, Department of Earth and Ocean Sciences, University of Liverpool, Liverpool L69 3GP, UK. (Received: 5 May 2004; accepted: 28 September 2004) Abstract. Organic-rich sediment samples collected from a transect... were immediately frozen ()20C176C) on board prior to transport to the laboratory where they were freeze-dried and stored at )20C176C prior to analysis. 2.2. METHODOLOGY Particulate Mn and Fe in sediments are distributed between a numbers of host...

Scheduling Driven Partitioning of Heterogeneous Embedded Systems

DEFF Research Database (Denmark)

Pop, Paul; Eles, Petru; Peng, Zebo

1998-01-01

In this paper we present an algorithm for system level hardware/software partitioning of heterogeneous embedded systems. The system is represented as an abstract graph which captures both data-flow and the flow of control. Given an architecture consisting of several processors, ASICs and shared...... busses, our partitioning algorithm finds the partitioning with the smallest hardware cost and is able to predict and guarantee the performance of the system in terms of worst case delay....

Remobilisation of uranium from contaminated freshwater sediments by bioturbation

Energy Technology Data Exchange (ETDEWEB)

Lagauzere, S.; Bonzom, J.M. [Institut de Radioprotection et de Surete Nucleaire (IRSN), Saint-Paul-Lez-Durance (France). Lab. d' Ecotoxicologie des Radionucleides; Motelica-Heino, M. [Orleans Univ. (France). ISTO; Viollier, E. [Paris Diderot Univ., Paris (France). Inst. de Physique du Globe de Paris; Stora, G. [Aix-Marseille Univ., Marseille (France). Mediterranean Inst. of Oceanography (MIO)

2014-07-01

Benthic macro-invertebrate bioturbation can influence the remobilisation of uranium (U) initially associated with freshwater sediments, resulting in a high release of this pollutant through the overlying water column. Given the potential negative effects on aquatic biocenosis and the global ecological risk, it appears crucial to improve our current knowledge concerning the biogeochemical behaviour of U in sediments. The present study aimed to assess the biogeochemical modifications induced by Tubifex tubifex (Annelida, Clitellata, Tubificidae) bioturbation within the sediment in order to explain such a release of U. To reach this goal, U distribution between solid and solute phases of a reconstructed benthic system (i.e. in mesocosms) inhabited or not by T. tubifex worms was assessed in a 12-day laboratory experiment. Thanks notably to fine-resolution (mm-scale) measurements (e.g. ''diffusive equilibrium in thin-films'' DET gel probes for porewater, bioaccumulation in worms) of U and main chemical species (iron, sulfate, nitrate and nitrite), this work (i) confirmed that the removal of bottom sediment particles to the surface through the digestive tract of worms greatly favoured oxidative loss of U in the water column, and (ii) demonstrated that both U contamination and bioturbation of T. tubifex substantially influenced major microbial-driven biogeochemical reactions in sediments (e.g. stimulation of denitrification, sulfate reduction and iron dissolutive reduction). This study provides the first demonstration of biogeochemical modifications induced by bioturbation in freshwater U-contaminated sediments.

Partition functions for supersymmetric black holes

NARCIS (Netherlands)

Manschot, J.

2008-01-01

This thesis presents a number of results on partition functions for four-dimensional supersymmetric black holes. These partition functions are important tools to explain the entropy of black holes from a microscopic point of view. Such a microscopic explanation was desired after the association of a

A constitutive mechanical model for gas hydrate bearing sediments incorporating inelastic mechanisms

KAUST Repository

Sánchez, Marcelo

2016-11-30

Gas hydrate bearing sediments (HBS) are natural soils formed in permafrost and sub-marine settings where the temperature and pressure conditions are such that gas hydrates are stable. If these conditions shift from the hydrate stability zone, hydrates dissociate and move from the solid to the gas phase. Hydrate dissociation is accompanied by significant changes in sediment structure and strongly affects its mechanical behavior (e.g., sediment stiffenss, strength and dilatancy). The mechanical behavior of HBS is very complex and its modeling poses great challenges. This paper presents a new geomechanical model for hydrate bearing sediments. The model incorporates the concept of partition stress, plus a number of inelastic mechanisms proposed to capture the complex behavior of this type of soil. This constitutive model is especially well suited to simulate the behavior of HBS upon dissociation. The model was applied and validated against experimental data from triaxial and oedometric tests conducted on manufactured and natural specimens involving different hydrate saturation, hydrate morphology, and confinement conditions. Particular attention was paid to model the HBS behavior during hydrate dissociation under loading. The model performance was highly satisfactory in all the cases studied. It managed to properly capture the main features of HBS mechanical behavior and it also assisted to interpret the behavior of this type of sediment under different loading and hydrate conditions.

Plutonium behavior during the early diagenesis of marine sediments: applications to two marine environments labelled by radionuclides released from reprocessing plants

International Nuclear Information System (INIS)

Gouzy, A.

2004-12-01

The plutonium released into the English Channel and the Irish Sea by nuclear fuel reprocessing plants is mainly associated to sediments. Nevertheless, this association is partially reversible. This work combines a field study, carried out on the Cumbrian mud patch and the Esk estuary (Eastern Irish Sea), and laboratory experiments performed on carbonaceous coarse-grained sediments collected in the Central Channel. It presents new data on the plutonium solid partition in sediments and suggests realistic scenarios for describing its release from sediments to the water column. The role of reactive sulphides acting as temporary sink phases is shown in anoxic sediments; those sulphides are liable to release dissolved plutonium upon their oxidation. The plutonium is also bound to carbonates within the carbonaceous matrix and as carbonate surface complexes. Conceptual schemes of the behaviour of the plutonium in marine sediments are proposed; they highlight the strong remobilization potential of plutonium from marine sediments to the interstitial water. Its plutonium content can be injected into the overlying water column. (author)

Post-tsunami beach recovery in Thailand: A case for punctuated equilibrium in coastal dynamics

Science.gov (United States)

Switzer, Adam D.; Gouramanis, Chris; Bristow, Charles; Yeo, Jeffrey; Kruawun, Jankaew; Rubin, Charles; Sin Lee, Ying; Tien Dat, Pham

2017-04-01

A morpho-geophysical investigation of two beaches in Thailand over the last decade shows that they have completely recovered from the 2004 Indian Ocean tsunami (IOT) without any human intervention. Although the beach systems show contrasting styles of recovery in both cases natural processes have reconstructed the beaches to comparable pre-tsunami morphologies in under a decade, demonstrating the existence of punctuated equilibrium in coastal systems and the resilience of natural systems to catastrophic events. Through a combination of remote sensing, field surveys and shallow geophysics we reconstruct the post-event recovery of beaches at Phra Thong Island, a remote, near pristine site that was severely impacted by the IOT. We identify periods of aggradation, progradation and washover sedimentation that match with local events including a storm in November 2007. The rapid recovery of these systems implies that majority of sediment scoured by the tsunami was not transported far offshore but remained in the littoral zone within reach of fair-weather waves that returned it (the sediment) to the beach naturally.

Aspects of system modelling in Hardware/Software partitioning

DEFF Research Database (Denmark)

Knudsen, Peter Voigt; Madsen, Jan

1996-01-01

This paper addresses fundamental aspects of system modelling and partitioning algorithms in the area of Hardware/Software Codesign. Three basic system models for partitioning are presented and the consequences of partitioning according to each of these are analyzed. The analysis shows...... the importance of making a clear distinction between the model used for partitioning and the model used for evaluation It also illustrates the importance of having a realistic hardware model such that hardware sharing can be taken into account. Finally, the importance of integrating scheduling and allocation...

An expression for the water-sediment moving layer in unsteady flows valid for open channels and embankments

Directory of Open Access Journals (Sweden)

A. M. Berta

2010-05-01

Full Text Available During the floods, the effects of sediment transport in river beds are particulary significant and can be studied through the evolution of the water-sediment layer which moves in the lower part of a flow, named "moving layer". Moving layer variations along rivers lead to depositions and erosions and are typically unsteady, but are often tackled with expressions developed for steady (equilibrium conditions. In this paper, we develop an expression for the moving layer in unsteady conditions and calibrate it with experimental data. During laboratory tests, we have in fact reproduced a rapidly changing unsteady flow by the erosion of a granular steep slope. Results have shown a clear tendency of the moving layer, for fixed discharges, toward equilibrium conditions. Knowing the equilibrium achievement has presented many difficulties, being influenced by the choice of the equilibrium expression and moreover by the estimation of the parameters involved (for example friction angle. Since we used only data relevant to hyper-concentrated mono-dimensional flows for the calibration – occurring for slope gradients in the range 0.03–0.20 – our model can be applied both on open channels and on embankments/dams, providing that the flows can be modelled as mono-dimensional, and that slopes and applied shear stress levels fall within the considered ranges.

Generating Milton Babbitt's all-partition arrays

DEFF Research Database (Denmark)

Bemman, Brian; Meredith, David

2016-01-01

In most of Milton Babbitt's (1916–2011) works written since the early 1960s, both the pitch and rhythmic content is organized according to a highly constrained structure known as the all-partition array. The all-partition array provides a framework that ensures that as many different forms...

River longitudinal profiles and bedrock incision models: Stream power and the influence of sediment supply