Enantiopure Chiral Coordination Polymers Based on Polynuclear Paddlewheel Helices and Arsenyl Tartrate

Directory of Open Access Journals (Sweden)

Ángela Valentín-Pérez

2018-03-01

Full Text Available Herein, we report the preparation of chiral, one-dimensional coordination polymers based on trinuclear paddlewheel helices [M3(dpa4]2+ (M = Co(II and Ni(II; dpa = the anion of 2,2′-dipyridylamine. Enantiomeric resolution of a racemic mixture of [M3(dpa4]2+ complexes was achieved by chiral recognition of the respective enantiomer by [Δ-As2(tartrate2]2− or [Λ-As2(tartrate2]2− in N,N-dimethylformamide (DMF, affording crystalline coordination polymers formed from [(Δ-Co3(dpa4(Λ-As2(tartrate2]·3DMF (Δ-1, [(Λ-Co3(dpa4(Δ-As2(tartrate2]·3DMF (Λ-1, [(Δ-Ni3(dpa4(Λ-As2(tartrate2]·(4 − nDMF∙nEt2O (Δ-2 or [(Λ-Ni3(dpa4(Δ-As2(tartrate2]·(4 − nDMF∙nEt2O (Λ-2 repeating units. UV-visible circular dichroism spectra of the complexes in DMF solutions demonstrate the efficient isolation of optically active species. The helicoidal [M3(dpa4]2+ units that were obtained display high stability towards racemization as shown by the absence of an evolution of the dichroic signals after several days at room temperature and only a small decrease of the signal after 3 h at 80 °C.

Construction of Polynuclear Lanthanide (Ln = Dy(III), Tb(III), and Nd(III)) Cage Complexes Using Pyridine-Pyrazole-Based Ligands: Versatile Molecular Topologies and SMM Behavior.

Science.gov (United States)

Bala, Sukhen; Sen Bishwas, Mousumi; Pramanik, Bhaskar; Khanra, Sumit; Fromm, Katharina M; Poddar, Pankaj; Mondal, Raju

2015-09-08

Employment of two different pyridyl-pyrazolyl-based ligands afforded three octanuclear lanthanide(III) (Ln = Dy, Tb) cage compounds and one hexanuclear neodymium(III) coordination cage, exhibiting versatile molecular architectures including a butterfly core. Relatively less common semirigid pyridyl-pyrazolyl-based asymmetric ligand systems show an interesting trend of forming polynuclear lanthanide cage complexes with different coordination environments around the metal centers. It is noteworthy here that construction of lanthanide complex itself is a challenging task in a ligand system as soft N-donor rich as pyridyl-pyrazol. We report herein some lanthanide complexes using ligand containing only one or two O-donors compare to five N-coordinating sites. The resultant multinuclear lanthanide complexes show interesting magnetic and spectroscopic features originating from different spatial arrangements of the metal ions. Alternating current (ac) susceptibility measurements of the two dysprosium complexes display frequency- and temperature-dependent out-of-phase signals in zero and 0.5 T direct current field, a typical characteristic feature of single-molecule magnet (SMM) behavior, indicating different energy reversal barriers due to different molecular topologies. Another aspect of this work is the occurrence of the not-so-common SMM behavior of the terbium complex, further confirmed by ac susceptibility measurement.

Three-dimensional tetranuclear Cd(II) coordination network based on a 1,3-alternate calix[4]arene derivative

Energy Technology Data Exchange (ETDEWEB)

Lee, Eun Ji; Ju, Hui Yeong; Park, Ki Min [Dept. of Chemistry and Research Institute of Natural Science, Gyeongsang National University, Jinju (Korea, Republic of); Moon, ASuk Hee [Dept. of Food and Nutrition, Kyungnam College of Inform ation and Technology, Busan (Korea, Republic of); Kang, Young Jin [Div. of cience Education, Kangwon National University, Chuncheon (Korea, Republic of)

2015-08-15

Polynuclear coordination polymers can exhibit more intriguing network topologies and better functionalities than those of common complexes because they have metal-cluster nodes for the construction of multidimensional frameworks and the potential applications induced by collaborative activities between metal ions. New tetranuclear Cd(II) coordination polymer 1 based on 1,3-alternate calix arene derivative (H{sub 4} CTA) with four carboxyl pendant arms has been synthesized by the solvo thermal reaction at 110 .deg. C for 2 days. Compound 1 shows a 3-D framework consisting of tetranuclear Cd(II) cluster core as a metal-cluster node and 1,3-alternate H{sub 4}CTA as a multidentate linker. The coordination polymer 1 displays intense blue emission, implying that this tetranuclear Cd(II) coordination polymer could be a suitable material in the area of luminescence research.

Polynuclear Hydroxido-Bridged Complexes of Platinum(IV) with Terminal Nitrato Ligands.

Science.gov (United States)

Vasilchenko, Danila; Berdugin, Semen; Tkachev, Sergey; Baidina, Iraida; Romanenko, Galina; Gerasko, Olga; Korenev, Sergey

2015-05-18

For the first time the polynuclear hydroxido-bridged platinum(IV) nitrato complexes with nuclearity higher than two were isolated from nitric acid solutions of [Pt(H2O)2(OH)4] and crystallized as supramolecular compounds of macrocyclic cavitands cucurbit[n]uril (CB[n], n = 6,8) and 18-crown-6 ether: [Pt4(μ3-OH)2(μ2-OH)4(NO3)10]·CB[6]·25H2O (I), [Pt6(μ3-OH)4(μ2-OH)6(NO3)12](NO3)2·CB[8]·50H2O (II), and [H3O⊂18-crown-6]2[Pt2(μ2-OH)2(NO3)8][Pt4(μ3-OH)2(μ2-OH)4(NO3)10] (III). The isolation of the compounds in the single crystalline state allows the determination of the structure of the tetranuclear and hexanuclear complexes [Pt4(μ3-OH)2(μ2-OH)4(NO3)10] and [Pt6(μ3-OH)4(μ2-OH)6(NO3)12](2+), which have been previously unknown in the solid state. Stability of Ptx(OH)y cores of the polynuclear nitrato complexes toward alkaline hydrolysis was verified by (195)Pt NMR spectroscopy. Analysis of (195)Pt NMR spectra of the compound III reveals that addition of every Pt(μ-OH)2Pt ring results in ∼260 ppm downfield shift relative to the mononuclear form, which allows the prediction of signal positions for complexes of higher nuclearity.

Prediction of the Iron-Based Polynuclear Magnetic Superhalogens with Pseudohalogen CN as Ligands.

Science.gov (United States)

Ding, Li-Ping; Shao, Peng; Lu, Cheng; Zhang, Fang-Hui; Liu, Yun; Mu, Qiang

2017-07-17

To explore stable polynuclear magnetic superhalogens, we perform an unbiased structure search for polynuclear iron-based systems based on pseudohalogen ligand CN using the CALYPSO method in conjunction with density functional theory. The superhalogen properties, magnetic properties, and thermodynamic stabilities of neutral and anionic Fe 2 (CN) 5 and Fe 3 (CN) 7 clusters are investigated. The results show that both of the clusters have superhalogen properties due to their electron affinities (EAs) and that vertical detachment energies (VDEs) are significantly larger than those of the chlorine element and their ligand CN. The distribution of the extra electron analysis indicates that the extra electron is aggregated mainly into pseudohalogen ligand CN units in Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ cluster. These features contribute significantly to their high EA and VDE. Besides superhalogen properties, these two anionic clusters carry a large magnetic moment just like the Fe 2 F 5 ¯ cluster. Additionally, the thermodynamic stabilities are also discussed by calculating the energy required to fragment the cluster into various smaller stable clusters. It is found that Fe(CN) 2 is the most favorable fragmentation product for anionic Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ clusters, and both of the anions are less stable against ejection of Fe atoms than Fe(CN) n-x .

Homogeneously catalysed hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols

NARCIS (Netherlands)

Stouthamer, B.; Vlugter, J.C.

1965-01-01

The use of copper and cadmium oxides or soaps as catalysts for the hydrogenation of unsaturated fatty acids to unsaturated fatty alcohols has been investigated. It is shown that copper soaps homogeneously activate hydrogen. When copper and cadmium oxides are used as catalysts, they react with the

Polynuclear Iron-Oxo/Hydroxy Complexes of Ketoacidoximate Ligands: Synthesis, Structures and Conversion to Ferric Oxide

KAUST Repository

Davaasuren, Bambar; Khanderi, Jayaprakash; Rothenberger, Alexander

2017-01-01

The polynuclear iron-oxo/hydroxy complexes containing ketoacidoximate ligands described in this report are [Fe3(μ3-O){O2C-C(C6H5)=NOCH3}6(py)3] (1) (py=pyridine), [Fe2(μ3-O){O2C-C(CH2-C6H5)=NO}2(H2O)(CH3OH)]2 (2) and [{Fe(μ2-OH)(O2C-C(CH3)=NO

Certification of selected polynuclear aromatic hydrocarbons in standard reference material 1580, 'Organics in Shale Oil'. Final report

Energy Technology Data Exchange (ETDEWEB)

May, W.E.; Brown-Thomas, J.M.; Hilpert, L.R.; Wise, S.A.

1981-01-01

Two independent analytical methods were developed and used to certify the concentrations of five polynuclear aromatic hydrocarbons (PAH) in a shale oil sample (SRM 1580). In the sequential high-performance liquid chromatographic method, PAH are isolated from the matrix by chromatography on an aminosilane column. The individual analyte species were separated, identified, and quantified by chromatography on an octadecylsilane column with spectrofluorimetric detection. Dilution of the sample in methylene chloride was the only sample preparation step necessary prior to analysis by gas chromatography/mass spectrometry (GC/MS). The GC/MS determinations were performed using selected ion monitoring (SIM) and a standard addition technique for quantification. The polynuclear aromatic hydrocarbons of interest were separated on a 30 m SE-52 wall coated open tubular column interfaced to a quadrupole mass spectrometer through a 25 cm length of Pt/Ir tubing (0.15 mm i.d.). Excellent agreement was observed between the data obtained from these methods.

The persistence of polynuclear aromatic hydrocarbons in sewage sludge-amended agricultural soils

International Nuclear Information System (INIS)

Wild, S.R.; Jones, K.C.; Berrow, M.L.

1992-01-01

In 1968 five metal enriched sewage sludges containing different concentrations of polynuclear aromatic hydrocarbons (PAHs) were applied to different plots on field soils at two experimental sites, Luddington and Lee Valley in the UK. This resulted in substantial increases in soil ΣPAH concentrations in all plots. Since application compound specific losses have occurred, with the high molecular weight PAHs being more persistent. Calculated half-lives range from under 2 years for naphthalene to over 9 years for benzo[ghi]perylene and coronene. The loss of PAH compounds in these field experiments can be related, in part, to certain physico-chemical properties, namely water solubility and the octanol:water partition coefficients. 20 refs., 3 figs., 1 tab

Hydrolysis of Zr(4) with formation of mono- and polynuclear hydroxocomplexes in solutions

International Nuclear Information System (INIS)

Davydov, Yu.P.; Zabrodskij, V.N.

1987-01-01

The state of Zr(4) has been studied in the wide range of H + -ions concentrations (10 -3 -3.0 mol/l) and in the wide range of Zr(4) concentrations (10 -13 -10 -12 mol/l) in the solution using a set of such physical-chemical methods as spectrophotometry, ion exchange, dialysis, centrifugation. The conditions of formation of hydrated cations, monochange, dialysis, centrifugation. The conditions of formation of hydrated cations, mono- and polynuclear hydrocomplexes, colloidal-size particles have been determined. The thermodynamic stability of ZrOH 3+ and Zr(OH) 2 2+ complexes has been determined by the ion exchange and spectrophotometry methods

Modeling the fate of polynuclear aromatic hydrocarbons in the rhizosphere

International Nuclear Information System (INIS)

Santharam, S.K.; Erickson, L.E.; Fan, L.T.

1994-01-01

Polynuclear aromatic hydrocarbons (PAHs) are major contaminants associated with wastes from manufactured gas plants, wood treating operations, and petroleum refining; they are potentially carcinogenic and mutagenic. It has been known that vegetation can enhance the rate and extent of degradation of PAHs in contaminated soil. Plant roots release exudates capable of supplying carbon and energy to microflora for degrading PAHs. It has also been well established that the population of microorganisms in the rhizosphere is significantly greater than that in the non-vegetated soil; these microorganisms are apparently responsible for the enhanced biodegradation of PAHs. A model has been derived for describing the rate of disappearance of a non-aqueous phase contaminant in the rhizosphere, which takes into account dissolution, adsorption, desorption and biodegradation of the contaminant, without neglecting the size distribution of the organic-phase droplets; the rate of biodegradation is expressed in terms of the Monod kinetics. The model is validated with the available experimental data for pyrene

The unsaturated bistable stochastic resonance system.

Science.gov (United States)

Zhao, Wenli; Wang, Juan; Wang, Linze

2013-09-01

We investigated the characteristics of the output saturation of the classical continuous bistable system (saturation bistable system) and its impact on stochastic resonance (SR). We further proposed a piecewise bistable SR system (unsaturated bistable system) and developed the expression of signal-to-noise ratio (SNR) using the adiabatic approximation theory. Compared with the saturation bistable system, the SNR is significantly improved in our unsaturated bistable SR system. The numerical simulation showed that the unsaturated bistable system performed better in extracting weak signals from strong background noise than the saturation bistable system.

Biodepuration of polynuclear aromatic hydrocarbons from a bivalve mollusc, Mercenaria mercenaria L

International Nuclear Information System (INIS)

Tanacredl, J.T.; Cardenas, R.R.

1991-01-01

Mercenaria mercenaria, exposed in vitro for 48 h to nine parent polynuclear aromatic hydrocarbons (PAHs) found in waste crankcase oil (WCCO) and analyzed by multiparametric analysis over a 45-day depuration period in an activated carbon filtration aquaria system, did not depurate PAHs, but rather maintained them at detectable levels. Uptake of PAHs was shown to be directly related to clam weight. A cluster analysis of empirical results reaffirmed a biostabilization in PAH groupings in clam tissue over a 45-day depuration period and exhibited no evidence of a decreasing trend in total PAHs when subjected to ANOVA. Due to the commercial importance of hard-shell clams, the practices of clam depuration and clam relaying are reviewed in light of potential long-terms public health exposures to low-level xenobiotics and the implications for human consumers

Evaluating sensitivity of unsaturated soil properties

International Nuclear Information System (INIS)

Abdel-Rahman, R.O.; El-Kamash, A.M.; Nagy, M.E.; Khalill, M.Y.

2005-01-01

The assessment of near surface disposal performance relay on numerical models of groundwater flow and contaminant transport. These models use the unsaturated soil properties as input parameters, which are subject to uncertainty due to measurements errors and the spatial variability in the subsurface environment. To ascertain how much the output of the model will depend on the unsaturated soil properties the parametric sensitivity analysis is used. In this paper, a parametric sensitivity analysis of the Van Genuchten moisture retention characteristic (VGMRC) model will be presented and conducted to evaluate the relative importance of the unsaturated soil properties under different pressure head values that represent various dry and wet conditions. (author)

Could the description on polynuclear superhalogens by DFT be comparable with high-level ab initio results? A comparison between DFT and CCSD(T)

International Nuclear Information System (INIS)

Sun, Yin-Yin; Li, Jin-Feng; Li, Miao-Miao; Zhou, Fu-Qiang; Li, Jian-Li; Yin, Bing

2016-01-01

A systematic density functional theory study including 17 exchange-correlation functionals was performed on different types of superhalogens with high level coupled-cluster single double including perturbative triple excitations (CCSD(T)) results as the reference. The superhalogens selected here cover the ranges from mononuclear to polynuclear structures and from structures with halogen-atom ligands to those with non-halogen ligands, e.g., [MgX 3 ] − , [Mg 2 X 5 ] − , and [Mg 3 X 7 ] − (X = F, Cl, CN). It is clearly indicated that three double-hybrid functionals B2T-PLYP, B2GP-PLYP, B2K-PLYP as well as the range-separated hybrid functional ωB97X are capable of providing results which approach the accuracy at the CCSD(T) level. The basis set effect is usually moderate and, in most cases, it is enough to utilize the basis set of triple-ξ quality, e.g., Def2-TZVP. In addition, the results of the HF and MP2 method are also acceptable here, especially for polynuclear superhalogens where CCSD(T) is probably unpractical

Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.

KAUST Repository

Alezi, Dalal

2015-04-07

Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly-connected nets. The topological exploration based on the non-compatibility of 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly-connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] and hexanuclear [RE6(OH)8(O2C–)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly-connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.

Photochemical activation and reactivity of polynuclear transition metal complex molecules. Final report

International Nuclear Information System (INIS)

Endicott, J.F.; Lintvedt, R.L.

1982-06-01

Several bi- and trinuclear metal complexes containing ligands from β-polyketonates have been synthesized and characterized including homo- and hetero-polynuclear complexes. New synthetic approaches to the preparation of heterobi- and trinuclear complexes have been developed that allow the preparation of a large number of molecules containing heavy-metal ions such as Pd 2+ or UO 2 2+ and a first-row transition-metal ion. The electrochemical properties of these complexes have been investigated and many exhibit the ability to transfer two electrons at very nearly the same potential. Photochemical studies on binuclear Cu(II) and Ni(II) showed that these compounds yielded reduced metal species and decomposition upon irradiation. Luminescence of hetero-complexes of uranyl polyketonates is observed at 77 0 K with the UO 2 2+ moiety functioning as an isolated chromophore in which emission is observed only on direct excitation of UO 2 2+ and energy transfer to lower states in the molecule is not observed

Coordination polymers: trapping of radionuclides and chemistry of tetravalent actinides (Th, U) carboxylates

International Nuclear Information System (INIS)

Falaise, Clement

2014-01-01

The use of nuclear energy obviously raises the question of the presence of radionuclides in the environment. Currently, their mitigation is a major issue associated with nuclear chemistry. This thesis focuses on both the trapping of radionuclides by porous solids called Metal-Organic Frameworks (MOF) and the crystal chemistry of the carboxylate of tetravalent actinides (AnIV). The academic knowledge of the reactivity of carboxylate of AnIV could help the understanding of actinides speciation in environment. We focused on the sequestration of iodine by aluminum based MOF. The functionalization (electron-donor group) of the MOF drastically enhances the iodine capture capacity. The removal of light actinides (Th and U) from aqueous solution was also investigated as well as the stability of (Al)-MOF under γ radiation. More than twenty coordination polymers based on tetravalent actinides have been synthesized and characterized by single crystal X-ray diffraction. The use of controlled hydrolysis promotes the formation of coordination polymers exhibiting polynuclear cluster ([U 4 ], [Th 6 ], [U 6 ] and [U 38 ]). In order to understand the formation of the largest cluster, the ex-situ study of the solvo-thermal synthesis of compound {U 38 } has also been investigated. (author)

Unsaturated fatty acids in the diet of inpatients

OpenAIRE

KONHEFROVÁ, Veronika

2015-01-01

The thesis with the name "Unsaturated fatty acids in the diet of inpatients" is divided into a theoretical and a research parts. The theoretical part is focused on sorting out lipids and the recommended daily dosing. Next there are described the chemical structure of fatty acids and basic differences between saturated (SFA) and unsaturated (trans and cis) fatty acids. The biggest part of the theory is formed by the unsaturated fatty acids, their characteristics, food source and their effect o...

Synthesis of porphyryl boronates with (un)saturated side-chains

OpenAIRE

SENGE, MATHIAS; SERGEEVA, NATALIA

2008-01-01

PUBLISHED Porphyrins with (un)saturated side?chains containing boron residues were developed as synthons for porphyrin functionalization. Porphyrins with mono and bis-substituted unsaturated boronyl residues were prepared in good yields (52?66 %) using a cross?metathesis approach in the presence of Grubbs I-generation catalysts. In all cases complete E?stereoselectivity (100 %) was observed. Furthermore, formal cross?metathesis products with ?,??unsaturated chains smoothly underwent additi...

Development of a screening method for the determination of total polynuclear aromatic hydrocarbons (PAH) in water and wastewater

International Nuclear Information System (INIS)

Riggin, R.; Strup, P.; Billets, S.

1983-01-01

Polynuclear aromatic hydrocarbons (PAHs) represent an important class of organic compounds from an environmental standpoint, due to known human carcinogenicity of some members. Consequently, there is a great need for monitoring the PAH concentration of a variety of media, including water and industrial wastewater. Recently, the United States Environmental Protection Agency (U.S. EPA) developed a sensitive analytical method, designated Test Method 610, for the determination of priority pollutant PAHs in aqueous industrial discharges. This method employs reversed phase high performance liquid chromatography (HPLC) with ultraviolet (UV) and fluorescence detection to determine all sixteen priority pollutant PAHs in a single chromatographic separation

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

Science.gov (United States)

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-01

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Analysis of Rainfall Infiltration Law in Unsaturated Soil Slope

OpenAIRE

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering t...

Engineered antibodies for monitoring of polynuclear aromatic hydrocarbons

International Nuclear Information System (INIS)

Karu, A.E.; Li, Q.X.; Roberts, V.A.

1998-01-01

'The long-term goal of this project is to develop antibodies and antibody-based methods for detection and recovery of polynuclear aromatic hydrocarbons (PAHs) and PAH adducts that are potential biomarkers in environmental and biological samples. The inherent cross-reactivity will be exploited by pattern recognition methods. Dr. Karu''s laboratory uses new haptens representing key PAHs to derive recombinant Fab (rFab) and single-chain Fv (scFv) antibodies from hybridoma lines and combinatorial phage display libraries. Computational models of the haptens and combining sites made by Dr. Roberts''s group are used to guide antibody engineering by mutagenesis. Dr. Li''s laboratory develops enzyme immunoassays (EIAs), sensors, and immunoaffinity methods that make use of the novel haptens and antibodies for practical analytical applications in support of DOE''s mission. This report summarizes work completed in one and one-half years of a 3-year project, with close collaboration between the three research groups. Dr. Alexander Karu''s laboratory: the authors proceeded with the two strategies described in the original proposal. Site-directed mutagenesis was used to correct differences in the rFab N-terminal amino acids that were introduced by the degenerate PCR primers used for gene amplification. The binding constants of the rFabs with the corrected sequences will be compared with those of the parent MAbs, and should be very similar. The 4D5 and 10C10 heavy and light chain sequences are being moved to the pCOMB3H phagemid vector to facilitate selection of new engineered mutants.'

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water.

Science.gov (United States)

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-11-30

The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu(3)(BTC)(2)(H(2)O)(3)](n) (HKUST-1, BTC=benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu(3)(BTC)(2)](n) samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N(2) sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu(3)(BTC)(2)](n) exhibited remarkably high adsorption affinity (K(d)=4.73 × 10(5)mL g(-1)) and high adsorption capacity (714.29 mg g(-1)) for Hg(2+) adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg(2+) under the same condition. Copyright © 2011 Elsevier B.V. All rights reserved.

Pumping Test Determination of Unsaturated Aquifer Properties

Science.gov (United States)

Mishra, P. K.; Neuman, S. P.

2008-12-01

Tartakovsky and Neuman [2007] presented a new analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering the unsaturated zone. In their solution three-dimensional, axially symmetric unsaturated flow is described by a linearized version of Richards' equation in which both hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value, the latter defining the interface between the saturated and unsaturated zones. Both exponential functions are characterized by a common exponent k having the dimension of inverse length, or equivalently a dimensionless exponent kd=kb where b is initial saturated thickness. The authors used their solution to analyze drawdown data from a pumping test conducted by Moench et al. [2001] in a Glacial Outwash Deposit at Cape Cod, Massachusetts. Their analysis yielded estimates of horizontal and vertical saturated hydraulic conductivities, specific storage, specific yield and k . Recognizing that hydraulic conductivity and water content seldom vary identically with incremental capillary pressure head, as assumed by Tartakovsky and Neuman [2007], we note that k is at best an effective rather than a directly measurable soil parameter. We therefore ask to what extent does interpretation of a pumping test based on the Tartakovsky-Neuman solution allow estimating aquifer unsaturated parameters as described by more common constitutive water retention and relative hydraulic conductivity models such as those of Brooks and Corey [1964] or van Genuchten [1980] and Mualem [1976a]? We address this question by showing how may be used to estimate the capillary air entry pressure head k and the parameters of such constitutive models directly, without a need for inverse unsaturated numerical simulations of the kind described by Moench [2003]. To assess the validity of such direct estimates we use maximum

Deuterium labelling studies with unsaturated acids and nitriles

International Nuclear Information System (INIS)

Desai, U.V.; Mane, R.B.

1986-01-01

α-Deuteriated α,β-unsaturated acids have been prepared by Knoevenagel condensation of aldehydes with deuteriated malonic acid. The decarboxylation of α,β-unsaturated cyano acid with pyridine/D 2 O yields α- and γ-labelled nitriles. The deuterium incorporation is studied by pmr spectroscopy. (author). 8 refs

Vertical hydrochemical profiles in the unsaturated zone of louga ...

African Journals Online (AJOL)

Solutions chemistry of the rainwater and the unsaturated zone interstitial water of Louga (Northern Senegal) local aquifer provide valuable ... together with chemical analysis of the interstitial water carried out through the entire unsaturated ...

Electrokinetic extraction of chromate from unsaturated soils

International Nuclear Information System (INIS)

Mattson, E.D.; Lindgren, E.R.

1993-01-01

Heavy-metal contamination of soil and groundwater is a widespread problem in industrial nations. Remediation by excavation of such sites may not be cost effective or politically acceptable. Electrokinetic remediation is one possible remediation technique for in situ removal of such contaminants from unsaturated soils. Previous papers discussing the work performed by researchers at Sandia National Laboratories (SNL) and Sat-Unsat, Inc. (SUI) (Lindgren et al., 1991, 1992, 1993) focused on the transport of contaminants and dyes by electrokinetics in unsaturated soils. These experiments were conducted with graphite electrodes with no extraction system. As the contaminants migrated through the soil, they increased in concentration at the electrode creating a diffusion flux in the opposite direction. This paper discusses a technique to remove the contaminants from unsaturated soils once they have reached an electrode

Electrokinetic extraction of chromate from unsaturated soils

Energy Technology Data Exchange (ETDEWEB)

Mattson, E.D. [SAT-UNSAT, Inc., Albuquerque, NM (United States); Lindgren, E.R. [Sandia National Labs., Albuquerque, NM (United States)

1993-11-01

Heavy-metal contamination of soil and groundwater is a widespread problem in industrial nations. Remediation by excavation of such sites may not be cost effective or politically acceptable. Electrokinetic remediation is one possible remediation technique for in situ removal of such contaminants from unsaturated soils. Previous papers discussing the work performed by researchers at Sandia National Laboratories (SNL) and Sat-Unsat, Inc. (SUI) (Lindgren et al., 1991, 1992, 1993) focused on the transport of contaminants and dyes by electrokinetics in unsaturated soils. These experiments were conducted with graphite electrodes with no extraction system. As the contaminants migrated through the soil, they increased in concentration at the electrode creating a diffusion flux in the opposite direction. This paper discusses a technique to remove the contaminants from unsaturated soils once they have reached an electrode.

Movement of radionuclides through unsaturated soils

International Nuclear Information System (INIS)

de Sousa, F.N.C.

1985-01-01

The advantages of the disposal of low-level radioactive wastes in the unsaturated zone above the fluctuations of the water table have been recognized for some time. However, most the numerical models used to simulate the environmental impact of a shallow land burial site assume that the soils surrounding the waste forms are saturated; this assumption may lead, in many cases, to unrealistic large leach and water flow rates. The main purpose of this study was the development of a procedure which could give a reliable prediction on the movement of radionuclides from shallow land burial sites located in the unsaturated zone. In order to accomplish this objective three different soils having different sand, silt, and clay fractions were selected and characterized. These soils were then used to fill a number of flow columns that were used in tests designed to provide input data for the flow and transport models. A one-dimensional finite element model was developed in order to simulate the water flow and radionuclide transport through unsaturated soils. The results obtained showed that the model accurately described the transport of radionuclides through saturated-unsaturated soils. Simulations were done, for all three soils, involving different degrees of soil saturation, and the results showed that assuming the soils are always saturated may lead to nuclide transport times which are orders of magnitude larger than the real ones, depending on the clay percentage present in the soil

Seismic response of earth dams considering dynamic properties of unsaturated zone

Directory of Open Access Journals (Sweden)

Ariyan M.

2016-01-01

Full Text Available It is conventionally assumed in the analysis and design of earth dams that the soil located above the phreatic line, i.e. the uppermost seepage flow line, is completely dry. However, there is often an unsaturated flow of water through an unsaturated zone above this borderline and variation in moisture content in this zone results in variation of matric suction throughout this region. Variation of matric suction, in turn, results in variation of effective stresses in this zone. In this research, the seismic response of earth dams in terms of the displacement and acceleration at the crown of the dam as well as the stress distribution in the dam body is investigated. Taking into account the effect of unsaturated zone, a comparison is made to investigate the effect of conventional simplification in ignoring the dynamic characteristics of the unsaturated zone above the phreatic line and the more complicated analysis which includes the unsaturated zone. A function for the soil-water retention curve (SWRC was assigned to the soil in the unsaturated zone to determine the variation of matric suction in this zone and analyses were made using finite difference software (FLAC. Results are then compared to the conventional method for homogeneous dams. In these analyzes the soil shear modulus was assumed to vary with the mean effective stress both for saturated and unsaturated zones. Among various results, it was notable that the history of crest x-displacement, and acceleration show higher values in models accounting for the unsaturated region. It was attributed to the considerably lower values of damping ratio in the crest region in the unsaturated models.

Infiltration in Unsaturated Soils

DEFF Research Database (Denmark)

Ghotbi, Abdoul R.; Omidvar, M.; Barari, Amin

2011-01-01

An approximate analytical solution has been established for the well known Richards’ equation for unsaturated flow of transports in soils. Despite the importance of Richards’ equation in geotechnical and geoenvironmental applications, most solutions to the problem are generally based on numerical...

Isotope based assessment of groundwater renewal in water scarce regions. Proceedings of a final research co-ordination meeting

International Nuclear Information System (INIS)

2001-10-01

The isotopic composition and chemical constituents of water infiltrating through the soil zone (unsaturated zone, or zone of aeration) into groundwater can be employed to determine the moisture transport in the unsaturated zone, thus enabling estimation of the water infiltration rate to the underlying aquifer. This was the basis on which this CRP was initiated in 1996. The overall results obtained from three years of applied field research related to study of moisture transport dynamics and estimation of natural recharge through use of isotope/hydrochemical depth profiles of the soil moisture in the unsaturated zone were presented and discussed at the final Research Co-ordination Meeting held in Vienna from 18 to 21 October 1999. A total of 44 sites were involved in the project on which detailed information on physiography, lithology, rainfall, unsaturated moisture content and a variety of chemical and isotopic determinants is now available. This publication contains 11 individual reports presented by CRP participants at the Meeting. Each of the reports have been indexed separately

Characterization of unsaturated hydraulic conductivity at the Hanford Site

Energy Technology Data Exchange (ETDEWEB)

Rockhold, M.L.; Fayler, M.J.; Gee, G.W.

1988-07-01

This report details some recent field measurements and compares predicted and measured values of hydraulic conductivities for three locations at the Hanford Site. Measurements from small (6-cm-dia) /open quotes/point/close quotes/ and large (2-m by 2-m) /open quotes/plot/close quotes/ areas utilized inflitration and drainage techniques to obtain in situ data for field-saturated and unsaturated hydraulic conductivity. The Guelph permeameter was used for point sampling, and the unsteady drainage-flux method was used on plots for field-saturated and unsaturated hydraulic conductivity measurements. Steady-state techniques were used to measure unsaturated hydraulic conductivities in small columns in the laboratory for one of the three soils tested to provide a comparison with data obtained from the field. Measured unsaturated hydraulic conductivities and those predicted from particle-size distribution and bulk density data agree within one-half to one and one-half orders of magnitude, depending on soil type. To use a particle-size distribution to estimate water retention characteristics and, subsequently, to predict unsaturated hydraulic conductivities, measurements of water-retention characteristics are necessary to determine a parameter value used in one of the models. No single method for measuring or calculating unsaturated hydraulic conductivities was found appropriate for all Hanford Site soils. Ideally, several methods should be used to take advantage of the strengths of each method, considering the data needs and resources available. 45 refs., 24 figs., 19 tabs.

Characterization of unsaturated hydraulic conductivity at the Hanford Site

International Nuclear Information System (INIS)

Rockhold, M.L.; Fayler, M.J.; Gee, G.W.

1988-07-01

This report details some recent field measurements and compares predicted and measured values of hydraulic conductivities for three locations at the Hanford Site. Measurements from small (6-cm-dia) /open quotes/point/close quotes/ and large (2-m by 2-m) /open quotes/plot/close quotes/ areas utilized inflitration and drainage techniques to obtain in situ data for field-saturated and unsaturated hydraulic conductivity. The Guelph permeameter was used for point sampling, and the unsteady drainage-flux method was used on plots for field-saturated and unsaturated hydraulic conductivity measurements. Steady-state techniques were used to measure unsaturated hydraulic conductivities in small columns in the laboratory for one of the three soils tested to provide a comparison with data obtained from the field. Measured unsaturated hydraulic conductivities and those predicted from particle-size distribution and bulk density data agree within one-half to one and one-half orders of magnitude, depending on soil type. To use a particle-size distribution to estimate water retention characteristics and, subsequently, to predict unsaturated hydraulic conductivities, measurements of water-retention characteristics are necessary to determine a parameter value used in one of the models. No single method for measuring or calculating unsaturated hydraulic conductivities was found appropriate for all Hanford Site soils. Ideally, several methods should be used to take advantage of the strengths of each method, considering the data needs and resources available. 45 refs., 24 figs., 19 tabs

Analysis of rainfall infiltration law in unsaturated soil slope.

Science.gov (United States)

Zhang, Gui-rong; Qian, Ya-jun; Wang, Zhang-chun; Zhao, Bo

2014-01-01

In the study of unsaturated soil slope stability under rainfall infiltration, it is worth continuing to explore how much rainfall infiltrates into the slope in a rain process, and the amount of rainfall infiltrating into slope is the important factor influencing the stability. Therefore, rainfall infiltration capacity is an important issue of unsaturated seepage analysis for slope. On the basis of previous studies, rainfall infiltration law of unsaturated soil slope is analyzed. Considering the characteristics of slope and rainfall, the key factors affecting rainfall infiltration of slope, including hydraulic properties, water storage capacity (θs - θr), soil types, rainfall intensities, and antecedent and subsequent infiltration rates on unsaturated soil slope, are discussed by using theory analysis and numerical simulation technology. Based on critical factors changing, this paper presents three calculation models of rainfall infiltrability for unsaturated slope, including (1) infiltration model considering rainfall intensity; (2) effective rainfall model considering antecedent rainfall; (3) infiltration model considering comprehensive factors. Based on the technology of system response, the relationship of rainfall and infiltration is described, and the prototype of regression model of rainfall infiltration is given, in order to determine the amount of rain penetration during a rain process.

Abstracts of the symposium on unsaturated flow and transport modeling

International Nuclear Information System (INIS)

1982-03-01

Abstract titles are: Recent developments in modeling variably saturated flow and transport; Unsaturated flow modeling as applied to field problems; Coupled heat and moisture transport in unsaturated soils; Influence of climatic parameters on movement of radionuclides in a multilayered saturated-unsaturated media; Modeling water and solute transport in soil containing roots; Simulation of consolidation in partially saturated soil materials; modeling of water and solute transport in unsaturated heterogeneous fields; Fluid dynamics and mass transfer in variably-saturated porous media; Solute transport through soils; One-dimensional analytical transport modeling; Convective transport of ideal tracers in unsaturated soils; Chemical transport in macropore-mesopore media under partially saturated conditions; Influence of the tension-saturated zone on contaminant migration in shallow water regimes; Influence of the spatial distribution of velocities in porous media on the form of solute transport; Stochastic vs deterministic models for solute movement in the field; and Stochastic analysis of flow and solute transport

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

International Nuclear Information System (INIS)

Yin, Bing; Wen, Zhen-Yi; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Jiang, Zhen-Yi

2014-01-01

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg 2 (CN) 5 ] − clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN −1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

Energy Technology Data Exchange (ETDEWEB)

Yin, Bing, E-mail: rayinyin@gmail.com; Wen, Zhen-Yi [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Institute of Modern Physics, Northwest University, Xi' an 710069 (China); Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Jiang, Zhen-Yi [Institute of Modern Physics, Northwest University, Xi' an 710069 (China)

2014-03-07

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg{sub 2}(CN){sub 5}]{sup −} clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN{sup −1} were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Principles of Physical Modelling of Unsaturated Soils

OpenAIRE

CAICEDO, Bernardo; THOREL, Luc

2014-01-01

Centrifuge modelling has been widely used to simulate the performance of a variety of geotechnical works, most of them focusing on saturated clays or dry sands. On the other hand, the performance of some geotechnical works depends on the behaviour of shallow layers in the soil deposit where it is frequently unsaturated. Centrifuge modelling could be a powerful tool to study the performance of shallow geotechnical works. However all the experimental complexities related to unsaturated soils, w...

Quantifying Preferential Flow and Seasonal Storage in an Unsaturated Fracture-Facial Domain

Science.gov (United States)

Nimmo, J. R.; Malek-Mohammadi, S.

2012-12-01

Preferential flow through deep unsaturated zones of fractured rock is hydrologically important to a variety of contaminant transport and water-resource issues. The unsaturated zone of the English Chalk Aquifer provides an important opportunity for a case study of unsaturated preferential flow in isolation from other flow modes. The chalk matrix has low hydraulic conductivity and stays saturated, owing to its fine uniform pores and the wet climate of the region. Therefore the substantial fluxes observed in the unsaturated chalk must be within fractures and interact minimally with matrix material. Price et al. [2000] showed that irregularities on fracture surfaces provide a significant storage capacity in the chalk unsaturated zone, likely accounting for volumes of water required to explain unexpected dry-season water-table stability during substantial continuing streamflow observed by Lewis et al. [1993] In this presentation we discuss and quantify the dynamics of replenishment and drainage of this unsaturated zone fracture-face storage domain using a modification of the source-responsive model of Nimmo [2010]. This model explains the processes in terms of two interacting flow regimes: a film or rivulet preferential flow regime on rough fracture faces, active on an individual-storm timescale, and a regime of adsorptive and surface-tension influences, resembling traditional diffuse formulations of unsaturated flow, effective mainly on a seasonal timescale. The modified model identifies hydraulic parameters for an unsaturated fracture-facial domain lining the fractures. Besides helping to quantify the unsaturated zone storage described by Price et al., these results highlight the importance of research on the topic of unsaturated-flow relations within a near-fracture-surface domain. This model can also facilitate understanding of mechanisms for reinitiation of preferential flow after temporary cessation, which is important in multi-year preferential flow through deep

Coordinate Regulation of Yeast Sterol Regulatory Element-binding Protein (SREBP) and Mga2 Transcription Factors.

Science.gov (United States)

Burr, Risa; Stewart, Emerson V; Espenshade, Peter J

2017-03-31

The Mga2 and Sre1 transcription factors regulate oxygen-responsive lipid homeostasis in the fission yeast Schizosaccharomyces pombe in a manner analogous to the mammalian sterol regulatory element-binding protein (SREBP)-1 and SREBP-2 transcription factors. Mga2 and SREBP-1 regulate triacylglycerol and glycerophospholipid synthesis, whereas Sre1 and SREBP-2 regulate sterol synthesis. In mammals, a shared activation mechanism allows for coordinate regulation of SREBP-1 and SREBP-2. In contrast, distinct pathways activate fission yeast Mga2 and Sre1. Therefore, it is unclear whether and how these two related pathways are coordinated to maintain lipid balance in fission yeast. Previously, we showed that Sre1 cleavage is defective in the absence of mga2 Here, we report that this defect is due to deficient unsaturated fatty acid synthesis, resulting in aberrant membrane transport. This defect is recapitulated by treatment with the fatty acid synthase inhibitor cerulenin and is rescued by addition of exogenous unsaturated fatty acids. Furthermore, sterol synthesis inhibition blocks Mga2 pathway activation. Together, these data demonstrate that Sre1 and Mga2 are each regulated by the lipid product of the other transcription factor pathway, providing a source of coordination for these two branches of lipid synthesis. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Degradation of phenolics, nitrogen-heterocyclics and polynuclear aromatic hydrocarbons in a rotating biological contactor.

Science.gov (United States)

Jeswani, Hansa; Mukherji, Suparna

2012-05-01

The degradation of phenolics, heterocyclics and polynuclear aromatic hydrocarbons (PAHs) in a synthetic biomass gasifier wastewater with average COD of 1388 mg/L was studied in a three stage rotating biological contactor (RBC) using the pyrene degrader, Exiguobacterium aurantiacum and activated sludge consortia (1:3 v/v). As the organic loading rate (OLR) was varied from 3.3 to 14 g/m(2)/d, the COD removal ranged from 63.3% to 92.6%. Complete removal of all the constituents was observed at the lowest OLR of 3.3g/m(2)/d. At 24h hydraulic retention time (HRT) and OLR of 6.6g/m(2)/d complete removal of pyridine, quinoline and benzene and 85-96% removal of phenol, naphthalene, phenanthrene, fluoranthene and pyrene was observed. E. aurantiacum was found to be the dominant bacteria in the biofilm. Clark's model provided good fits to data for all the three stages of the RBC. Copyright © 2012 Elsevier Ltd. All rights reserved.

Virus movement in soil during saturated and unsaturated flow.

Science.gov (United States)

Lance, J C; Gerba, C P

1984-02-01

Virus movement in soil during saturated and unsaturated flow was compared by adding poliovirus to sewage water and applying the water at different rates to a 250-cm-long soil column equipped with ceramic samplers at different depths. Movement of viruses during unsaturated flow of sewage through soil columns was much less than during saturated flow. Viruses did not move below the 40-cm level when sewage water was applied at less than the maximum infiltration rate; virus penetration in columns flooded with sewage was at least 160 cm. Therefore, virus movement in soils irrigated with sewage should be less than in flooded groundwater recharge basins or in saturated soil columns. Management of land treatment systems to provide unsaturated flow through the soil should minimize the depth of virus penetration. Differences in virus movement during saturated and unsaturated flow must be considered in the development of any model used to simulate virus movement in soils.

Oyster polynuclear aromatic hydrocarbon fingerprinting applied to the Apex barge oil spill

International Nuclear Information System (INIS)

Wade, T.L.; Jackson, T.J.; McDonald, T.J.; Sericano, J.L.; Brooks, J.M.

1993-01-01

An estimated 692,000 gallons of catalytic feed stock oil was spilled into Galveston Bay on July 28, 1990, when a tanker collided with three Apex barges in the Houston Ship Channel. Oysters were collected and analyzed from Galveston Bay Todd's Dump (GBRD) before the spill and after the spill. Oysters were also collected from Galveston Bay Redfish Island (GBRI), a site known to be impacted by the spill, 37 and 110 days after the spill. The spilled oil was also analyzed. The concentration of 18 polynuclear aromatic hydrocarbons (PAH) measured as part of the National Oceanic and Atmospheric Administration's National Status ampersand Trends (NS ampersand T) showed a sharp increase from 100 ng/g to over 600 ng/g. Concentrations of these 18 PAHs were also found at GBRI. Fingerprinting techniques applied to data from oyster analyses demonstrated the presence of bioavailable Apex Barge oil 37, 110, and 132 days after the spill at GHTD and GBRI. Fingerprinting becomes less diagnostic with time due to possible environmental weathering of the oil. The fingerprint from GBTD 495 and 851 days after the spill will be presented and discussed

Waste migration in shallow burial sites under unsaturated flow conditions

International Nuclear Information System (INIS)

Eicholz, G.G.; Whang, J.

1987-01-01

Unsaturated conditions prevail in many shallow-land burial sites, both in arid and humid regions. Unless a burial site is allowed to flood and possibly overflow, a realistic assessment of any migration scenario must take into account the conditions of unsaturated flow. These are more difficult to observe and to model, but introduce significant changes into projected rates of waste leaching and waste migration. Column tests have been performed using soils from the Southeastern coastal plain to observe the effects of varying degrees of ''unsaturation'' on the movement of radioactive tracers. The moisture content in the columns was controlled by maintaining various levels of hydrostatic suction on soil columns whose hydrodynamic characteristics had been determined carefully. Tracer tests, employing Cs-137, I-131 and Ba-133 were used to determine migration profiles and to follow their movement down the column for different suction values. A calculational model has been developed for unsaturated flow and seems to match the observations fairly well. It is evident that a full description of migration processes must take into account the reduced migration rates under unsaturated conditions and the hysteresis effects associated with wetting-drying cycles

Analyzing Unsaturated Flow Patterns in Fractured Rock Using an Integrated Modeling Approach

International Nuclear Information System (INIS)

Y.S. Wu; G. Lu; K. Zhang; L. Pan; G.S. Bodvarsson

2006-01-01

Characterizing percolation patterns in unsaturated fractured rock has posed a greater challenge to modeling investigations than comparable saturated zone studies, because of the heterogeneous nature of unsaturated media and the great number of variables impacting unsaturated flow. This paper presents an integrated modeling methodology for quantitatively characterizing percolation patterns in the unsaturated zone of Yucca Mountain, Nevada, a proposed underground repository site for storing high-level radioactive waste. The modeling approach integrates a wide variety of moisture, pneumatic, thermal, and isotopic geochemical field data into a comprehensive three-dimensional numerical model for modeling analyses. It takes into account the coupled processes of fluid and heat flow and chemical isotopic transport in Yucca Mountain's highly heterogeneous, unsaturated fractured tuffs. Modeling results are examined against different types of field-measured data and then used to evaluate different hydrogeological conceptualizations and their results of flow patterns in the unsaturated zone. In particular, this model provides a much clearer understanding of percolation patterns and flow behavior through the unsaturated zone, both crucial issues in assessing repository performance. The integrated approach for quantifying Yucca Mountain's flow system is demonstrated to provide a practical modeling tool for characterizing flow and transport processes in complex subsurface systems

A framework for the behaviour of unsaturated expansive clays

International Nuclear Information System (INIS)

Gens, A.; Alonso, E.E.

1992-01-01

The paper presents a framework for describing the mechanical behaviour of unsaturated expansive clays. It is an extension of an existing formulation developed for unsaturated soils of low activity. The extended framework is based on the distinction within the material of a microstructural level where the basic swelling of the active minerals takes place, and a macrostructural level responsible for major structural rearrangements. Bu adopting simple assumptions concerning the coupling between the two levels, it is possible to reproduce major features of the behaviour of unsaturated expansive clays. Some selected qualitative comparisons between model predictions and experimental results reported in the literature are presented. Despite the simplified hypotheses made, a very encouraging agreement is obtained

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg2+ from water

International Nuclear Information System (INIS)

Ke, Fei; Qiu, Ling-Guang; Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua; Zhu, Jun-Fa

2011-01-01

Highlights: ► A novel type of functionalized MOF for heavy metal removal. ► Functionalization of MOF by a facile coordination-based postsynthetic strategy. ► Thiol-functionalization of MOF has been realized for the first time. ► Enhanced removal of Hg 2+ by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu 3 (BTC) 2 (H 2 O) 3 ] n (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu 3 (BTC) 2 ] n samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with –SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N 2 sorption–desorption isothermal. Significantly, the thiol-functionalized [Cu 3 (BTC) 2 ] n exhibited remarkably high adsorption affinity (K d = 4.73 × 10 5 mL g −1 ) and high adsorption capacity (714.29 mg g −1 ) for Hg 2+ adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg 2+ under the same condition.

Effect of Unsaturated Flow on Delayed Response of Unconfined Aquifiers to Pumping

Science.gov (United States)

Tartakovsky, G.; Neuman, S. P.

2005-12-01

A new analytical solution is presented for the delayed response process characterizing flow to a partially penetrating well in an unconfined aquifer. The new solution generalizes that of Neuman [1972, 1974] by accounting for unsaturated flow above the water table. Axially symmetric three-dimensional flow in the unsaturated zone is described by a linearized version of Richards' equation in which hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value (defining the interface between the saturated and unsaturated zones). Unsaturated soil properties are characterized by an exponent κ having the dimension of inverse length and a dimensionless exponent κD = κb where b is initial saturated thickness. Our treatment of the unsaturated zone is similar to that of Kroszynski and Dagan [1975] who however have ignored internal (artesian) aquifer storage. It has been suggested by Boulton [1954, 1963, 1970] and Neuman [1972, 1974], and is confirmed by our solution, that internal storage is required to reproduce the early increase in drawdown characterizing delayed response to pumping in typical aquifers. According to our new solution such aquifers are characterized by relatively large κ_ D values, typically 10 or larger; in the limit as κD tends to infinity (the soil unsaturated water retention capacity becomes insignificant and/or aquifer thickness become large), unsaturated flow becomes unimportant and our solution reduces to that of Neuman. In typical cases corresponding to κD larger than or equal to 10, unsaturated flow is found to have little impact on early and late dimensionless time behaviors of drawdown measured wholly or in part at some distance below the water table; unsaturated flow causes drawdown to increase slightly at intermediate dimensionless time values that represent transition from an early artesian dominated to a late water-table dominated flow regime. The increase in drawdown

Stochastic analysis of radionuclide migration in saturated-unsaturated soils

International Nuclear Information System (INIS)

Kawanishi, Moto

1988-01-01

In Japan, LLRW (low level radioactive wastes) generated from nuclear power plants shall be started to store concentrically in the Shimokita site from 1990, and those could be transformed into land disposal if the positive safety is confirmed. Therefore, it is hoped that the safety assessment method shall be successed for the land disposal of LLRW. In this study, a stochastic model to analyze the radionuclide migration in saturated-unsaturated soils was constructed. The principal results are summarized as follows. 1) We presented a generalized idea for the modeling of the radionuclide migration in saturated-unsaturated soils as an advective-dispersion phenomena followed by the decay of radionuclides and those adsorption/desorption in soils. 2) Based on the radionuclide migration model mentioned above, we developed a stochastic analysis model on radionuclide migration in saturated-unsaturated soils. 3) From the comparison between the simulated results and the exact solution on a few simple one-dimensional advective-dispersion problems of radionuclides, the good validity of this model was confirmed. 4) From the comparison between the simulated results by this model and the experimental results of radionuclide migration in a one-dimensional unsaturated soil column with rainfall, the good applicability was shown. 5) As the stochastic model such as this has several advantages that it is easily able to represent the image of physical phenomena and has basically no numerical dissipation, this model should be more applicable to the analysis of the complicated radionuclide migration in saturated-unsaturated soils. (author)

Hydrogenation of the alpha,beta-Unsaturated Aldehydes Acrolein, Crotonaldehyde, and Prenal over Pt Single Crystals: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

Energy Technology Data Exchange (ETDEWEB)

Kliewer, C.J.; Somorjai, G.A.

2008-11-26

Sum-frequency generation vibrational spectroscopy (SFG-VS) and kinetic measurements using gas chromatography have been used to study the surface reaction intermediates during the hydrogenation of three {alpha},{beta}-unsaturated aldehydes, acrolein, crotonaldehyde, and prenal, over Pt(111) at Torr pressures (1 Torr aldehyde, 100 Torr hydrogen) in the temperature range of 295K to 415K. SFG-VS data showed that acrolein has mixed adsorption species of {eta}{sub 2}-di-{sigma}(CC)-trans, {eta}{sub 2}-di-{sigma}(CC)-cis as well as highly coordinated {eta}{sub 3} or {eta}{sub 4} species. Crotonaldehyde adsorbed to Pt(111) as {eta}{sub 2} surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the {eta}{sub 2} adsorption species, and became more highly coordinated as the temperature was raised to 415K, in agreement with its enhanced C=O hydrogenation. The effect of catalyst surface structure was clarified by carrying out the hydrogenation of crotonaldehyde over both Pt(111) and Pt(100) single crystals while acquiring the SFG-VS spectra in situ. Both the kinetics and SFG-VS showed little structure sensitivity. Pt(100) generated more decarbonylation 'cracking' product while Pt(111) had a higher selectivity for the formation of the desired unsaturated alcohol, crotylalcohol.

Gas-phase polynuclear aromatic hydrocarbons (PAH) in vehicle exhaust: A method for collection and analysis

International Nuclear Information System (INIS)

Seigl, W.O.; Chladek, E.

1990-01-01

Gas-phase polynuclear aromatic hydrocarbons (PAH) are emitted at low levels in vehicle exhaust compared to other hydrocarbon emissions. A method has been developed involving the trapping of gas phase emissions on Tenax, a macrorecticular porous polymer, followed by thermal desorption onto a capillary gas chromatography column. Gas chromatography/mass spectrometry (GC/MS) was used for the chemical analysis. A detection limit of 0.05 ng was achieved for several gas-phase PAH. This high sensitivity enables the speciation and quantitation of gas-phase PAH collected from a dilution tube during standard driving (test) cycles. The method was demonstrated for the analysis of 9 PAH in the exhaust from a 1987 vehicle (with and without catalyst) during the hot start transient phase of the EPA urban dynamometer driving schedule. The PAH measured include naphthalene, 2-methyl- and 1-methylnaphthalene, biphenyl, fluorene, phenanthrene, anthracene, fluoranthene and pyrene. The four most abundant PAH observed are naphthalene, 2-methyl and 1-methylnaphthalene, and biphenyl, in that order

Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

KAUST Repository

Riache, Nassima; Callens, Emmanuel; Talbi, Karima; Basset, Jean-Marie

2015-01-01

Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate

Unsaturated zone investigation at the radioactive waste storage facility site

Energy Technology Data Exchange (ETDEWEB)

Skuratovic, Zana; Mazeika, Jonas; Petrosius, Rimantas; Jakimaviciute-Maseliene, Vaidote [Nature Research Centre, Akademijos St. 2, LT-08412, Vilnius (Lithuania); Klizas, Petras; Mokrik, Robert [Vilnius University, M.K. Ciurlionio St. 21/27, LT-03101 Vilnius (Lithuania)

2014-07-01

Unsaturated zone is an important part of water circulation cycle and an integral part of many hydrological and hydrogeological factors and processes. The soils of unsaturated zone are regarded as the first natural barrier to a large extent able to limit the spread of contaminants. Nuclear waste disposal site (Maisiagala radioactive waste storage facility site) was analysed in terms of the moisture movement through the unsaturated zone. Extensive data sets of the hydraulic properties, water content and isotope composition have been collected and summarized. The main experimental and observational tasks included the collection of soil samples; determination of the physical properties and the hydraulic conductivity values of soil samples, moisture extraction from the soil sample for isotopic studies; observation of the groundwater dynamics at the Maisiagala piezometer; groundwater sampling for isotopic analysis ({sup 3}H, {sup 18}O/{sup 16}O, {sup 2}H/{sup 1}H ); and monthly precipitation isotopic analysis. Distribution features of globally widespread radionuclide tritium ({sup 3}H) and the water molecule tracer isotopes in precipitation, unsaturated zone soil moisture profiles and groundwater were determined. It was used the well-known unsaturated flow and transport model of HYDRUS-1D (Simunek et al., 2008). In this study, van Genuchten equations for the retention and conductivity estimations have been used. The retention characteristics and van Genuchten model parameters were estimated internally by HYDRUS based on the empirical equations involved in the program. Basic inputs of the tritium transport simulation are the tritium input function and meteorological variables (precipitation and potential evapotranspiration). In order to validate the representativeness of the hydraulic parameters, the model has been used to estimate the tritium distribution in the unsaturated zone, which properly represents the dynamics of the unsaturated zone. The uniformity of the daily

Isotope Investigations of Groundwater Movement in a Coarse Gravel Unsaturated Zone

Energy Technology Data Exchange (ETDEWEB)

Mali, N. [Geological Survey of Slovenia, Department of Hydrogeology, Ljubljana (Slovenia); Kozar-Logar, J. [Jozef Stefan Institute, Ljubljana (Slovenia); Leis, A. [Institute of Water Resources Management, Hydrogeology and Geophysics, Joanneum Research Forschungsgesellschaft mbH, Graz (Austria)

2013-07-15

The unsaturated zone above an aquifer serves as a water reservoir which discharges water and possible pollution to the saturated zone. This paper presents the application of oxygen-18 and tritium isotope methods in the study of groundwater transport processes in the unsaturated zone of Selniska Dobrava coarse gravel aquifer. The Selniska Dobrava gravel aquifer is an important water resource for Maribor and its surroundings, therefore the determination of transport processes in the unsaturated zone is important regarding its protection. Groundwater flow characteristics were estimated using isotopes and based on experimental work in a lysimeter. Tritium investigation results were compared with the results of long term oxygen-18 isotope investigation. In this paper the analytical approach, results and interpretation of {delta}{sup 18}O and tritium measurements in the unsaturated zone are presented. (author)

Polynuclear aromatic hydrocarbons (PAHs) mediate cadmium toxicity to an emergent wetland species

International Nuclear Information System (INIS)

Zhang, Zhenhua; Rengel, Zed; Meney, Kathy; Pantelic, Ljiljana; Tomanovic, Radmila

2011-01-01

Growth and pollutant removal by emergent wetland plants may be influenced by interactions among mixed pollutants in constructed wetlands. A glasshouse experiment was conducted to investigate interactive effects of cadmium (Cd) x polynuclear aromatic hydrocarbons (PAHs) x plant treatments on growth of Juncus subsecundus, Cd and PAH removal from soil and the total number of microorganisms in soil. Growth and biomass of J. subsecundus were significantly influenced by interaction of Cd and PAHs, significantly decreasing with either Cd or PAH additions, but with the effect of Cd on plant growth being stronger than that of PAHs. The mixture of low Cd and low PAH lessened Cd toxicity to plants, resulting in improved plant growth and increased Cd accumulation in plant tissues, thus enhancing Cd removal by plants. The dissipation of PAHs in soils was significantly influenced by interactions of Cd, PAH and plant presence or absence. The total number of microorganisms in soils was significantly increased by the PAH additions. The interactive effect of Cd and PAHs on plant growth may be linked to the changes in the abundance of microorganisms in the rhizosphere, probably via a positive effect of PAH metabolites and/or phytohormones produced by microorganisms on plant growth.

Transport of citrate-coated silver nanoparticles in unsaturated sand

Science.gov (United States)

Kumahor, Samuel; Hron, Pavel; Metreveli, George; Schaumann, Gabriele; Vogel, Hans-Jörg

2015-04-01

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Unlike for saturated transport, studies on unsaturated transport as typical for soil are currently scarce. We investigated the mobility of citrate-coated Ag NPs in unsaturated sand (grain diameter: 0.1-0.3 mm). For three flux rates and a given pore-water ionic strength (1 mM KNO3), the citrate-coated Ag NPs were less mobile at pH = 5 compared to pH = 9. The classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory suggests unfavorable deposition conditions at both, the air-water interface and solid-water interface. Breakthrough curves measured under quasi-steady state unsaturated flow showed retardation of the citrate-coated Ag NPs compared to inert solute (KBr). After flushing with nanoparticle-free 1 mM KNO3 solution (pH-adjusted), retention was much lower in deeper depths compared to the surface where the particles entered the flow field. The results show a non-linear dependence of nanoparticle (NP) mobility on flux rate and water content. Especially the observed retardation similar to equilibrium sorption is in contrast to observations under saturated flow conditions. A convection-dispersion and reaction model that combines a reversible equilibrium process and a non-equilibrium interaction process reproduced the measured breakthrough curves reasonably well. From comparison between saturated and unsaturated experiments we conclude that the air-water interface is responsible for the reversible equilibrium process while the water-solid interface accounts for irreversible soption.

A mathematical model in charactering chloride diffusivity in unsaturated cementitious material

NARCIS (Netherlands)

Zhang, Y.; Ye, G.; Pecur, I.B.; Baricevic, A.; Stirmer, N; Bjegovic, D.

2017-01-01

In this paper, a new analytic model for predicting chloride diffusivity in unsaturated cementitious materials is developed based on conductivity theory and Nernst-Einstein equation. The model specifies that chloride diffusivity in unsaturated cementitious materials can be mathematically described as

Estimating the Spatial Extent of Unsaturated Zones in Heterogeneous River-Aquifer Systems

Science.gov (United States)

Schilling, Oliver S.; Irvine, Dylan J.; Hendricks Franssen, Harrie-Jan; Brunner, Philip

2017-12-01

The presence of unsaturated zones at the river-aquifer interface has large implications on numerous hydraulic and chemical processes. However, the hydrological and geological controls that influence the development of unsaturated zones have so far only been analyzed with simplified conceptualizations of flow processes, or homogeneous conceptualizations of the hydraulic conductivity in either the aquifer or the riverbed. We systematically investigated the influence of heterogeneous structures in both the riverbed and the aquifer on the development of unsaturated zones. A stochastic 1-D criterion that takes both riverbed and aquifer heterogeneity into account was developed using a Monte Carlo sampling technique. The approach allows the reliable estimation of the upper bound of the spatial extent of unsaturated areas underneath a riverbed. Through systematic numerical modeling experiments, we furthermore show that horizontal capillary forces can reduce the spatial extent of unsaturated zones under clogged areas. This analysis shows how the spatial structure of clogging layers and aquifers influence the propensity for unsaturated zones to develop: In riverbeds where clogged areas are made up of many small, spatially disconnected patches with a diameter in the order of 1 m, unsaturated areas are less likely to develop compared to riverbeds where large clogged areas exist adjacent to unclogged areas. A combination of the stochastic 1-D criterion with an analysis of the spatial structure of the clogging layers and the potential for resaturation can help develop an appropriate conceptual model and inform the choice of a suitable numerical simulator for river-aquifer systems.

Unsaturated and Saturated Permeabilities of Fiber Reinforcement: Critics and Suggestions

Directory of Open Access Journals (Sweden)

Chung Hae ePARK

2015-04-01

Full Text Available In general, permeability measurement results show a strong scattering according to the measurement method, the type of test fluid and the fluid injection condition, even though permeability is regarded as a unique property of porous medium. In particular, the discrepancy between the unsaturated and saturated permeabilities for the same fabric has been widely reported. In the literature, relative permeability has been adopted to model the unsaturated flow. This approach has some limits in the modeling of double-scale porosity medium. We address this issue of permeability measurement by rigorously examining the mass conservation condition. Finally, we identify that the pressure gradient is non-linear with positive curvature in the unsaturated flow and a misinterpretation of pressure gradient is the main reason for the difference between the saturated and unsaturated permeabilities of the same fiber reinforcement. We propose to use a fixed value of permeability and to modify the mass conservation equation if there are air voids which are entrapped inside the fiber tow. Finally, we also suggest some guidelines and future perspectives to obtain more consistent permeability measurement results.

A New Polynuclear Coordination Type for (Salicylaldoxime)copper(II) Complexes: Structure and Magnetic Properties of an (Oxime)Cu₆ Cluster

DEFF Research Database (Denmark)

Wenzel, Marco; Forgan, Ross S.; Faure, Anaëlle

2009-01-01

A previously unseen coordination mode is reported for (salicylaldoxime)copper complexes utilising a linked zwitterionic NO22- donor set. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)...

Reactive distillation: an attractive alternative for the synthesis of unsaturated polyester

NARCIS (Netherlands)

Shah, M.R.; Zondervan, E.; Oudshoorn, M.L.; Haan, de A.B.

2011-01-01

Unsaturated polyester is traditionally produced in a batch wise operating reaction vessel connected to a distillation unit. An attractive alternative for the synthesis of unsaturated polyester is a reactive distillation. To value such alternative synthesis route reliable process models need to be

Sensitivity Analysis of Unsaturated Flow and Contaminant Transport with Correlated Parameters

Science.gov (United States)

Relative contributions from uncertainties in input parameters to the predictive uncertainties in unsaturated flow and contaminant transport are investigated in this study. The objectives are to: (1) examine the effects of input parameter correlations on the sensitivity of unsaturated flow and conta...

Thiol-functionalization of metal-organic framework by a facile coordination-based postsynthetic strategy and enhanced removal of Hg{sup 2+} from water

Energy Technology Data Exchange (ETDEWEB)

Ke, Fei [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Qiu, Ling-Guang, E-mail: lgqiu@ahu.edu.cn [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Yuan, Yu-Peng; Peng, Fu-Min; Jiang, Xia; Xie, An-Jian; Shen, Yu-Hua [Laboratory of Advanced Porous Materials, School of Chemistry and Chemical Engineering, Anhui University, Hefei 230039 (China); Zhu, Jun-Fa [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)

2011-11-30

Highlights: Black-Right-Pointing-Pointer A novel type of functionalized MOF for heavy metal removal. Black-Right-Pointing-Pointer Functionalization of MOF by a facile coordination-based postsynthetic strategy. Black-Right-Pointing-Pointer Thiol-functionalization of MOF has been realized for the first time. Black-Right-Pointing-Pointer Enhanced removal of Hg{sup 2+} by thiol-functionalized MOFs. - Abstract: The presence of coordinatively unsaturated metal centers in metal-organic frameworks (MOFs) provides an accessible way to selectively functionalize MOFs through coordination bonds. In this work, we describe thiol-functionalization of MOFs by choosing a well known three-dimensional (3D) Cu-based MOF, i.e. [Cu{sub 3}(BTC){sub 2}(H{sub 2}O){sub 3}]{sub n} (HKUST-1, BTC = benzene-1,3,5-tricarboxylate), by a facile coordination-based postsynthetic strategy, and demonstrate their application for removal of heavy metal ion from water. A series of [Cu{sub 3}(BTC){sub 2}]{sub n} samples stoichiometrically decorated with thiol groups has been prepared through coordination bonding of coordinatively unsaturated metal centers in HKUST-1 with -SH group in dithioglycol. The obtained thiol-functionalized samples were characterized by powder X-ray diffraction, scanning electron microscope, energy dispersive X-ray spectroscopy, infrared spectroscopy, and N{sub 2} sorption-desorption isothermal. Significantly, the thiol-functionalized [Cu{sub 3}(BTC){sub 2}]{sub n} exhibited remarkably high adsorption affinity (K{sub d} = 4.73 Multiplication-Sign 10{sup 5} mL g{sup -1}) and high adsorption capacity (714.29 mg g{sup -1}) for Hg{sup 2+} adsorption from water, while the unfunctionalized HKUST-1 showed no adsorption of Hg{sup 2+} under the same condition.

Oxygenated gasoline release in the unsaturated zone - Part 1: Source zone behavior.

Science.gov (United States)

Freitas, Juliana G; Barker, James F

2011-11-01

Oxygenates present in gasoline, such as ethanol and MTBE, are a concern in subsurface contamination related to accidental spills. While gasoline hydrocarbon compounds have low solubility, MTBE and ethanol are more soluble, ethanol being completely miscible with water. Consequently, their fate in the subsurface is likely to differ from that of gasoline. To evaluate the fate of gasoline containing oxygenates following a release in the unsaturated zone shielded from rainfall/recharge, a controlled field test was performed at Canadian Forces Base Borden, in Ontario. 200L of a mixture composed of gasoline with 10% ethanol and 4.5% MTBE was released in the unsaturated zone, into a trench 20cm deep, about 32cm above the water table. Based on soil cores, most of the ethanol was retained in the source, above the capillary fringe, and remained there for more than 100 days. Ethanol partitioned from the gasoline to the unsaturated pore-water and was retained, despite the thin unsaturated zone at the site (~35cm from the top of the capillary fringe to ground surface). Due to its lower solubility, most of the MTBE remained within the NAPL as it infiltrated deeper into the unsaturated zone and accumulated with the gasoline on top of the depressed capillary fringe. Only minor changes in the distribution of ethanol were noted following oscillations in the water table. Two methods to estimate the capacity of the unsaturated zone to retain ethanol are explored. It is clear that conceptual models for sites impacted by ethanol-fuels must consider the unsaturated zone. Copyright © 2011 Elsevier B.V. All rights reserved.

Saturated versus unsaturated hydrocarbon interactions with carbon nanostructures

Directory of Open Access Journals (Sweden)

Deivasigamani eUmadevi

2014-09-01

Full Text Available The interactions of various acyclic and cyclic hydrocarbons in both saturated and unsaturated forms with the carbon nanostructures (CNSs have been explored by using density functional theory (DFT calculations. Model systems representing armchair and zigzag carbon nanotubes (CNTs and graphene have been considered to investigate the effect of chirality and curvature of the CNSs towards these interactions. Results of this study reveal contrasting binding nature of the acyclic and cyclic hydrocarbons towards CNSs. While the saturated molecules show stronger binding affinity in acyclic hydrocarbons; the unsaturated molecules exhibit higher binding affinity in cyclic hydrocarbons. In addition, acyclic hydrocarbons exhibit stronger binding affinity towards the CNSs when compared to their corresponding cyclic counterparts. The computed results excellently corroborate the experimental observations. The interaction of hydrocarbons with graphene is more favourable when compared with CNTs. Bader’s theory of atoms in molecules has been invoked to characterize the noncovalent interactions of saturated and unsaturated hydrocarbons. Our results are expected to provide useful insights towards the development of rational strategies for designing complexes with desired noncovalent interaction involving CNSs.

Application of isotopes to the assessment of pollutant behaviour in the unsaturated zone for groundwater protection. Final report of a coordinated research project 2004-2005

International Nuclear Information System (INIS)

2009-05-01

A coordinated research project (CRP) was conducted by the IAEA with the purpose of studying what isotopic and other ancillary data are required to help understand migration of potential contaminants through the unsaturated zone (UZ) into the underlying groundwater. To this end, research projects were conducted in ten countries to study recharge and infiltration processes, as well as contaminant migration in a wide variety of UZ environments. This publication contains the reports of these ten projects and a summary of the accomplishments of the individual projects. The IAEA-TECDOC reviews the usefulness and current status of application of the combined use of isotope and other hydrogeochemical tools for the assessment of flow and transport processes in the UZ. A number of isotope and hydrochemical tools have been used to simultaneously study groundwater recharge and transport of pollutants in the UZ. This information is relevant for assessing the vulnerability of groundwater to contamination. The ten projects covered climates ranging from humid to arid, and water table depths from the near surface to over 600 m. The studies included measuring movement of water, solutes, and gases through the UZ using an assortment of isotope and geochemical tracers and approaches. Contaminant issues have been studied at most of the ten sites and the UZ was found to be very effective in protecting groundwater from most heavy metal contaminants. The publication is expected to be of interest to hydrologists, hydrogeologists and soil scientists dealing with pollution aspects and protection of groundwater resources, as well as counterparts of TC projects in Member States

Investigations of the unsaturated zone at two radioactive waste disposal sites in Lithuania.

Science.gov (United States)

Skuratovič, Žana; Mažeika, Jonas; Petrošius, Rimantas; Martma, Tõnu

2016-01-01

The unsaturated zone is an important part of the water cycle, governed by many hydrological and hydrogeological factors and processes and provide water and nutrients to the terrestrial ecosystem. Besides, the soils of the unsaturated zone are regarded as the first natural barrier to a large extent and are able to limit the spread of contaminants depending on their properties. The unsaturated zone provides a linkage between atmospheric moisture, groundwater, and seepage of groundwater to streams, lakes, or other surface water bodies. The major difference between water flow in saturated and unsaturated soils is that the hydraulic conductivity, which is conventionally assumed to be a constant in saturated soils, is a function of the degree of saturation or matrix suction in the unsaturated soils. In Lithuania, low and intermediate level radioactive wastes generated from medicine, industry and research were accumulated at the Maisiagala radioactive waste repository. Short-lived low and intermediate levels radioactive waste, generated during the operation of the Ignalina Nuclear Power Plant (INPP) and arising after the INPP decommissioning will be disposed of in the near surface repository close to the INPP (Stabatiske site). Extensive data sets of the hydraulic properties and water content attributed to unsaturated zone soil profiles of the two radioactive waste disposal sites have been collected and summarized. Globally widespread radionuclide tritium ((3)H) and stable isotope ratio ((18)O/(16)O and (2)H/(1)H) distribution features were determined in precipitation, unsaturated zone soil moisture profiles and groundwater.

Unsaturated soil moisture drying and wetting diffusion coefficient measurements in the laboratory.

Science.gov (United States)

2009-09-01

ABSTRACTTransient moisture flow in an unsaturated soil in response to suction changes is controlled by the unsaturated moisture diffusion coefficient. The moisture diffusion coefficient can be determined by measuring suction profiles over time. The l...

Second European Conference on Unsaturated Soils, E-UNSAT 2012

CERN Document Server

Jommi, Cristina; D’Onza, Francesca; Unsaturated Soils: Research and Applications

2012-01-01

These volumes contain the contributions to the Second European Conference on Unsaturated Soils, E-UNSAT 2012, held in Napoli, Italy, in June 2012. The event is the second of a series of European conferences, and follows the first successful one, organised in Durham, UK, in 2008. The conference series is supported by Technical Committee 106 of the International Society of Soil Mechanics and Geotechnical Engineering on Unsaturated Soils. The published contributions were selected after a careful peer-review process. A collection of more than one hundred papers is included, addressing the three thematic areas experimental, including advances in testing techniques and soil behaviour, modelling, covering theoretical and constitutive issues together with numerical and physical modelling, and engineering, focusing on approaches, case histories and geo-environmental themes. The areas of application of the papers embrace most of the geotechnical problems related to unsaturated soils. Increasing interest in geo-environm...

Saturated-unsaturated flow in a compressible leaky-unconfined aquifer

Science.gov (United States)

Mishra, Phoolendra K.; Vesselinov, Velimir V.; Kuhlman, Kristopher L.

2012-06-01

An analytical solution is developed for three-dimensional flow towards a partially penetrating large-diameter well in an unconfined aquifer bounded below by a leaky aquitard of finite or semi-infinite extent. The analytical solution is derived using Laplace and Hankel transforms, then inverted numerically. Existing solutions for flow in leaky unconfined aquifers neglect the unsaturated zone following an assumption of instantaneous drainage due to Neuman. We extend the theory of leakage in unconfined aquifers by (1) including water flow and storage in the unsaturated zone above the water table, and (2) allowing the finite-diameter pumping well to partially penetrate the aquifer. The investigation of model-predicted results shows that aquitard leakage leads to significant departure from the unconfined solution without leakage. The investigation of dimensionless time-drawdown relationships shows that the aquitard drawdown also depends on unsaturated zone properties and the pumping-well wellbore storage effects.

Transport of citrate-coated silver nanoparticles in unsaturated sand

Energy Technology Data Exchange (ETDEWEB)

Kumahor, Samuel K., E-mail: samuel.kumahor@ufz.de [Department of Soil Physics, Helmholtz Centre for Environmental Research–UFZ, Theodor-Lieser-Strasse 4, 06120 Halle-Saale (Germany); Hron, Pavel, E-mail: pavel.hron@iwr.uni-heidelberg.de [Interdisciplinary Center for Scientific Computing, University of Heidelberg, Im Neuenheimer Feld 368, Raum 422, 69120 Heidelberg (Germany); Metreveli, George, E-mail: metreveli@uni-landau.de [Universität Koblenz-Landau, Institute for Environmental Sciences, Group of Environmental and Soil Chemistry, Fortstr. 7, D-76829 Landau (Germany); Schaumann, Gabriele E., E-mail: schaumann@uni-landau.de [Universität Koblenz-Landau, Institute for Environmental Sciences, Group of Environmental and Soil Chemistry, Fortstr. 7, D-76829 Landau (Germany); Vogel, Hans-Jörg, E-mail: hans-joerg.vogel@ufz.de [Department of Soil Physics, Helmholtz Centre for Environmental Research–UFZ, Theodor-Lieser-Strasse 4, 06120 Halle-Saale (Germany); Institute of Soil Science and Plant Nutrition, Martin-Luther-University Halle-Wittenberg, Von-Seckendorff-Platz 3, 06120 Halle-Saale (Germany)

2015-12-01

Chemical factors and physical constraints lead to coupled effects during particle transport in unsaturated porous media. Studies on unsaturated transport as typical for soils are currently scarce. In unsaturated porous media, particle mobility is determined by the existence of an air–water interface in addition to a solid–water interface. To this end, we measured breakthrough curves and retention profiles of citrate-coated Ag nanoparticles in unsaturated sand at two pH values (5 and 9) and three different flow rates corresponding to different water contents with 1 mM KNO{sub 3} as background electrolyte. The classical DLVO theory suggests unfavorable deposition conditions at the air–water and solid–water interfaces. The breakthrough curves indicate modification in curve shapes and retardation of nanoparticles compared to inert solute. Retention profiles show sensitivity to flow rate and pH and this ranged from almost no retention for the highest flow rate at pH = 9 to almost complete retention for the lowest flow rate at pH = 5. Modeling of the breakthrough curves, thus, required coupling two parallel processes: a kinetically controlled attachment process far from equilibrium, responsible for the shape modification, and an equilibrium sorption, responsible for particle retardation. The non-equilibrium process and equilibrium sorption are suggested to relate to the solid–water and air–water interfaces, respectively. This is supported by the DLVO model extended for hydrophobic interactions which suggests reversible attachment, characterized by a secondary minimum (depth 3–5 kT) and a repulsive barrier at the air–water interface. In contrast, the solid–water interface is characterized by a significant repulsive barrier and the absence of a secondary minimum suggesting kinetically controlled and non-equilibrium interaction. This study provides new insights into particle transport in unsaturated porous media and offers a model concept representing the

Uncertainty analyses of unsaturated zone travel time at Yucca Mountain

International Nuclear Information System (INIS)

Nichols, W.E.; Freshley, M.D.

1993-01-01

Uncertainty analysis method can be applied to numerical models of ground-water flow to estimate the relative importance of physical and hydrologic input variables with respect to ground-water travel time. Monte Carlo numerical simulations of unsaturated flow in the Calico Hills nonwelded zeolitic (CHnz) layer at Yucca Mountain, Nevada, indicate that variability in recharge, and to a lesser extent in matrix porosity, explains most of the variability in predictions of water travel time through the unsaturated zone. Variations in saturated hydraulic conductivity and unsaturated curve-fitting parameters were not statistically significant in explaining variability in water travel time through the unsaturated CHnz unit. The results of this study suggest that the large uncertainty associated with recharge rate estimates for the Yucca Mountain site is of concern because the performance of the potential repository would be more sensitive to uncertainty in recharge than to any other parameter evaluated. These results are not exhaustive because of the limited site characterization data available and because of the preliminary nature of this study, which is limited to a single stratigraphic unit, one dimension, and does not account for fracture flow or other potential fast pathways at Yucca Mountain

Polynuclear Iron-Oxo/Hydroxy Complexes of Ketoacidoximate Ligands: Synthesis, Structures and Conversion to Ferric Oxide

KAUST Repository

Davaasuren, Bambar

2017-06-13

The polynuclear iron-oxo/hydroxy complexes containing ketoacidoximate ligands described in this report are [Fe3(μ3-O){O2C-C(C6H5)=NOCH3}6(py)3] (1) (py=pyridine), [Fe2(μ3-O){O2C-C(CH2-C6H5)=NO}2(H2O)(CH3OH)]2 (2) and [{Fe(μ2-OH)(O2C-C(CH3)=NO)}(dmso)]6 (3) (dmso=dimethyl sulfoxide). 1–3 are isolated from the reaction of Fe(NO3)3⋅9H2O and in situ generated anions of ketoacidoximate ligand [(HO2C-C(R1)=NOR2), where R1=CH3, C6H5 and CH2-C6H5; R2=H or CH3] in H2O, followed by crystallization in donor solvents. 1–3 undergo thermal decomposition above 200 °C and form crystalline α-Fe2O3 at 600 °C.

Adsorption of polynuclear aromatic hydrocarbons from aqueous solution: Agrowaste-modified kaolinite vs surfactant modified bentonite

Directory of Open Access Journals (Sweden)

E. I. Unuabonah

2017-01-01

Full Text Available The adsorption efficiency of a new hybrid clay adsorbent for polynuclear aromatic hydrocarbons (PAHs is compared with known modified clay adsorbents. The new hybrid clay adsorbent (HYCA showed far higher adsorption capacities for the adsorption of various PAH molecules compared with sodium dodecyl sulfate modified and humic acid modified Bentonite clay adsorbents. With the new hybrid clay adsorbent (HYCA, the adsorption of some of the larger PAH molecules was complete in the first 1 h as compared with ≈ 62% and ≈ 76% observed for both humic acid modified and sodium dodecyl sulfate modified Bentonite clay adsorbents respectively. In 24 h adsorption of the PAHs was complete for all adsorbents with HYCA adsorbent showing better efficiency in the removal of the PAH molecules from aqueous solutions. No significant change was observed with increase in time up to 48 h. The adsorption was observed to be more spontaneous with HYCA adsorbent than with either modified Bentonite adsorbents. The enthalpy of adsorption did not follow any specific order and were not consistent for all PAH molecules considered.

Electrokinetic remediation of anionic contaminants from unsaturated soils

International Nuclear Information System (INIS)

Lindgren, E.R.; Kozak, M.W.; Mattson, E.D.

1992-01-01

Heavy-metal contamination of soil and groundwater is a widespread problem in the DOE weapons complex, and for the nation as a whole. Electrokinetic remediation is one possible technique for in situ removal of such contaminants from unsaturated soils. In previous studies at Sandia National Laboratories, the electromigration of chromate ions and anionic dye ions have been demonstrated. This paper reports on a series of experiments that were conducted to study the effect of moisture content on the electromigration rate of anionic contaminants in unsaturated soil and determine the limiting moisture content for which electromigration occurs

Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

KAUST Repository

Riache, Nassima

2015-11-14

Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

Repository site data report for unsaturated tuff, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Tien, P.L.; Updegraff, C.D.; Siegel, M.D.; Wahi, K.K.; Guzowski, R.V.

1985-11-01

The US Department of Energy is currently considering the thick sequences of unsaturated, fractured tuff at Yucca Mountain, on the southwestern boundary of the Nevada Test Site, as a possible candidate host rock for a nuclear-waste repository. Yucca Mountain is in one of the most arid areas in the United States. The site is within the south-central part of the Great Basin section of the Basin and Range physiographic province and is located near a number of silicic calderas of Tertiary age. Although localized zones of seismic activity are common throughout the province, and faults are present at Yucca Mountain, the site itself is basically aseismic. No data are available on the composition of ground water in the unsaturated zone at Yucca Mountain. It has been suggested that the composition is bounded by the compositions of water from wells USW-H3, UE25p-1, J-13, and snow or rain. There are relatively few data available from Yucca Mountain on the moisture content and saturation, hydraulic conductivity, and characteristic curves of the unsaturated zone. The available literature on thermomechanical properties of tuff does not always distinguish between data from the saturated zone and data from the unsaturated zone. Geochemical, hydrologic, and thermomechanical data available on the unsaturated tuffs of Yucca Mountain are tabulated in this report. Where the data are very sparse, they have been supplemented by data from the saturated zone or from areas other than Yucca Mountain. 316 refs., 58 figs., 37 tabs

Repository site data report for unsaturated tuff, Yucca Mountain, Nevada

Energy Technology Data Exchange (ETDEWEB)

Tien, P.L.; Updegraff, C.D.; Siegel, M.D.; Wahi, K.K.; Guzowski, R.V.

1985-11-01

The US Department of Energy is currently considering the thick sequences of unsaturated, fractured tuff at Yucca Mountain, on the southwestern boundary of the Nevada Test Site, as a possible candidate host rock for a nuclear-waste repository. Yucca Mountain is in one of the most arid areas in the United States. The site is within the south-central part of the Great Basin section of the Basin and Range physiographic province and is located near a number of silicic calderas of Tertiary age. Although localized zones of seismic activity are common throughout the province, and faults are present at Yucca Mountain, the site itself is basically aseismic. No data are available on the composition of ground water in the unsaturated zone at Yucca Mountain. It has been suggested that the composition is bounded by the compositions of water from wells USW-H3, UE25p-1, J-13, and snow or rain. There are relatively few data available from Yucca Mountain on the moisture content and saturation, hydraulic conductivity, and characteristic curves of the unsaturated zone. The available literature on thermomechanical properties of tuff does not always distinguish between data from the saturated zone and data from the unsaturated zone. Geochemical, hydrologic, and thermomechanical data available on the unsaturated tuffs of Yucca Mountain are tabulated in this report. Where the data are very sparse, they have been supplemented by data from the saturated zone or from areas other than Yucca Mountain. 316 refs., 58 figs., 37 tabs.

Role of Lipid Peroxidation-Derived α, β-Unsaturated Aldehydes in Vascular Dysfunction

Directory of Open Access Journals (Sweden)

Seung Eun Lee

2013-01-01

Full Text Available Vascular diseases are the most prominent cause of death, and inflammation and vascular dysfunction are key initiators of the pathophysiology of vascular disease. Lipid peroxidation products, such as acrolein and other α, β-unsaturated aldehydes, have been implicated as mediators of inflammation and vascular dysfunction. α, β-Unsaturated aldehydes are toxic because of their high reactivity with nucleophiles and their ability to form protein and DNA adducts without prior metabolic activation. This strong reactivity leads to electrophilic stress that disrupts normal cellular function. Furthermore, α, β-unsaturated aldehydes are reported to cause endothelial dysfunction by induction of oxidative stress, redox-sensitive mechanisms, and inflammatory changes such as induction of cyclooxygenase-2 and cytokines. This review provides an overview of the effects of lipid peroxidation products, α, β-unsaturated aldehydes, on inflammation and vascular dysfunction.

Investigating Unsaturated Zone Travel Times with Tritium and Stable Isotopes

Science.gov (United States)

Visser, A.; Thaw, M.; Van der Velde, Y.

2017-12-01

Travel times in the unsaturated zone are notoriously difficult to assess. Travel time tracers relying on the conservative transport of dissolved (noble) gases (tritium-helium, CFCs or SF6) are not applicable. Large water volume requirements of other cosmogenic radioactive isotopes (sulfur-35, sodium-22) preclude application in the unsaturated zone. Prior investigations have relied on models, introduced tracers, profiles of stable isotopes or tritium, or a combination of these techniques. Significant unsaturated zone travel times (UZTT) complicate the interpretation of stream water travel time tracers by ranked StorAge Selection (rSAS) functions. Close examination of rSAS functions in a sloping soil lysimeter[1] show the effect of the UZTT on the shape of the rSAS cumulative distribution function. We studied the UZTT at the Southern Sierra Critical Zone Observatory (SS-CZO) using profiles of tritium and stable isotopes (18O and 2H) in the unsaturated zone, supported by soil water content data. Tritium analyses require 100-500 mL of soil water and therefore large soil samples (1-5L), and elaborate laboratory procedures (oven drying, degassing and noble gas mass spectrometry). The high seasonal and interannual variability in precipitation of the Mediterranean climate, variable snow pack and high annual ET/P ratios lead to a dynamic hydrology in the deep unsaturated soils and regolith and highly variable travel time distributions. Variability of the tritium concentration in precipitation further complicates direct age estimates. Observed tritium profiles (>3 m deep) are interpreted in terms of advective and dispersive vertical transport of the input variability and radioactive decay of tritium. Significant unsaturated zone travel times corroborate previously observed low activities of short-lived cosmogenic radioactive nuclides in stream water. Under these conditions, incorporating the UZTT is critical to adequately reconstruct stream water travel time distributions. 1

Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double-Bridged [Mg2 (CN)5 ](-1) Anions.

Science.gov (United States)

Li, Jin-Feng; Li, Miao-Miao; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

2015-12-01

An ab initio study of the superhalogen properties of eighteen binuclear double-bridged [Mg2 (CN)5 ](-1) clusters is reported herein by using various theoretical methods. High-level CCSD(T) results indicate that all the clusters possess strong superhalogen properties owing to their high vertical electron detachment energies (VDEs), which exceed 6.8 eV (highest: 8.15 eV). The outer valence Green's function method provides inaccurate relative VDE values; hence, this method is not suitable for this kind of polynuclear superhalogens. Both the HF and MP2 results are generally consistent with the CCSD(T) level regarding the relative VDE values and-especially interesting-the average values of the HF and MP2 VDEs are extremely close to the CCSD(T) results. The distributions of the extra electrons of the anions are mainly aggregated into the terminal CN units. These distributions are apparently different from those of previously reported triple-bridged isomers and may be the reason for the decreased VDE values of the clusters. In addition, comparisons of the VDEs of binuclear and mononuclear superhalogens as well as studies of the thermodynamic stabilities with respect to the detachment of various CN(-1) ligands are also performed. These results confirm that polynuclear structures with pseudohalogen ligands can be considered as probable new superhalogens with enhanced properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation behavior of polymer blend of isotactic polypropylenes with and without unsaturated chain end group

International Nuclear Information System (INIS)

Nakatani, Hisayuki; Kurniawan, Dodik; Taniike, Toshiaki; Terano, Minoru

2008-01-01

In this work, the relationship between the unsaturated chain end group content and the thermal oxidative degradation rate was systematically studied with binary polymer blends of isotactic polypropylene (iPP) with and without the unsaturated chain end group. The iPPs with and without the unsaturated chain end group were synthesized by a metallocene catalyst in the absence of hydrogen and by a Ziegler catalyst in the presence of one, respectively. The thermal oxidative degradation rate of the binary iPP blends was estimated from the molecular weight and the apparent activation energy (ΔE), which were obtained through size exclusion chromatography (SEC) and thermogravimetric analysis (TGA) measurements, respectively. These values exhibited a negative correlation against the mole content of the unsaturated chain end group. The thermal oxidative degradation rate apparently depends on the content of the unsaturated chain end group. This tendency suggests that the unsaturated chain end acts as a radical initiator of the iPP degradation reaction.

Saturated and unsaturated stability analysis of slope subjected to rainfall infiltration

Directory of Open Access Journals (Sweden)

Gofar Nurly

2017-01-01

Full Text Available This paper presents results of saturated and unsaturated stability analysis of typical residual slopes subjected to rainfall infiltration corresponds to 50 years rainfall return period. The slope angles considered were 45° and 70°. The saturated stability analyses were carried out for original and critical ground water level commonly considered by practicing engineer. The analyses were conducted using limit equilibrium method. Unsaturated stability analyses used combination of coupled stress–pore-water pressure analysis to evaluate the effect of rainfall infiltration on the deformation and transient pore-water pressure on slope stability. Slope stability analyses were performed at some times during and after rainfall infiltration. Results show that the critical condition for slope made by sandy material was at the end of rainfall while for clayey material was at some specified times after the rainfall ceased. Unsaturated stability analysis on sandy soil gives higher factor of safety because the soil never reached saturation. Transient analysis using unsaturated soil concept could predict more critical condition of delayed failure of slopes made up of clayey soil.

Determination of Polybutadiene Unsaturation Content in Thermal and Thermo-Oxidative Degradation Processes by NMR

Directory of Open Access Journals (Sweden)

Farshid Ziaee

2013-01-01

Full Text Available The unsaturation content of various polybutadiene (PBD types of 1,4-cis, 1,4-trans and 1,2-vinyl isomers with different molecular weights was investigated. An important parameter for unsaturation content of polybutadiene would be the determination of olefnic and aliphatic contents for three types of isomers. For this purpose, proton and carbon nuclear magnetic resonance spectroscopy methods were employed for determination of 1,4-cis, 1,4-trans and 1,2-vinyl contents. A change of adjustable parameter of NMR software was made for accurate integrals giving better results. The accuracy in calculation of low molecular weight PBD, surface area of chain end group decreased in aliphatic region. Furthermore, the changing of unsaturation content versus time was considered for 1,2-PBD and 1,4-PBD in thermal degradation conditions at 250°C. NMR results showed that during heating, the unsaturation content decreased for 1,2-PBD and was not changed for 1,4-PBD. In fact, the basic factor responsible for changing of unsaturation content in thermal degradation of PBD may be due to the presence of 1,2-vinyl isomer. Finally, changing in unsaturation content versus time was observed for 1,2-PBD and 1,4-PBD in thermo-oxidative degradation conditions at 100°C. The NMR results showed that at extended time, the unsaturation content decreased for 1,4-PBD and was not changed for 1,2-PBD. Moreover, the basic factor for changes in unsaturation content in thermo-oxidative degradation of PBD is due to the presence of 1,4-cis and 1,4-trans isomers.

Modelling the effects of pore-water chemistry on the behaviour of unsaturated clays

Directory of Open Access Journals (Sweden)

Lei Xiaoqin

2016-01-01

Full Text Available Due to their various applications in geo-environmental engineering, such as in landfill and nuclear waste disposals, the coupled chemo-hydro-mechanical analysis of expansive soils has gained more and more attention recently. These expansive soils are usually unsaturated under field conditions; therefore the capillary effects need to be taken into account appropriately. For this purpose, based on a rigorous thermodynamic framework (Lei et al., 2014, the authors have extended the chemo-mechanical model of Loret el al. (2002 for saturated homoionic expansive soils to the unsaturated case (Lei, 2015. In this paper, this chemo-mechanical unsaturated model is adopted to simulate the chemo-elastic-plastic consolidation process of an unsaturated expansive soil layer. Logical tendencies of changes in the chemical, mechanical and hydraulic field quantities are obtained.

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

International Nuclear Information System (INIS)

Whelan, Joseph F.; Neymark, Leonid A.; Moscati, Richard J.; Marshall, Brian D.; Roedder, Edwin

2008-01-01

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (T h ) up to ∼80 deg. C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite δ 18 O values, and depositional timing is constrained by the 207 Pb/ 235 U ages of chalcedony or opal in the deposits. Fluid inclusion T h from 50 samples of calcite and four samples of fluorite range from ∼35 to ∼90 deg. C. Calcite δ 18 O values range from ∼0 to ∼22 per mille (SMOW) but most fall between 12 and 20 per mille . The highest T h and the lowest δ 18 O values are found in the older calcite. Calcite T h and δ 18 O values indicate that most calcite precipitated from water with δ 18 O values between -13 and -7 per mille , similar to modern meteoric waters. Twenty-two 207 Pb/ 235 U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from ∼9.5 to 1.9 Ma. New and published 207 Pb/ 235 U and 230 Th/Uages coupled with the T h values and estimates of temperature from calcite δ 18 O values indicate that maximum unsaturated zone temperatures probably predate ∼10 Ma and that the unsaturated zone had cooled to near-present-day temperatures

Flame Retardance and Physical Properties of Novel Cured Blends of Unsaturated Polyester and Furan Resins

Directory of Open Access Journals (Sweden)

Baljinder Kaur Kandola

2015-02-01

Full Text Available Novel blends of two furan resins with an unsaturated polyester have been prepared and cured by parallel free radical (for the unsaturated polyester and acid-catalysed crosslinking (for the furan resin to give co-cured composite materials. Although these materials have inferior physical properties, such as low Tg and low storage modulus compared with those of unsaturated polyester and furan resins alone, they show markedly improved flame retardance compared with that of the normally highly flammable unsaturated polyester. This increased flame retardance arises from a condensed phase mechanism in which the furanic component forms a semi-protective char, reducing rates of thermal degradation and total heat release and heat of combustion. The blends also burn with reduced smoke output compared with that from unsaturated polyester alone.

Waste package performance in unsaturated rock

International Nuclear Information System (INIS)

Pigford, T.H.; Lee, W.W.-L.

1989-03-01

The unsaturated rock and near-atmospheric pressure of the potential nuclear waste repository at Yucca Mountain present new problems of predicting waste package performance. In this paper we present some illustrations of predictions of waste package performance and discuss important data needs. 11 refs., 9 figs., 1 tab

Hydrocarbons biodegradation in unsaturated porous medium

International Nuclear Information System (INIS)

Gautier, C.

2007-12-01

Biological processes are expected to play an important role in the degradation of petroleum hydrocarbons in contaminated soils. However, factors influencing the kinetics of biodegradation are still not well known, especially in the unsaturated zone. To address these biodegradation questions in the unsaturated zone an innovative experimental set up based on a physical column model was developed. This experimental set up appeared to be an excellent tool for elaboration of a structured porous medium, with well defined porous network and adjusted water/oil saturations. Homogeneous repartition of both liquid phases (i.e., aqueous and non aqueous) in the soil pores, which also contain air, was achieved using ceramic membranes placed at the bottom of the soil column. Reproducible interfaces (and connectivity) are developed between gas, and both non mobile water and NAPL phases, depending on the above-defined characteristics of the porous media and on the partial saturations of these three phases (NAPL, water and gas). A respirometric apparatus was coupled to the column. Such experimental set up have been validated with hexadecane in dilution in an HMN phase. This approach allowed detailed information concerning n-hexadecane biodegradation, in aerobic condition, through the profile of the oxygen consumption rate. We have taken benefit of this technique, varying experimental conditions, to determine the main parameters influencing the biodegradation kinetics and compositional evolution of hydrocarbons, under steady state unsaturated conditions and with respect to aerobic metabolism. Impacts of the nitrogen quantity and of three different grain sizes have been examined. Biodegradation of petroleum cut, as diesel cut and middle distillate without aromatic fraction, were, also studied. (author)

Hydrogeology of the unsaturated zone, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Montazer, P.; Wilson, W.E.

1985-01-01

The unsaturated volcanic tuff beneath Yucca Mountain, Nevada, is being evaluated by the US Department of Energy as a host rock for a potential mined geologic repository for high-level radioactive waste. Assessment of site suitability needs an efficient and focused investigative program. A conceptual hydrogeologic model that simulates the flow of fluids through the unsaturated zone at Yucca Mountain was developed to guide the program and to provide a basis for preliminary assessment of site suitability. The study was made as part of the Nevada Nuclear Waste Storage Investigations Project of the US Department of Energy. Thickness of the unsaturated zone is about 1640 to 2460 feet (500 to 750 meters). Based on physical properties, the rocks in the unsaturated zone are grouped for the purpose of this paper into five informal hydrogeologic units. From top to bottom these units are: Tiva Canyon welded unit, Paintbrush nonwelded unit. Topopah Spring welded unit, Calico Hills nonwelded unit, and Crater Flat unit. Welded units have a mean fracture density of 8 to 40 fractures per unit cubic meter, mean matrix porosities of 12 to 23%, matrix hydraulic conductivities with geometric means ranging from 6.5 x 10 -6 to 9.8 x 10 -6 foot per day (2 x 10 -6 to 3 x 10 -6 meter per day), and bulk hydraulic conductivities of 0.33 to 33 feet per day (0.1 to 10 meters per day). The nonwelded units have a mean fracture density of 1 to 3 fractures per unit cubic meter, mean matrix porosities of 31 to 46%, and saturated hydraulic conductivities with geometric means ranging from 2.6 x 10 -5 to 2.9 x 10 -2 foot per day (8 x 10 -6 to 9 x 10 -3 meter per day). 15 refs., 4 figs., 1 tab

Improved forward and inverse analyses of saturated-unsaturated flow toward a well in a compressible unconfined aquifer

Science.gov (United States)

Mishra, Phoolendra Kumar; Neuman, Shlomo P.

2010-07-01

We present an analytical solution for flow to a partially penetrating well in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from drawdowns recorded in the saturated and/or unsaturated zone. We improve upon a previous such solution due to Tartakovsky and Neuman (2007) by (1) adopting a more flexible representation of unsaturated zone constitutive properties and (2) allowing the unsaturated zone to have finite thickness. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of unsaturated zone constitutive parameters and thickness on drawdowns in the saturated and unsaturated zones as functions of position and time; demonstrate the development of significant horizontal hydraulic gradients in the unsaturated zone in response to pumping; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten-Mualem constitutive model; use our solution to analyze drawdown data from a pumping test conducted by the U.S. Geological Survey at Cape Cod, Massachusetts; and compare our estimates of van Genuchten-Mualem parameters with laboratory values obtained for similar materials in the area.

Groundwater recharge dynamics in unsaturated fractured chalk: a case study

Science.gov (United States)

Cherubini, Claudia; Pastore, Nicola; Giasi, Concetta I.; Allegretti, Nicolaetta M.

2016-04-01

The heterogeneity of the unsaturated zone controls its hydraulic response to rainfall and the extent to which pollutants are delayed or attenuated before reaching groundwater. It plays therefore a very important role in the recharge of aquifers and the transfer of pollutants because of the presence of temporary storage zones and preferential flows. A better knowledge of the physical processes in the unsaturated zone would allow an improved assessment of the natural recharge in a heterogeneous aquifer and of its vulnerability to surface-applied pollution. The case study regards the role of the thick unsaturated zone of the Cretaceous chalk aquifer in Picardy (North of France) that controls the hydraulic response to rainfall. In the North Paris Basin, much of the recharge must pass through a regional chalk bed that is composed of a porous matrix with embedded fractures. Different types of conceptual models have been formulated to explain infiltration and recharge processes in the unsaturated fractured rock. The present study analyses the episodic recharge in fractured Chalk aquifer using the kinematic diffusion theory to predict water table fluctuation in response to rainfall. From an analysis of the data, there is the evidence of 1) a seasonal behavior characterized by a constant increase in the water level during the winter/spring period and a recession period, 2) a series of episodic behaviors during the summer/autumn. Kinematic diffusion models are useful for predict preferential fluxes and dynamic conditions. The presented approach conceptualizes the unsaturated flow as a combination of 1) diffusive flow refers to the idealized portion of the pore space of the medium within the flow rate is driven essentially by local gradient of potential; 2) preferential flow by which water moves across macroscopic distances through conduits of macropore length.

The foam drainage equation for drainage dynamics in unsaturated porous media

Science.gov (United States)

Lehmann, P.; Hoogland, F.; Assouline, S.; Or, D.

2017-07-01

Similarity in liquid-phase configuration and drainage dynamics of wet foam and gravity drainage from unsaturated porous media expands modeling capabilities for capillary flows and supplements the standard Richards equation representation. The governing equation for draining foam (or a soil variant termed the soil foam drainage equation—SFDE) obviates the need for macroscopic unsaturated hydraulic conductivity function by an explicit account of diminishing flow pathway sizes as the medium gradually drains. The study provides new and simple analytical expressions for drainage rates and volumes from unsaturated porous media subjected to different boundary conditions. Two novel analytical solutions for saturation profile evolution were derived and tested in good agreement with a numerical solution of the SFDE. The study and the proposed solutions rectify the original formulation of foam drainage dynamics of Or and Assouline (2013). The new framework broadens the scope of methods available for quantifying unsaturated flow in porous media, where the intrinsic conductivity and geometrical representation of capillary drainage could improve understanding of colloid and pathogen transport. The explicit geometrical interpretation of flow pathways underlying the hydraulic functions used by the Richards equation offers new insights that benefit both approaches.

Study on the concentration of unsaturated fatty acid methyl esters by urea complexation

International Nuclear Information System (INIS)

Jiang, B.; Liu, Y.

2014-01-01

This study was done to obtain concentrated unsaturated fatty acid methyl esters (FAME) by urea complexation from soybean derived FAME. Effects of urea-to-FAME ratio, 95% ethanol-to-FAME ratio, crystallization temperature and time on the purification of unsaturated FAME were investigated through single factor experiments. Optimum conditions to obtain maximum FAME yield of NUCF with the purity of unsaturated FAME greater than 98% were established using Box-Behnken design (BBD) method and response surface methodology (RSM). Under optimal conditions, the FAME yield was 58.08%, and the purity of unsaturated FAME was 98% at a urea-to-FAME ratio of 1.23, 95% ethanol-to-FAME ratio of 7 and crystallization temperature of 0 degree C. Verification results revealed that the predicted values were reasonably close to experimentally observed values of 56.93% and 98.01%. (author)

Polynuclear and one-dimensional cyanide-bridged heterobimetallic ...

Indian Academy of Sciences (India)

JINGWEN SHI

2018-02-07

Feb 7, 2018 ... complexes: synthesis, crystal structures and magnetic properties. JINGWEN ... Introduction. In the recent past decades, many effective strategies have ..... organization of single molecule magnets on surfaces. Chem. Soc. Rev. ... Spin Crossover Coordination Polymer Cryst. Growth. Des. 17 2736. 17. Kaneko ...

Process for making unsaturated hydrocarbons using microchannel process technology

Science.gov (United States)

Tonkovich, Anna Lee [Dublin, OH; Yuschak, Thomas [Lewis Center, OH; LaPlante, Timothy J [Columbus, OH; Rankin, Scott [Columbus, OH; Perry, Steven T [Galloway, OH; Fitzgerald, Sean Patrick [Columbus, OH; Simmons, Wayne W [Dublin, OH; Mazanec, Terry Daymo, Eric

2011-04-12

The disclosed invention relates to a process for converting a feed composition comprising one or more hydrocarbons to a product comprising one or more unsaturated hydrocarbons, the process comprising: flowing the feed composition and steam in contact with each other in a microchannel reactor at a temperature in the range from about 200.degree. C. to about 1200.degree. C. to convert the feed composition to the product, the process being characterized by the absence of catalyst for converting the one or more hydrocarbons to one or more unsaturated hydrocarbons. Hydrogen and/or oxygen may be combined with the feed composition and steam.

Studies estimating the dermal bioavailability of polynuclear aromatic hydrocarbons from manufactured plant tar-contaminated soils

International Nuclear Information System (INIS)

Roy, T.A.; Krueger, A.J.; Taylor, B.B.; Mauro, D.M.; Goldstein, L.S.

1998-01-01

In vitro percutaneous absorption studies were performed with contaminated soils or organic extracts of contaminated soils collected at manufactured gas plant (MGP) sites. The MGP tar contaminated soils were found to contain a group of targeted polynuclear aromatic hydrocarbons (PAH) at levels ranging from 10 to 2400 mg/kg. The soil extracts contained target PAH at levels ranging from 12 000 - 34 000 mg/kg. Dermal penetration rates of target PAH from the MGP tar-contaminated soils/soil extracts were determined experimentally through human skin using 3 H-benzo(a)pyrene (BaP) as a surrogate. Results from three MGP sites showed reductions of 2-3 orders of magnitude in PAH absorption through human skin from the most contaminated soils in comparison to the soil extracts. Reduction in PAH penetration can be attributed to PAH concentration and (soil) matrix properties. PAH dermal flux values are used to determine site-specific dermally absorbed dose (DAD) and chronic daily intake (CDI) which are essential terms required to estimate risk associated with human exposure to MGP tar and MGP tar-contaminated soils. 21 refs., 4 figs., 3 tabs

Thermal history of the unsaturated zone at Yucca Mountain, Nevada, USA

Energy Technology Data Exchange (ETDEWEB)

Whelan, Joseph F. [U.S. Geological Survey, Box 25046, M.S. 963, Denver Federal Center, Denver, CO 80225 (United States)], E-mail: jfwhelan@usgs.gov; Neymark, Leonid A.; Moscati, Richard J.; Marshall, Brian D. [U.S. Geological Survey, Box 25046, M.S. 963, Denver Federal Center, Denver, CO 80225 (United States); Roedder, Edwin [Department of Earth and Planetary Science, Harvard University, Cambridge, MA 02138 (United States)

2008-05-15

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (T{sub h}) up to {approx}80 deg. C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite {delta}{sup 18}O values, and depositional timing is constrained by the {sup 207}Pb/{sup 235}U ages of chalcedony or opal in the deposits. Fluid inclusion T{sub h} from 50 samples of calcite and four samples of fluorite range from {approx}35 to {approx}90 deg. C. Calcite {delta}{sup 18}O values range from {approx}0 to {approx}22 per mille (SMOW) but most fall between 12 and 20 per mille . The highest T{sub h} and the lowest {delta}{sup 18}O values are found in the older calcite. Calcite T{sub h} and {delta}{sup 18}O values indicate that most calcite precipitated from water with {delta}{sup 18}O values between -13 and -7 per mille , similar to modern meteoric waters. Twenty-two {sup 207}Pb/{sup 235}U ages of chalcedony or opal that generally postdate elevated depositional temperatures range from {approx}9.5 to 1.9 Ma. New and published {sup 207}Pb/{sup 235}U and {sup 230}Th/Uages coupled with the T{sub h} values and estimates of temperature from calcite {delta}{sup 18}O values indicate

Growth of Synthrophomonas wolfei on unsaturated short chain fatty acids

Energy Technology Data Exchange (ETDEWEB)

Amos, D.A.; McInerney, M.J. (Univ. of Oklahoma, Norman, OK (United States))

1990-01-01

The anaerobic fatty acid-degrading syntrophic bacterium, Syntrophomonas wolfei, was grown in pure culture with either trans-2-pentenoate, trans-2-hexenoate, trans-3-hexenoate, or trans, trans-2, 4-hexadienoate as the substrate. Trans-2-pentenoate was fermented to acetate, propionate, butyrate, and valerate. Acetate, butyrate and hexanoate were produced from the six-carbon mono- and di-unsaturated acids. Propionate was also product from the trans, trans-2, 4-hexadienoate which suggested that compound was degraded by another pathway in addition to [beta]-oxidation. The transient production of trans-2-hexenoate from trans-3-hexenoate suggested that the position of the double bound shifted from carbon-3 to carbon-2 prior to [beta]-oxidation. The specific growth rate decreased with increasing carbon length and degree of unsaturation. Molar growth yields ranged from 8.4 to 17.5 mg (dry wt.) per mmol and suggested that energy was conserved not only from substrate-level phosphorylation, but also from the reduction of unsaturated substrate.

Two-dimensional steady unsaturated flow through embedded elliptical layers

Science.gov (United States)

Bakker, Mark; Nieber, John L.

2004-12-01

New analytic element solutions are presented for unsaturated, two-dimensional steady flow in vertical planes that include nonoverlapping impermeable elliptical layers and elliptical inhomogeneities. The hydraulic conductivity, which is represented by an exponential function of the pressure head, differs between the inside and outside of an elliptical inhomogeneity; both the saturated hydraulic conductivity and water retention parameters are allowed to differ between the inside and outside. The Richards equation is transformed, through the Kirchhoff transformation and a second standard transformation, into the modified Helmholtz equation. Analytic element solutions are obtained through separation of variables in elliptical coordinates. The resulting equations for the Kirchhoff potential consist of infinite sums of products of exponentials and modified Mathieu functions. In practical applications the series are truncated but still fulfill the differential equation exactly; boundary conditions are met approximately but up to machine accuracy, provided that enough terms are used. The pressure head, saturation, and flow may be computed analytically at any point in the vadose zone. Examples are given of the shadowing effect of an impermeable elliptical layer in a uniform flow field and funnel-type flow between two elliptical inhomogeneities. The presented solutions may be applied to study transport processes in vadose zones containing many impermeable elliptical layers or elliptical inhomogeneities.

Unsaturated flow characterization utilizing water content data collected within the capillary fringe

Science.gov (United States)

Baehr, Arthur; Reilly, Timothy J.

2014-01-01

An analysis is presented to determine unsaturated zone hydraulic parameters based on detailed water content profiles, which can be readily acquired during hydrological investigations. Core samples taken through the unsaturated zone allow for the acquisition of gravimetrically determined water content data as a function of elevation at 3 inch intervals. This dense spacing of data provides several measurements of the water content within the capillary fringe, which are utilized to determine capillary pressure function parameters via least-squares calibration. The water content data collected above the capillary fringe are used to calculate dimensionless flow as a function of elevation providing a snapshot characterization of flow through the unsaturated zone. The water content at a flow stagnation point provides an in situ estimate of specific yield. In situ determinations of capillary pressure function parameters utilizing this method, together with particle-size distributions, can provide a valuable supplement to data libraries of unsaturated zone hydraulic parameters. The method is illustrated using data collected from plots within an agricultural research facility in Wisconsin.

Is the regulation of the electronic properties of organic molecules by polynuclear superhalogens more effective than that by mononuclear superhalogens? A high-level ab initio case study.

Science.gov (United States)

Li, Miao-Miao; Li, Jin-Feng; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

2015-08-21

The regulation of the electronic properties of organic molecules induced by polynuclear superhalogens is theoretically explored here for sixteen composite structures. It is clearly indicated by the higher vertical electron detachment energy (VDE) that polynuclear superhalogens are more effective in regulating the electronic properties than mononuclear structures. However, this enhanced regulation is not only determined by superhalogens themselves but also related to the distribution of the extra electron of the final composites. The composites, in which the extra electron is mainly aggregated into the superhalogen moiety, will possess higher VDE values, as reported in the case of C1', 7.12 eV at the CCSD(T) level. This is probably due to the fact that, compared with organic molecules, superhalogens possess stronger attraction towards the extra electron and thus should lead to lower energies of the extra electrons and to higher VDE values eventually. Compared with CCSD(T), the Outer Valence Green's Function (OVGF) method fails completely for composite structures containing Cl atoms, while MP2 results are generally consistent in terms of the relative order of VDEs. Actually if the extra electron distribution of the systems could be approximated by the HOMO, the results at the OVGF level will be consistent with the CCSD(T) results. Conversely, the difference in VDEs between OVGF and CCSD(T) is significantly large. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to various fragmentation channels were also investigated for all the composite structures.

Saturated and unsaturated stability analysis of slope subjected to rainfall infiltration

OpenAIRE

Gofar Nurly; Rahardjo Harianto

2017-01-01

This paper presents results of saturated and unsaturated stability analysis of typical residual slopes subjected to rainfall infiltration corresponds to 50 years rainfall return period. The slope angles considered were 45° and 70°. The saturated stability analyses were carried out for original and critical ground water level commonly considered by practicing engineer. The analyses were conducted using limit equilibrium method. Unsaturated stability analyses used combination of coupled stress–...

Creep model of unsaturated sliding zone soils and long-term deformation analysis of landslides

Science.gov (United States)

Zou, Liangchao; Wang, Shimei; Zhang, Yeming

2015-04-01

Sliding zone soil is a special soil layer formed in the development of a landslide. Its creep behavior plays a significant role in long-term deformation of landslides. Due to rainfall infiltration and reservoir water level fluctuation, the soils in the slide zone are often in unsaturated state. Therefore, the investigation of creep behaviors of the unsaturated sliding zone soils is of great importance for understanding the mechanism of the long-term deformation of a landslide in reservoir areas. In this study, the full-process creep curves of the unsaturated soils in the sliding zone in different net confining pressure, matric suctions and stress levels were obtained from a large number of laboratory triaxial creep tests. A nonlinear creep model for unsaturated soils and its three-dimensional form was then deduced based on the component model theory and unsaturated soil mechanics. This creep model was validated with laboratory creep data. The results show that this creep model can effectively and accurately describe the nonlinear creep behaviors of the unsaturated sliding zone soils. In order to apply this creep model to predict the long-term deformation process of landslides, a numerical model for simulating the coupled seepage and creep deformation of unsaturated sliding zone soils was developed based on this creep model through the finite element method (FEM). By using this numerical model, we simulated the deformation process of the Shuping landslide located in the Three Gorges reservoir area, under the cycling reservoir water level fluctuation during one year. The simulation results of creep displacement were then compared with the field deformation monitoring data, showing a good agreement in trend. The results show that the creeping deformations of landslides have strong connections with the changes of reservoir water level. The creep model of unsaturated sliding zone soils and the findings obtained by numerical simulations in this study are conducive to

Chemo-hydro-mechanical behaviour of unsaturated clays

International Nuclear Information System (INIS)

Mokni, N.; Olivella, S.; Alonso, E.E.; Romero, E.

2010-01-01

Document available in extended abstract form only. Understanding of the chemical effects on clays is essential for many problems ranging from pollution studies and waste-containment. Several studies examined the effect of changes in pore fluid composition on the mechanical and hydraulic properties. Volume changes (contraction/ expansion) have been measured on clay specimens upon exposure to salt solutions or permeation with organic liquids. Moreover, it was shown that permeation of clay with brine induces an increase of the shear strength. In addition, several models have been proposed to describe the chemo-mechanical behaviour of saturated clays under saturated conditions. A new chemo-hydro-mechanical model for unsaturated clays is under development. The chemo-mechanical effects are described within an elasto-plastic framework using the concept that chemical effects act on the plastic properties by increasing or decreasing the pre-consolidation stress. The model is based on the distinction within the material of a microstructural and a macro-structural levels. Chemical loading has a significant effect on the microstructure. The negative pressure associated with the capillary water plays its role in the interconnected macro pores. By adopting simple assumptions concerning the coupling between the two levels it is intended to reproduce the features of the behaviour of unsaturated clays when there is a change in pore fluid composition (increase or decrease of concentration). A yield surface which defines the set of yield pre-consolidation stress values, for each associated capillary suction and concentration of pore fluid should be defined. In addition, the behaviour of clays under unsaturated condition and the behaviour at full saturation under chemical loading represent two limiting cases of the framework. Studies on the compatibility of Boom Clay with large amounts of nitrate- bearing bituminized radioactive waste have recently raised a particular interest on the

Unsaturated fatty acids protect trophoblast cells from saturated fatty acid-induced autophagy defects.

Science.gov (United States)

Hong, Ye-Ji; Ahn, Hyo-Ju; Shin, Jongdae; Lee, Joon H; Kim, Jin-Hoi; Park, Hwan-Woo; Lee, Sung Ki

2018-02-01

Dysregulated serum fatty acids are associated with a lipotoxic placental environment, which contributes to increased pregnancy complications via altered trophoblast invasion. However, the role of saturated and unsaturated fatty acids in trophoblastic autophagy has yet to be explored. Here, we demonstrated that prolonged exposure of saturated fatty acids interferes with the invasiveness of human extravillous trophoblasts. Saturated fatty acids (but not unsaturated fatty acids) inhibited the fusion of autophagosomes and lysosomes, resulting in the formation of intracellular protein aggregates. Furthermore, when the trophoblast cells were exposed to saturated fatty acids, unsaturated fatty acids counteracted the effects of saturated fatty acids by increasing degradation of autophagic vacuoles. Saturated fatty acids reduced the levels of the matrix metalloproteinases (MMP)-2 and MMP-9, while unsaturated fatty acids maintained their levels. In conclusion, saturated fatty acids induced decreased trophoblast invasion, of which autophagy dysfunction plays a major role. Copyright © 2017 Elsevier B.V. All rights reserved.

FITTING OF THE DATA FOR DIFFUSION COEFFICIENTS IN UNSATURATED POROUS MEDIA

Energy Technology Data Exchange (ETDEWEB)

B. Bullard

1999-05-01

The purpose of this calculation is to evaluate diffusion coefficients in unsaturated porous media for use in the TSPA-VA analyses. Using experimental data, regression techniques were used to curve fit the diffusion coefficient in unsaturated porous media as a function of volumetric water content. This calculation substantiates the model fit used in Total System Performance Assessment-1995 An Evaluation of the Potential Yucca Mountain Repository (TSPA-1995), Section 6.5.4.

FITTING OF THE DATA FOR DIFFUSION COEFFICIENTS IN UNSATURATED POROUS MEDIA

International Nuclear Information System (INIS)

B. Bullard

1999-01-01

The purpose of this calculation is to evaluate diffusion coefficients in unsaturated porous media for use in the TSPA-VA analyses. Using experimental data, regression techniques were used to curve fit the diffusion coefficient in unsaturated porous media as a function of volumetric water content. This calculation substantiates the model fit used in Total System Performance Assessment-1995 An Evaluation of the Potential Yucca Mountain Repository (TSPA-1995), Section 6.5.4

Unsaturated carbone and allenylidene ruthenium complexes from alkynes

International Nuclear Information System (INIS)

Bozek, Yu.L.; Diznev, P.A.

1995-01-01

The author's studies aimed at activation of terminal alkynes by metal complexes, reactivity patterns and selective preparations of unsaturated carbene, allenylidene and cumulenylidene derivatives of (arene)ruthenium complexes are reviewed. 48 refs

Oxygenation of saturated and unsaturated hydrocarbons with ...

Indian Academy of Sciences (India)

Unknown

Oxygenation of saturated and unsaturated hydrocarbons with sodium periodate. 431. Table 1. Competitive oxygenation of tetralin and cyclooctene with sodium periodate catalyzed by different manga- .... Teacher Education University. My grateful thanks also extend to Dr D Mohajer for his useful sugges- tions. References. 1.

Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to β,γ-Unsaturated α-Keto Esters

Energy Technology Data Exchange (ETDEWEB)

Suh, Chang Won; Han, Tae Hyun; Kim, Dae Young [Soonchunhyang Univ., Asan (Korea, Republic of)

2013-06-15

In conclusion, we have developed organocatalytic enantioselective conjugate addition reaction of 4-hydroxycoumarin (1) to β,γ-unsaturated α-keto esters 2 to afford biologically valuable warfarin derivatives 3. The process is efficiently catalyzed by a binaphthyl-modified thiourea organocatalyst. The coumarin core is present as a characteristic structural motif in a large number of natural products and biologically active molecules.1 Particularly, many of these naturally occurring 4-hydroxycoumarin and their synthetic analogues are important precursors for the synthesis of natural products and pharmaceuticals. Enantioselective organocatalytic conjugate addition of 4-hydroxycoumarin to α,β-unsaturated ketones is a straightforward method to access warfarin which is an effective anticoagulants. Although a number of reactions of α,β-unsaturated ketones as Michael acceptors have been reported, the corresponding β,γ-unsaturated α-keto esters have received relatively little attention as Michael acceptors. Recently, several groups have reported the asymmetric Michael addition of 4-hydroxycoumarin to β,γ-unsaturated α-keto esters catalyzed by Cu(II)-bisoxazoline, N,N'-dioxide-Ni(II) complexes, thiourea catalysts. Although several efficient methods have been achieved by these systems, an effective method for the synthesis of warfarin analogues is still a challenge.

Organocatalytic Asymmetric Michael Addition of 4-Hydroxycoumarin to β,γ-Unsaturated α-Keto Esters

International Nuclear Information System (INIS)

Suh, Chang Won; Han, Tae Hyun; Kim, Dae Young

2013-01-01

In conclusion, we have developed organocatalytic enantioselective conjugate addition reaction of 4-hydroxycoumarin (1) to β,γ-unsaturated α-keto esters 2 to afford biologically valuable warfarin derivatives 3. The process is efficiently catalyzed by a binaphthyl-modified thiourea organocatalyst. The coumarin core is present as a characteristic structural motif in a large number of natural products and biologically active molecules.1 Particularly, many of these naturally occurring 4-hydroxycoumarin and their synthetic analogues are important precursors for the synthesis of natural products and pharmaceuticals. Enantioselective organocatalytic conjugate addition of 4-hydroxycoumarin to α,β-unsaturated ketones is a straightforward method to access warfarin which is an effective anticoagulants. Although a number of reactions of α,β-unsaturated ketones as Michael acceptors have been reported, the corresponding β,γ-unsaturated α-keto esters have received relatively little attention as Michael acceptors. Recently, several groups have reported the asymmetric Michael addition of 4-hydroxycoumarin to β,γ-unsaturated α-keto esters catalyzed by Cu(II)-bisoxazoline, N,N'-dioxide-Ni(II) complexes, thiourea catalysts. Although several efficient methods have been achieved by these systems, an effective method for the synthesis of warfarin analogues is still a challenge

Saturated-unsaturated flow to a partially penetrating well with storage in a compressible aquifer

Science.gov (United States)

Mishra, P. K.; Neuman, S. P.

2010-12-01

Mishra and Neuman [2010] developed an analytical solution for flow to a partially penetrating well of zero radius in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from responses recorded in the saturated and/or the unsaturated zone. We extend their solution to the case of a finite diameter pumping well with storage. Both solutions account for horizontal as well as vertical flows throughout the system. We investigate the effects of storage in the pumping well and delayed piezometer response on drawdowns in the saturated and unsaturated zones as functions of position and time; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the van Genuchten - Mualem constitutive model; and use our solution to analyze drawdown data from a pumping test conducted at the Borden site in Ontario, Canada.

Quantification of groundwater recharge through application of pilot techniques in the unsaturated zone.

Science.gov (United States)

Kallioras, Andreas; Piepenbrink, Matthias; Schuth, Christoph; Pfletschinger, Heike; Dietrich, Peter; Koeniger, Franz; Rausch, Randolf

2010-05-01

Accurate determination of groundwater recharge is a key issue for the "smart mining" of groundwater resources. Groundwater recharge estimation techniques depend on the investigated hydrologic zone, and therefore main approaches are based on (a) unsaturated zone, (b) saturated zone and (c) surface water studies. This research contributes to the determination of groundwater recharge by investigating the infiltration of groundwater through the unsaturated zone. The investigations are conducted through the application of a combination of different pilot field as well as lab techniques. The field techniques include the installation of specially designed Time Domain Reflectometry (TDR) sensors, at different depths within the unsaturated zone for in-situ and continuous measurements of the volumetric pore water content. Additionally, the extraction of pore water -for analysis of its isotopic composition- from multilevel undisturbed soil samples through significant depths within the unsaturated zone column, enables the dating of the groundwater age through the determination of its isotopic composition. The in-situ investigation of the unsaturated zone is complemented by the determination of high resolution temperature profiles. The installation of the pilot TDR sensors is achieved by using direct push methods at significant depths within the unsaturated zone, providing continuous readings of the soil moisture content. The direct push methods are also ideal for multilevel sampling of undisturbed -without using any drilling fluids which affect the isotopic composition of the containing pore water- soil and consequent extraction of the included pore water for further isotopic determination. The pore water is extracted by applying the method of azeotropic distillation; a method which has the least isotopic fractionation effects on groundwater samples. The determination of different isotopic signals such as 18O, 2H, 3H, and 36Cl, aims to the investigation of groundwater transit

Complex Binding of the FabR Repressor of Bacterial Unsaturated Fatty Acid Biosynthesis to its Cognate Promoters

OpenAIRE

Feng, Youjun; Cronan, John E.

2011-01-01

Two transcriptional regulators, the FadR activator and the FabR repressor control biosynthesis of unsaturated fatty acids in Escherichia coli. FabR represses expression of the two genes, fabA and fabB, required for unsaturated fatty acid synthesis and has been reported to require the presence of an unsaturated thioester (of either acyl carrier protein or CoA) in order to bind the fabA and fabB promoters in vitro. We report in vivo experiments in which unsaturated fatty acid synthesis was bloc...

Biodegradation of vapor-phase toluene in unsaturated porous media: Column experiments

International Nuclear Information System (INIS)

Khan, Ali M.; Wick, Lukas Y.; Harms, Hauke; Thullner, Martin

2016-01-01

Biodegradation of organic chemicals in the vapor phase of soils and vertical flow filters has gained attention as promising approach to clean up volatile organic compounds (VOC). The drivers of VOC biodegradation in unsaturated systems however still remain poorly understood. Here, we analyzed the processes controlling aerobic VOC biodegradation in a laboratory setup mimicking the unsaturated zone above a shallow aquifer. The setup allowed for diffusive vapor-phase transport and biodegradation of three VOC: non-deuterated and deuterated toluene as two compounds of highly differing biodegradability but (nearly) identical physical and chemical properties, and MTBE as (at the applied experimental conditions) non-biodegradable tracer and internal control. Our results showed for toluene an effective microbial degradation within centimeter VOC transport distances despite high gas-phase diffusivity. Degradation rates were controlled by the reactivity of the compounds while oxic conditions were found everywhere in the system. This confirms hypotheses that vadose zone biodegradation rates can be extremely high and are able to prevent the outgassing of VOC to the atmosphere within a centimeter range if compound properties and site conditions allow for sufficiently high degradation rates. - Highlights: • The column setup allows resolving vapor-phase VOC concentration gradients at cm scale resolution. • Vapor-phase and liquid-phase concentrations are measured simultaneously. • Isotopically labelled VOC was used as reference species of low biodegradability. • Biodegradation rates in the unsaturated zone can be very high and act at a cm scale. • Unsaturated material can be an effective bio-barrier avoiding biodegradable VOC emissions. - Microbial degradation activity can be sufficient to remove VOC from unsaturated porous media after a few centimeter of vapor-phase diffusive transport and mayeffectively avoid atmospheric emissions.

Improved solution for saturated-unsaturated flow to a partially penetrating well in a compressible unconfined aquifer

Science.gov (United States)

Mishra, P. K.; Neuman, S. P.

2009-12-01

Tartakovsky and Neuman [2007] developed an analytical solution for flow to a partially penetrating well pumping at a constant rate from a compressible unconfined aquifer considering an unsaturated zone of infinite thickness. In their solution three-dimensional, axially symmetric unsaturated flow was described by a linearized version of Richards’ equation in which both relative hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value. Both exponential functions were characterized by a common exponent. We present an improved solution in which relative hydraulic conductivity and water content are characterized by separate parameters and the unsaturated zone has finite thickness. Our four-parameter representation of these functions is more flexible than the three-parameter version of Mathias and Butler [2006], who consider flow in the unsaturated zone to be strictly vertical and the pumping well to be fully penetrating. We investigate the effects of unsaturated zone thickness and constitutive parameters on drawdown in the unsaturated and saturated zones as functions of position and time. We then use our new solution to analyze data from synthetic and real pumping tests.

Enhanced Attenuation of Unsaturated Chlorinated Solvent Source Zones using Direct Hydrogen Delivery

Science.gov (United States)

2013-01-01

solvents. This approach for bioremediation of unsaturated soils containing chlorinated solvents was originally proposed in a patent by Hughes et al...have been conducted on the use of hydrogen as an electron donor for the anaerobic bioremediation of saturated and unsaturated porous media (Evans and...proven to be very effective in remediating releases of petroleum products including gasoline, jet fuels, kerosene, and diesel fuel. Several field

Water transport monitoring in an unsaturated zone – Case study: lysimeter Selniška dobrava (Slovenia

Directory of Open Access Journals (Sweden)

Nina Mali

2002-12-01

Full Text Available Pollution transport in an aquifer depends on its structure, upper unsaturated zone and lower saturated zone. In order to understand processes in the unsaturated zone, several hydrogeological field measurements must be done. A field laboratory- lysimeter in Selni{kadobrava was installed for the improvement of field measurements, and explanation of the parameters and processes in the unsaturated zone. The problems, which can be solved by means of investigations in a lysimeter, are defined in this paper. Described are also:concept of investigation planning, construction and equipment of the lysimeter, measurements of unsaturated zone parameters and processes, water sampling for physical, chemical and isotope analysis.

Residual mitochondrial transmembrane potential decreases unsaturated fatty acid level in sake yeast during alcoholic fermentation

Directory of Open Access Journals (Sweden)

Kazutaka Sawada

2016-01-01

Full Text Available Oxygen, a key nutrient in alcoholic fermentation, is rapidly depleted during this process. Several pathways of oxygen utilization have been reported in the yeast Saccharomyces cerevisiae during alcoholic fermentation, namely synthesis of unsaturated fatty acid, sterols and heme, and the mitochondrial electron transport chain. However, the interaction between these pathways has not been investigated. In this study, we showed that the major proportion of unsaturated fatty acids of ester-linked lipids in sake fermentation mash is derived from the sake yeast rather than from rice or koji (rice fermented with Aspergillus. Additionally, during alcoholic fermentation, inhibition of the residual mitochondrial activity of sake yeast increases the levels of unsaturated fatty acids of ester-linked lipids. These findings indicate that the residual activity of the mitochondrial electron transport chain reduces molecular oxygen levels and decreases the synthesis of unsaturated fatty acids, thereby increasing the synthesis of estery flavors by sake yeast. This is the first report of a novel link between residual mitochondrial transmembrane potential and the synthesis of unsaturated fatty acids by the brewery yeast during alcoholic fermentation.

Volatile organic compounds in the unsaturated zone from radioactive wastes

Science.gov (United States)

Baker, Ronald J.; Andraski, Brian J.; Stonestrom, David A.; Luo, Wentai

2012-01-01

Volatile organic compounds (VOCs) are often comingled with low-level radioactive wastes (LLRW), but little is known about subsurface VOC emanations from LLRW landfills. The current study systematically quantified VOCs associated with LLRW over an 11-yr period at the USGS Amargosa Desert Research Site (ADRS) in southwestern Nevada. Unsaturated-zone gas samples of VOCs were collected by adsorption on resin cartridges and analyzed by thermal desorption and GC/MS. Sixty of 87 VOC method analytes were detected in the 110-m-thick unsaturated zone surrounding a LLRW disposal facility. Chlorofluorocarbons (CFCs) were detected in 100% of samples collected. Chlorofluorocarbons are powerful greenhouse gases, deplete stratospheric ozone, and are likely released from LLRW facilities worldwide. Soil-gas samples collected from a depth of 24 m and a horizontal distance 100 m south of the nearest waste-disposal trench contained >60,000 ppbv total VOCs, including >37,000 ppbv CFCs. Extensive sampling in the shallow unsaturated zone (0–2 m deep) identified areas where total VOC concentrations exceeded 5000 ppbv at the 1.5-m depth. Volatile organic compound concentrations exceeded background levels up to 300 m from the facility. Maximum vertical diffusive fluxes of total VOCs were estimated to be 1 g m-2 yr-1. Volatile organic compound distributions were similar but not identical to those previously determined for tritium and elemental mercury. To our knowledge, this study is the first to characterize the unsaturated zone distribution of VOCs emanating from a LLRW landfill. Our results may help explain anomalous transport of radionuclides at the ADRS and elsewhere.

Combined effects of headgroup charge and tail unsaturation of lipids on lateral organization and diffusion of lipids in model biomembranes

International Nuclear Information System (INIS)

Chen Xiao-Jie; Liang Qing

2017-01-01

Lateral organization and dynamics of lipids in plasma membranes are crucial for several cellular processes such as signal transduction across the membrane and still remain elusive. In this paper, using coarse-grained molecular dynamics simulation, we theoretically study the combined effects of headgroup charge and tail unsaturation of lipids on the lateral organization and diffusion of lipids in ternary lipid bilayers. In neutral ternary lipid bilayers composed of saturated lipids, unsaturated lipids, and cholesterols, under the conditions of given temperature and components, the main factor for the phase separation is the unsaturation of unsaturated lipids and the bilayers can be separated into liquid-ordered domains enriched in saturated lipids and cholesterols and liquid-disordered domains enriched in unsaturated lipids. Once the headgroup charge is introduced, the electrostatic repulsion between the negatively charged lipid headgroups will increase the distance between the charged lipids. We find that the lateral organization and diffusion of the lipids in the (partially) charged ternary lipid bilayers are determined by the competition between the headgroup charge and the unsaturation of the unsaturated lipids. In the bilayers containing unsaturated lipids with lower unsaturation, the headgroup charge plays a crucial role in the lateral organization and diffusion of lipids. The headgroup charge may make the lipid domains unstable and even can suppress phase separation of the lipids in some systems. However, in the bilayers containing highly unsaturated lipids, the lateral organization and diffusion of lipids are mainly dominated by the unsaturation of the unsaturated lipids. This work may provide some theoretical insights into understanding the formation of nanosized domains and lateral diffusion of lipids in plasma membranes. (paper)

Thermo-hydro mechanical modeling in unsaturated hard clay: application to nuclear waste storage

International Nuclear Information System (INIS)

Jia, Y.

2006-07-01

This work presents an elastoplastic damage model for argillite in unsaturated conditions. A short resume of experimental investigations is presented in the first part. The results obtained show an important plastic deformation coupled with damage induced by initiation and growth of microcracks. Influences of water content on the mechanical behaviour are also investigated. Based on experimental data and micro-mechanical considerations, a general constitutive model is proposed for the poro-mechanical behavior of argillite in unsaturated conditions. The time dependent creep has also been incorporated in they model. The performance of the model is examined by comparing numerical simulation with experimental data in various load paths under saturated and unsaturated conditions. Finally, the model is applied to hydro-mechanical coupling study of the REP experiment and thermo-hydro-mechanical coupling study of the HE-D experiment. A good agreement is obtained between experimental data and numerical predictions. It has been shown that the proposed model describe correctly the main features of the mechanical behaviour of unsaturated rocks. (author)

Review and selection of unsaturated flow models

Energy Technology Data Exchange (ETDEWEB)

Reeves, M.; Baker, N.A.; Duguid, J.O. [INTERA, Inc., Las Vegas, NV (United States)

1994-04-04

Since the 1960`s, ground-water flow models have been used for analysis of water resources problems. In the 1970`s, emphasis began to shift to analysis of waste management problems. This shift in emphasis was largely brought about by site selection activities for geologic repositories for disposal of high-level radioactive wastes. Model development during the 1970`s and well into the 1980`s focused primarily on saturated ground-water flow because geologic repositories in salt, basalt, granite, shale, and tuff were envisioned to be below the water table. Selection of the unsaturated zone at Yucca Mountain, Nevada, for potential disposal of waste began to shift model development toward unsaturated flow models. Under the US Department of Energy (DOE), the Civilian Radioactive Waste Management System Management and Operating Contractor (CRWMS M&O) has the responsibility to review, evaluate, and document existing computer models; to conduct performance assessments; and to develop performance assessment models, where necessary. This document describes the CRWMS M&O approach to model review and evaluation (Chapter 2), and the requirements for unsaturated flow models which are the bases for selection from among the current models (Chapter 3). Chapter 4 identifies existing models, and their characteristics. Through a detailed examination of characteristics, Chapter 5 presents the selection of models for testing. Chapter 6 discusses the testing and verification of selected models. Chapters 7 and 8 give conclusions and make recommendations, respectively. Chapter 9 records the major references for each of the models reviewed. Appendix A, a collection of technical reviews for each model, contains a more complete list of references. Finally, Appendix B characterizes the problems used for model testing.

Review and selection of unsaturated flow models

International Nuclear Information System (INIS)

Reeves, M.; Baker, N.A.; Duguid, J.O.

1994-01-01

Since the 1960's, ground-water flow models have been used for analysis of water resources problems. In the 1970's, emphasis began to shift to analysis of waste management problems. This shift in emphasis was largely brought about by site selection activities for geologic repositories for disposal of high-level radioactive wastes. Model development during the 1970's and well into the 1980's focused primarily on saturated ground-water flow because geologic repositories in salt, basalt, granite, shale, and tuff were envisioned to be below the water table. Selection of the unsaturated zone at Yucca Mountain, Nevada, for potential disposal of waste began to shift model development toward unsaturated flow models. Under the US Department of Energy (DOE), the Civilian Radioactive Waste Management System Management and Operating Contractor (CRWMS M ampersand O) has the responsibility to review, evaluate, and document existing computer models; to conduct performance assessments; and to develop performance assessment models, where necessary. This document describes the CRWMS M ampersand O approach to model review and evaluation (Chapter 2), and the requirements for unsaturated flow models which are the bases for selection from among the current models (Chapter 3). Chapter 4 identifies existing models, and their characteristics. Through a detailed examination of characteristics, Chapter 5 presents the selection of models for testing. Chapter 6 discusses the testing and verification of selected models. Chapters 7 and 8 give conclusions and make recommendations, respectively. Chapter 9 records the major references for each of the models reviewed. Appendix A, a collection of technical reviews for each model, contains a more complete list of references. Finally, Appendix B characterizes the problems used for model testing

A quasilinear model for solute transport under unsaturated flow

International Nuclear Information System (INIS)

Houseworth, J.E.; Leem, J.

2009-01-01

We developed an analytical solution for solute transport under steady-state, two-dimensional, unsaturated flow and transport conditions for the investigation of high-level radioactive waste disposal. The two-dimensional, unsaturated flow problem is treated using the quasilinear flow method for a system with homogeneous material properties. Dispersion is modeled as isotropic and is proportional to the effective hydraulic conductivity. This leads to a quasilinear form for the transport problem in terms of a scalar potential that is analogous to the Kirchhoff potential for quasilinear flow. The solutions for both flow and transport scalar potentials take the form of Fourier series. The particular solution given here is for two sources of flow, with one source containing a dissolved solute. The solution method may easily be extended, however, for any combination of flow and solute sources under steady-state conditions. The analytical results for multidimensional solute transport problems, which previously could only be solved numerically, also offer an additional way to benchmark numerical solutions. An analytical solution for two-dimensional, steady-state solute transport under unsaturated flow conditions is presented. A specific case with two sources is solved but may be generalized to any combination of sources. The analytical results complement numerical solutions, which were previously required to solve this class of problems.

Analysis of pumping-induced unsaturated regions beneath aperennial river

Energy Technology Data Exchange (ETDEWEB)

Su, G.W.; Jasperse, J.; Seymour, D.; Constantz, J.; Zhou, Q.

2007-05-15

The presence of an unsaturated region beneath a streambedduring groundwater pumping near streams reduces the pumping capacity whenit reaches the well screens, changes flow paths, and alters the types ofbiological transformations in the streambed sediments. Athree-dimensional, multi-phase flow model of two horizontal collectorwells along the Russian River near Forestville, California was developedto investigate the impact of varying the ratio of the aquifer tostreambed permeability on (1) the formation of an unsaturated regionbeneath the stream, (2) the pumping capacity, (3) stream-water fluxesthrough the streambed, and (4) stream-water travel times to the collectorwells. The aquifer to streambed permeability ratio at which theunsaturated region was initially observed ranged from 10 to 100. The sizeof the unsaturated region beneath the streambed increased as the aquiferto streambed permeability ratio increased. The simulations also indicatedthat for a particular aquifer permeability, decreasing the streambedpermeability by only a factor of 2-3 from the permeability wheredesaturation initially occurred resulted in reducing the pumpingcapacity. In some cases, the stream-water fluxes increased as thestreambed permeability decreased. However, the stream water residencetimes increased and the fraction of stream water that reached that thewells decreased as the streambed permeability decreased, indicating thata higher streambed flux does not necessarily correlate to greaterrecharge of stream water around the wells.

Unsaturated flow and transport through fractured rock related to high-level waste repositories

International Nuclear Information System (INIS)

Evans, D.D.; Rasmussen, T.C.

1991-01-01

Research results are summarized for a US Nuclear Regulatory Commission contract with the University of Arizona focusing on field and laboratory methods for characterizing unsaturated fluid flow and solute transport related to high-level radioactive waste repositories. Characterization activities are presented for the Apache Leap Tuff field site. The field site is located in unsaturated, fractured tuff in central Arizona. Hydraulic, pneumatic, and thermal characteristics of the tuff are summarized, along with methodologies employed to monitor and sample hydrologic and geochemical processes at the field site. Thermohydrologic experiments are reported which provide laboratory and field data related to the effects conditions and flow and transport in unsaturated, fractured rock. 29 refs., 17 figs., 21 tabs

Measurement of polynuclear aromatic hydrocarbon concentrations in the plume of Kuwait oil well fires

International Nuclear Information System (INIS)

Olsen, K.B.; Wright, C.W.; Veverka, C.; Ball, J.C.; Stevens, R.

1995-03-01

Following their retreat from Kuwait during February and March of 1991, the Iraqi Army set fire to over 500 oil wells dispersed throughout the Kuwait oil fields. During the period of sampling from July to August 1991, it was estimated that between 3.29 x 10 6 barrels per day of crude oil were combusted. The resulting fires produced several plumes of black and white smoke that coalesced to form a composite ''super'' plume. Because these fires were uncontrolled, significant quantities of organic materials were dispersed into the atmosphere and drifted throughout the Middle East. The organic particulants associated with the plume of the oil well fires had a potential to be rich in polynuclear aromatic hydrocarbon (PAH) compounds. Based on the extreme mutagenic and carcinogenic activities of PAHs found in laboratory testing, a serious health threat to the population of that region potentially existed. Furthermore, the Kuwait oil fire plumes represented a unique opportunity to study the atmospheric chemistry associated with PAHs in the plume. If samples were collected near the plume source and from the plume many kilometers downwind from the source, comparisons could be made to better understand atmospheric reactions associated with particle-bound and gas-phase PAHs. To help answer health-related concerns and to better understand the fate and transport of PAHs in an atmospheric environment, a sampling and analysis program was developed

BUILDING CONCEPTUAL AND MATHEMATICAL MODEL FOR WATER FLOW AND SOLUTE TRANSPORT IN THE UNSATURATED ZONE AT KOSNICA SITE

Directory of Open Access Journals (Sweden)

Stanko Ružičić

2012-12-01

Full Text Available Conceptual model of flow and solute transport in unsaturated zone at Kosnica site, which is the basis for modeling pollution migration through the unsaturated zone to groundwater, is set up. The main characteristics of the unsaturated zone of the Kosnica site are described. Detailed description of investigated profile of unsaturated zone, with all necessary analytical results performed and used in building of conceptual models, is presented. Experiments that are in progress and processes which are modeled are stated. Monitoring of parameters necessary for calibration of models is presented. The ultimate goal of research is risk assessment of groundwater contamination at Kosnica site that has its source in or on unsaturated zone.

Unsaturated polyester resin composition curable with ionizing radiations

International Nuclear Information System (INIS)

Maruyama, Tsutomu; Murata, Koichiro.

1971-01-01

An unsaturated polyester resin composition curable with ionizing radiations and excellent in weather resistance is provided. The composition is obtained by reacting 10-12 moles of a polyhydric alcohol (e.g. ethylene glycol) with 10 moles of an acid mixture (25.45% by mole of endo-cis-bicyclo (2,2,1)-5-heptene-2-3-dicarboxylic acid (A), 20-40% of unsaturated dibasic acid and 15-55% of saturated dibasic acid) so that the acid value reaches 4-11. The composition is useful as coating, laminating and molding materials. As a coating material it is excellent in surface hardening property. The ionizing radiation used is preferably β-, α-rays or electron beams. In one example, and unsaturated polyester was prepared by reacting 3 moles of fumaric acid, 2 moles of phthalic anhydride, 3 moles of adipic acid 3, moles of (A), 10 moles of neopentyl glycol and 1 mole of trimethylolpropane. The resin was dissolved into a mixture of styrene, methyl methacrylate and butyl acrylate (50:8:42) and incorporated with titanium white. An ABS plate was coated with the enamel thus obtained and irradiated with electron beams (12 Mrad). In exposure test at 60 0 C, luster of the film was 92 before exposure and 83 after 30 months. In a comparative run in which (A) was not used, luster of the film decreased from 90 to 45 in 30 months. (Sakaichi, S.)

Unanticipated coordination of tris buffer to the Radical SAM cluster of the RimO methylthiotransferase.

Science.gov (United States)

Molle, Thibaut; Clémancey, Martin; Latour, Jean-Marc; Kathirvelu, Velavan; Sicoli, Giuseppe; Forouhar, Farhad; Mulliez, Etienne; Gambarelli, Serge; Atta, Mohamed

2016-07-01

Radical SAM enzymes generally contain a [4Fe-4S](2+/1+) (RS cluster) cluster bound to the protein via the three cysteines of a canonical motif CxxxCxxC. The non-cysteinyl iron is used to coordinate SAM via its amino-carboxylate moiety. The coordination-induced proximity between the cluster acting as an electron donor and the adenosyl-sulfonium bond of SAM allows for the homolytic cleavage of the latter leading to the formation of the reactive 5'-deoxyadenosyl radical used for substrate activation. Most of the structures of Radical SAM enzymes have been obtained in the presence of SAM, and therefore, little is known about the situation when SAM is not present. In this report, we show that RimO, a methylthiotransferase belonging to the radical SAM superfamily, binds a Tris molecule in the absence of SAM leading to specific spectroscopic signatures both in Mössbauer and pulsed EPR spectroscopies. These data provide a cautionary note for researchers who work with coordinative unsaturated iron sulfur clusters.

Modeling of flow and mass transport processes in unsaturated soils in combination with technical facilities

International Nuclear Information System (INIS)

Hasan, Issa

2014-01-01

The modelling of complex systems such as the underground is a means to describe the processes occurring in the reality. The conducting of experiments on a model to obtain qualitative evidence about a real system is referred to as a simulation. Thereby, various models (e.g. physical and mathematical models) can be used. The unsaturated zone (vadose zone) is the region between the land surface and the water table, in which the water content is less than full saturation, and the pressure is lower than the atmospheric pressure. The unsaturated zone is very significant for agriculture, geobiology, aerobic degradation processes and groundwater recharge. The processes of water flow and solute transport in the unsaturated zone can be described by means of numerical simulation programs. The aim of the present work is a comprehensive validation of the simulation program PCSiWaPro registered (developed at the TU-Dresden, Institute of Waste Management and Contaminated Site Treatment) for different applications. Another aim of this work is to investigate the applicability of the current version of PCSiWaPro registered for different cases of a combination between the unsaturated zone and technical facilities. Four application cases with different objectives were investigated within the present work, which are: the simulation of decentralized wastewater infiltration with corresponding column and field experiments, the computation of groundwater recharge by means of lysimeters, the water balance of earth dams and the modelling of landfill covering systems. The application cases differ from each other by the objective of the simulation, the geometry, the size, the specified initial and boundary conditions, the simulation time, the applied materials, the coordinate system, the input and output data. The simulation results clearly showed that PCSiWaPro registered is applicable for all investigated cases under consideration of different flow and solute transport regimes, parameters

Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species; Chimie de l'uranium (VI) a l'interface solution/mineraux (quartz et hydroxyde d'aluminium): experiences et caracterisations spectroscopiques

Energy Technology Data Exchange (ETDEWEB)

Froideval, A.

2004-09-15

This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO{sub 3} solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 {mu}mol/m{sup 2}) to high (26 {mu}mol/m{sup 2}) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range {approx_equal} 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 {mu}M). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 {mu}mol/m{sup 2}). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

Uranium (VI) chemistry at the interface solution/minerals (quartz and aluminium hydroxide): experiments and spectroscopic investigations of the uranyl surface species

International Nuclear Information System (INIS)

Froideval, A.

2004-09-01

This study deals with the understanding of the uranyl chemistry at the 0.1 M NaNO 3 solution/mineral (quartz and aluminium hydroxide) interface. The aims are:(i) to identify and to characterize the different uranyl surface species (mononuclear, polynuclear complexes and/or precipitates...), i.e. the coordination environments of sorbed/precipitated uranyl ions, by using X-ray photoelectron spectroscopy (XPS), extended X-ray absorption fine structure (EXAFS) and time-resolved laser-induced fluorescence spectroscopy (TRLFS), and;(ii) to investigate the influence of pH, initial uranyl aqueous concentration and hydroxyl ligand concentration on the uranyl surface speciation. Our study on the speciation of uranyl ions at the quartz surface (i) confirms the formation of uranyl polynuclear/oligomers on quartz from moderate (1 μmol/m 2 ) to high (26 μmol/m 2 ) uranyl surface concentrations and (ii) show that theses polynuclear species coexist with uranyl mononuclear surface species over a pH range ≅ 5-8.5 and a wide range of initial uranyl concentration o f the solutions (10-100 μM). The uranyl concentration of these surface species depends on pH and on the initial uranyl aqueous concentration. Hydrate (surface-) precipitates and/or adsorbed polynuclear species and monomeric uranyl surface complexes are formed on aluminium hydroxide. Uranyl mononuclear complexes are predominant at acidic pH, as well as uranyl in solution or on the surface. Besides mononuclear species, precipitates and/or adsorbed polynuclear species are predominantly formed at neutral pH values on aluminium hydroxide. A main contribution of our investigations is that precipitation and/or adsorption of polynuclear species seem to occur at low uranyl surface concentrations (0.01-0.4 μmol/m 2 ). The uranyl surface speciation is mainly dependent on the pH and the aluminol ligand concentration. (author)

Unsaturated Zone Effects in Predicting Landslide and Debris-Flow Initiation

Science.gov (United States)

Baum, R. L.; Godt, J. W.; Savage, W. Z.

2006-12-01

Many destructive debris flows begin as shallow landslides induced by direct infiltration of intense rainfall and storm runoff into hillside materials. Predicting the timing and location of debris-flow initiation is needed to assess the debris-flow hazard of an area. Theoretical models and real-time monitoring of rainfall infiltration into unsaturated hillside materials provide useful insights into the mechanisms and timing of rainfall-induced landslides. We modeled the infiltration process using a two-layer system that consists of an unsaturated zone above a saturated zone, and then implemented this model in a GIS framework. The model couples analytical solutions for transient, unsaturated, vertical infiltration above the water table to pressure-diffusion solutions for pressure changes below the water table. The solutions are coupled through a transient water table that rises as water accumulates at the base of the unsaturated zone. This scheme, though limited to simplified soil- water characteristics and moist initial conditions, greatly improves computational efficiency over numerical models in spatially distributed modeling applications. Pore pressures computed by these coupled models are subsequently used in slope-stability computations to estimate the timing and locations of slope failures. Preliminary model results indicate that the unsaturated layer attenuates and delays the rainfall-induced pore- pressure response at depth, consistent with observations at an instrumented hillside near Edmonds, Washington. This attenuation reduces the area of false-positive predictions (when compared with results of linear models for suction-saturated initial conditions) in distributed application of the model over an area. Modeling indicates that initial wetness of the hillside materials affects the intensity and duration of rainfall required to trigger shallow landslides and consequently the timing of their occurrence, a result that is also consistent with observations of

Effects of Unsaturated Zones on Baseflow Recession: Analytical Solution and Application

Science.gov (United States)

Zhan, H.; Liang, X.; Zhang, Y. K.

2017-12-01

Unsaturated flow is an important process in baseflow recessions and its effect is rarely investigated. A mathematical model for a coupled unsaturated-saturated flow in a horizontally unconfined aquifer with time-dependent infiltrations is presented. Semi-analytical solutions for hydraulic heads and discharges are derived using Laplace transform and Cosine transform. The solutions are compared with solutions of the linearized Boussinesq equation (LB solution) and the linearized Laplace equation (LL solution), respectively. The result indicates that a larger dimensionless constitutive exponent κD of the unsaturated zone leads to a smaller discharge during the infiltration period and a larger discharge after the infiltration. The lateral discharge of the unsaturated zone is significant when κD≤1, and becomes negligible when κD≥100. For late times, the power index b of the recession curve-dQ/dt aQb, is 1 and independent of κD, where Q is the baseflow and a is a constant lumped aquifer parameter. For early times, b is approximately equal to 3 but it approaches infinity when t→1. The present solution is applied to synthetic and field cases. The present solution matched the synthetic data better than both the LL and LB solutions, with a minimum relative error of 16% for estimate of hydraulic conductivity. The present solution was applied to the observed streamflow discharge in Iowa, and the estimated values of the aquifer parameters were reasonable.

Characterization of unsaturated hydraulic parameters for homogeneous and heterogeneous soils

Energy Technology Data Exchange (ETDEWEB)

Wildenschild, Dorthe

1997-09-01

Application of numerical models for predicting future spreading of contaminants into ground water aquifers is dependent on appropriate characterization of the soil hydraulic properties controlling flow and transport in the unsaturated zone. This thesis reviews the current knowledge on two aspects of characterization of unsaturated hydraulic parameters; estimation of the basic hydraulic parameters for homogeneous soils and statistical representation of heterogeneity for spatially variable soils. The retention characteristic is traditionally measured using steady-state procedures, but new ideas based on dynamic techniques have been developed that reduce experimental efforts and that produce retention curves which compare to those measured by traditional techniques. The unsaturated hydraulic conductivity is difficult to establish by steady-state procedures, and extensive research efforts have been focused on alternative methods that are based on inverse estimation. The inverse methods have commonly been associated with problems of numerical instability and ill-posedness of the parameter estimates, but recent investigations have shown that the uniqueness of parameter estimates can be improved by including additional, independent information on, for instance, the retention characteristic. Also, uniqueness may be improved by careful selection of experimental conditions are parametric functions. (au) 234 refs.

A study on in-situ measuring method and modeling technique of an unsaturated zone

Energy Technology Data Exchange (ETDEWEB)

Imai, Hisashi [Hazama Corp., Tsukuba, Ibaraki (Japan). Technical Research Inst.; Amemiya, Kiyoshi; Nishida, Kaoru; Lin, Weiren; Lei, Xinglin

1997-03-01

It is generally considered that an unsaturated zone is generated in the vicinity of a drift after excavation. In such a zone, invasion of air containing oxygen possibly changes geochemical environment (redox condition) of the rock mass. However, no measurement technique for quantitative understanding of this unsaturated zone is currently available. This study has been started to develop the measuring method in the several years. This year, fundamental information has been obtained through analysis, laboratory experiments using homogeneous rock samples and field measurement described below. (1) experiments on the mechanism of undersaturation in rock. (2) experiments on the measuring method of the extend of unsaturated zone. (author)

36Cl measurements of the unsaturated zone flux at Yucca Mountain

International Nuclear Information System (INIS)

Norris, A.E.; Wolfsberg, K.; Gifford, S.K.

1985-01-01

Determining the unsaturated zone percolation rate, or flux, is an extremely important site characterization issue for the proposed Yucca Mountain nuclear waste repository. A new technique that measures the 36 Cl content of tuff from the Exploratory Shaft will be used to calculate flux through the unsaturated zone over longer times than could be measured by the more conventional 14 C method. Measurements of the 36 Cl ''bomb pulse'' in soil samples from Yucca Mountain have been used to confirm that infiltration is not an important recharge mechanism. 5 refs., 3 figs

Gas breakthrough and emission through unsaturated compacted clay in landfill final cover

International Nuclear Information System (INIS)

Ng, C.W.W.; Chen, Z.K.; Coo, J.L.; Chen, R.; Zhou, C.

2015-01-01

Highlights: • Explore feasibility of unsaturated clay as a gas barrier in landfill cover. • Gas breakthrough pressure increases with clay thickness and degree of saturation. • Gas emission rate decreases with clay thickness and degree of saturation. • A 0.6 m-thick clay layer may be sufficient to meet gas emission rate limit. - Abstract: Determination of gas transport parameters in compacted clay plays a vital role for evaluating the effectiveness of soil barriers. The gas breakthrough pressure has been widely studied for saturated swelling clay buffer commonly used in high-level radioactive waste disposal facility where the generated gas pressure is very high (in the order of MPa). However, compacted clay in landfill cover is usually unsaturated and the generated landfill gas pressure is normally low (typically less than 10 kPa). Furthermore, effects of clay thickness and degree of saturation on gas breakthrough and emission rate in the context of unsaturated landfill cover has not been quantitatively investigated in previous studies. The feasibility of using unsaturated compacted clay as gas barrier in landfill covers is thus worthwhile to be explored over a wide range of landfill gas pressures under various degrees of saturation and clay thicknesses. In this study, to evaluate the effectiveness of unsaturated compacted clay to minimize gas emission, one-dimensional soil column tests were carried out on unsaturated compacted clay to determine gas breakthrough pressures at ultimate limit state (high pressure range) and gas emission rates at serviceability limit state (low pressure range). Various degrees of saturation and thicknesses of unsaturated clay sample were considered. Moreover, numerical simulations were carried out using a coupled gas–water flow finite element program (CODE-BRIGHT) to better understand the experimental results by extending the clay thickness and varying the degree of saturation to a broader range that is typical at different

Gas breakthrough and emission through unsaturated compacted clay in landfill final cover

Energy Technology Data Exchange (ETDEWEB)

Ng, C.W.W.; Chen, Z.K.; Coo, J.L. [Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong); Chen, R., E-mail: chenrui1005@hotmail.com [Shenzhen Key Laboratory of Urban and Civil Engineering for Disaster Prevention and Mitigation, Harbin Institute of Technology Shenzhen Graduate School, Shenzhen 518055 (China); Zhou, C. [Department of Civil and Environmental Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon (Hong Kong)

2015-10-15

Highlights: • Explore feasibility of unsaturated clay as a gas barrier in landfill cover. • Gas breakthrough pressure increases with clay thickness and degree of saturation. • Gas emission rate decreases with clay thickness and degree of saturation. • A 0.6 m-thick clay layer may be sufficient to meet gas emission rate limit. - Abstract: Determination of gas transport parameters in compacted clay plays a vital role for evaluating the effectiveness of soil barriers. The gas breakthrough pressure has been widely studied for saturated swelling clay buffer commonly used in high-level radioactive waste disposal facility where the generated gas pressure is very high (in the order of MPa). However, compacted clay in landfill cover is usually unsaturated and the generated landfill gas pressure is normally low (typically less than 10 kPa). Furthermore, effects of clay thickness and degree of saturation on gas breakthrough and emission rate in the context of unsaturated landfill cover has not been quantitatively investigated in previous studies. The feasibility of using unsaturated compacted clay as gas barrier in landfill covers is thus worthwhile to be explored over a wide range of landfill gas pressures under various degrees of saturation and clay thicknesses. In this study, to evaluate the effectiveness of unsaturated compacted clay to minimize gas emission, one-dimensional soil column tests were carried out on unsaturated compacted clay to determine gas breakthrough pressures at ultimate limit state (high pressure range) and gas emission rates at serviceability limit state (low pressure range). Various degrees of saturation and thicknesses of unsaturated clay sample were considered. Moreover, numerical simulations were carried out using a coupled gas–water flow finite element program (CODE-BRIGHT) to better understand the experimental results by extending the clay thickness and varying the degree of saturation to a broader range that is typical at different

Aquifer Recharge Estimation In Unsaturated Porous Rock Using Darcian And Geophysical Methods.

Science.gov (United States)

Nimmo, J. R.; De Carlo, L.; Masciale, R.; Turturro, A. C.; Perkins, K. S.; Caputo, M. C.

2016-12-01

Within the unsaturated zone a constant downward gravity-driven flux of water commonly exists at depths ranging from a few meters to tens of meters depending on climate, medium, and vegetation. In this case a steady-state application of Darcy's law can provide recharge rate estimates.We have applied an integrated approach that combines field geophysical measurements with laboratory hydraulic property measurements on core samples to produce accurate estimates of steady-state aquifer recharge, or, in cases where episodic recharge also occurs, the steady component of recharge. The method requires (1) measurement of the water content existing in the deep unsaturated zone at the location of a core sample retrieved for lab measurements, and (2) measurement of the core sample's unsaturated hydraulic conductivity over a range of water content that includes the value measured in situ. Both types of measurements must be done with high accuracy. Darcy's law applied with the measured unsaturated hydraulic conductivity and gravitational driving force provides recharge estimates.Aquifer recharge was estimated using Darcian and geophysical methods at a deep porous rock (calcarenite) experimental site in Canosa, southern Italy. Electrical Resistivity Tomography (ERT) and Vertical Electrical Sounding (VES) profiles were collected from the land surface to water table to provide data for Darcian recharge estimation. Volumetric water content was estimated from resistivity profiles using a laboratory-derived calibration function based on Archie's law for rock samples from the experimental site, where electrical conductivity of the rock was related to the porosity and water saturation. Multiple-depth core samples were evaluated using the Quasi-Steady Centrifuge (QSC) method to obtain hydraulic conductivity (K), matric potential (ψ), and water content (θ) estimates within this profile. Laboratory-determined unsaturated hydraulic conductivity ranged from 3.90 x 10-9 to 1.02 x 10-5 m

Role of unsaturated soil in a waste containment system

Energy Technology Data Exchange (ETDEWEB)

Lim, P.C.; Tay, J.H. [Nanyang Technological Univ. (Singapore)

1996-12-31

The role of the unsaturated properties of sand as a drainage layer in a composite liner system for landfills is investigated. The effect of the unsaturated properties of coarse-grained soil on contaminant migration was evaluated by means of a series of simulations using a one-dimensional model of a two- and a three-layer soil liner system for advection and diffusion, respectively. The results showed that under seepage conditions, the effect of an unsaturated sand layer on the advancement of the concentration front was quite insignificant. The arrival time of the C/C{sub o} = 0.5 concentration front increased from 651 days for the case with no sand layer to approximately 951 days for the case with a 1.0-m sand layer. A steady-state flow condition was ultimately established in the sand, and this fact suggests that the capillary action might not be effective. For diffusion, the arrival time of the concentration front increased nonlinearly with a decrease in the degree of saturation and linearly with increasing depths of the sand layer. At a residual degree of saturation, the arrival times of the C/C{sub o} = 0.01 and 0.5 concentration front at the base of the 1-m sand layer were 26.9 and 877.4 years as compared to 1.52 and 2.62 years by advection, respectively. 17 refs., 11 figs.

Discrete Element Method for Modeling the Mechanical Behavior of Unsaturated Granular Material

Directory of Open Access Journals (Sweden)

K. Tourani

2016-09-01

Full Text Available Although a significant portion of conditions encountered in geotechnical engineering, for investigating engineering behavior of soil, involves unsaturated soils; the traditional analysis and design approach has been to assume the limiting conditions of soils being either completely dry or completely saturated. In unsaturated soils the capillary force produce attractive forces between particles. Discrete Element Method (DEM is an appropriate tool to consider the capillary effects. The calculations performed in DEM is based on iterative application of Newton’s second law to the particles and force-displacement law at the contacts. In the present study, the behavior of unsaturated soils in pendular regime is simulated utilizing DEM. Triaxial  compression tests were modeled as two-dimensional, considering capillary force effects. Finally, capillary effects on Macro parameters of a simulated granular soil (stress, axial strain, volumetric strain and void ratio and Mohr Coulomb failure criteria parameters were studied.

Geologic character of tuffs in the unsaturated zone at Yucca Mountain, southern Nevada

International Nuclear Information System (INIS)

Scott, R.B.; Spengler, R.W.; Diehl, S.; Lappin, A.R.; Chornack, M.P.

1982-01-01

At Yucca Mountain, a potential site for a high-level nuclear waste repository on the Nevada Test Site in southern Nevada, evaluation of the geologic setting and rock physical properties, along with previous regional hydrologic studies, has provided background that can be used for construction of a preliminary conceptual hydrologic model of the unsaturated zone. The 500-m-thick unsaturated portion of Yucca Mountain consists of alternating layers of two contrasting types of tuff. One type consists of highly fractured, densely welded, relatively nonporous but highly transmissive ash-flow tuffs. The other type consists of relatively unfractured, nonwelded, highly porous but relatively nontransmissive, argillic and zeolitic bedded tuffs and ash-flow tuffs. The contrast between these two sets of distinctive physical properties results in a stratified sequence best described as ''physical-property stratigraphy'' as opposed to traditional petrologic stratigraphy of volcanic rocks. The vast majority of recharge through the unsaturated zone is assumed to be vertical; the dominant migration may occur in fractures of densely welded tuffs and in the matrix of nonwelded tuff, but the mode of fluid flow in these unsaturated systems is undetermined. Limited lateral flow of recharge may occur at horizons where local perched water tables may exist above relatively nontransmissive zeolitized nonwelded tuffs. The pervasive north-northwest-striking fractures may control the direction of lateral flow of recharge, if any, in the unsaturated zone, and certainly that direction coincides closely with the observed southeasterly flow direction in the saturated zone under Yucca Mountain. Empirical evaluation of this conceptual hydrologic model has begun. 41 refs., 18 figs., 2 tabs

Geologic character of tuffs in the unsaturated zone at Yucca Mountain, southern Nevada

Energy Technology Data Exchange (ETDEWEB)

Scott, R.B.; Spengler, R.W.; Diehl, S.; Lappin, A.R.; Chornack, M.P.

1982-12-31

At Yucca Mountain, a potential site for a high-level nuclear waste repository on the Nevada Test Site in southern Nevada, evaluation of the geologic setting and rock physical properties, along with previous regional hydrologic studies, has provided background that can be used for construction of a preliminary conceptual hydrologic model of the unsaturated zone. The 500-m-thick unsaturated portion of Yucca Mountain consists of alternating layers of two contrasting types of tuff. One type consists of highly fractured, densely welded, relatively nonporous but highly transmissive ash-flow tuffs. The other type consists of relatively unfractured, nonwelded, highly porous but relatively nontransmissive, argillic and zeolitic bedded tuffs and ash-flow tuffs. The contrast between these two sets of distinctive physical properties results in a stratified sequence best described as "physical-property stratigraphy" as opposed to traditional petrologic stratigraphy of volcanic rocks. The vast majority of recharge through the unsaturated zone is assumed to be vertical; the dominant migration may occur in fractures of densely welded tuffs and in the matrix of nonwelded tuff, but the mode of fluid flow in these unsaturated systems is undetermined. Limited lateral flow of recharge may occur at horizons where local perched water tables may exist above relatively nontransmissive zeolitized nonwelded tuffs. The pervasive north-northwest-striking fractures may control the direction of lateral flow of recharge, if any, in the unsaturated zone, and certainly that direction coincides closely with the observed southeasterly flow direction in the saturated zone under Yucca Mountain. Empirical evaluation of this conceptual hydrologic model has begun. 41 refs., 18 figs., 2 tabs.

Conceptual hydrologic model of flow in the unsaturated zone, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Montazer, P.; Wilson, W.E.

1984-01-01

The purpose of this report is to propose a conceptual hydrologic model that reasonably describes the flow of fluids through the unsaturated zone at Yucca Mountain, for use as a basis for preliminary site-performance assessment and as a guide to further investigations. Scott and others (1983) presented an initial conceptual hydrogeologic model for the unsaturated zone at Yucca Mountain, based on detailed geologic, but very limited hydrologic, information. In this report, some of their concepts are examined and either supported or modified, and new concepts are developed. The model describes the manner in which flow probably occurs at Yucca Mountain and is based on: (1) current understanding of the hydrogeologic framework; (2) application of the principles of unsaturated flow; and (3) interpretation of some preliminary data from ongoing field and laboratory investigations. Included are extensive geologic information but relatively few hydrologic data that currently exist from the unsaturated zone in the Yucca Mountain area. Many uncertainties remain to be resolved concerning hydrologic conditions and processes. As a result, most of the concepts presented are intentionally descriptive and conjectural, with little quantitative basis provided. However, for the sake of directness and simplicity of expression, the model is presented as if it were a true expression of the facts. The authors recognize, and the reader should be aware, that the proposed model probably is not the only reasonable description that could be made at this point, and it certainly is subject to revision and quantification as more data become available. Although various alternative models probably could be developed, the one described in this report seems to fit current understanding of the unsaturated flow through a section of layered, fractured-rock formations with contrasting hydrologic properties, such as occurs at Yucca Mountain. 41 refs., 14 figs., 1 tab

Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides.

Science.gov (United States)

Hoang, G L; Zhang, S; Takacs, J M

2018-05-08

γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal in the sense of π-facial selectivity.

Application of Stochastic Unsaturated Flow Theory, Numerical Simulations, and Comparisons to Field Observations

DEFF Research Database (Denmark)

Jensen, Karsten Høgh; Mantoglou, Aristotelis

1992-01-01

unsaturated flow equation representing the mean system behavior is solved using a finite difference numerical solution technique. The effective parameters are evaluated from the stochastic theory formulas before entering them into the numerical solution for each iteration. The stochastic model is applied...... seems to offer a rational framework for modeling large-scale unsaturated flow and estimating areal averages of soil-hydrological processes in spatially variable soils....

Uranium Sequestration by Aluminum Phosphate Minerals in Unsaturated Soils

International Nuclear Information System (INIS)

Jerden, James L. Jr.

2007-01-01

A mineralogical and geochemical study of soils developed from the unmined Coles Hill uranium deposit (Virginia) was undertaken to determine how phosphorous influences the speciation of uranium in an oxidizing soil/saprolite system typical of the eastern United States. This paper presents mineralogical and geochemical results that identify and quantify the processes by which uranium has been sequestered in these soils. It was found that uranium is not leached from the saturated soil zone (saprolites) overlying the deposit due to the formation of a sparingly soluble uranyl phosphate mineral of the meta-autunite group. The concentration of uranium in the saprolites is approximately 1000 mg uranium per kg of saprolite. It was also found that a significant amount of uranium was retained in the unsaturated soil zone overlying uranium-rich saprolites. The uranium concentration in the unsaturated soils is approximately 200 mg uranium per kg of soil (20 times higher than uranium concentrations in similar soils adjacent to the deposit). Mineralogical evidence indicates that uranium in this zone is sequestered by a barium-strontium-calcium aluminum phosphate mineral of the crandallite group (gorceixite). This mineral is intimately inter-grown with iron and manganese oxides that also contain uranium. The amount of uranium associated with both the aluminum phosphates (as much as 1.4 weight percent) has been measured by electron microprobe micro-analyses and the geochemical conditions under which these minerals formed has been studied using thermodynamic reaction path modeling. The geochemical data and modeling results suggest the meta-autunite group minerals present in the saprolites overlying the deposit are unstable in the unsaturated zone soils overlying the deposit due to a decrease in soil pH (down to a pH of 4.5) at depths less than 5 meters below the surface. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group

Focused Flow During Infiltration Into Ethanol-Contaminated Unsaturated Porous Media

Science.gov (United States)

Jazwiec, A.; Smith, J. E.

2017-12-01

The increasing commercial and industrial use of ethanol, e.g. in biofuels, has generated increased incidents of vadose zone contamination by way of ethanol spills and releases. This has increased the interest in better understanding behaviors of ethanol in unsaturated porous media and it's multiphase interactions in the vadose zone. This study uses highly controlled laboratory experiments in a 2-D (0.6mx0.6mx0.01m) flow cell to investigate water infiltration behaviors into ethanol-contaminated porous media. Ethanol and water were applied by either constant head or constant flux methods onto the surface of sands homogenously packed into the flow cell. The constant flux experiments at both low and high application rates were conducted using a rainulator with a row of hypodermic needles connected to a peristaltic pump. The constant head experiments were conducted using an 8cm diameter tension disk infiltrometer set to both low and high tensions. The presence of ethanol contamination generated solute-dependent capillarity induced focused flow (SCIFF) of water infiltration, which was primarily due to decreases in interfacial tensions at the air-liquid interfaces in the unsaturated sands as a function of ethanol concentration. SCIFF was clearly expressed as an unsaturated water flow phenomenon comprised of narrowly focused vertical flow fingers of water within the initially ethanol contaminated porous media. Using analyses of photos and video, comparisons were made between constant flux and constant head application methods. Further comparisons were made between low and high infiltration rates and the two sand textures used. A high degree of sensitivity to minor heterogeneity in relatively homogeneous sands was also observed. The results of this research have implications for rainfall infiltration into ethanol contaminated vadose zones expressing SCIFF, including implications for associated mass fluxes and the nature of flushing of ethanol from the unsaturated zone to

Hydrochemical investigations in characterizing the unsaturated zone at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Yang, I.C.; Rattray, G.W.; Ferarese, J.S.; Yu, P.; Ryan, J.N.

1998-01-01

Hydrochemical and isotopic investigations of ground water at Yucca Mountain, Nevada, site of a potential permanent national nuclear-waste repository, demonstrate that younger rocks are dominated by calcium-sulfate or calcium-chloride water and that older rocks contain sodium-carbonate or sodium-bicarbonate water. Furthermore, unsaturated-zone pore water has significantly larger concentrations of major ions and dissolved solids than does the saturated-zone water. Recharge of perched or saturated-zone water, therefore, requires rapid flow through fractures or permeable regions in the unsaturated zone to avoid mixing with the chemically concentrated water in the unsaturated zone. This conceptual model is consistent with observations of rapidly moved post-bomb (post-1954) tritium and chlorine-36 in the deep unsaturated zone at Yucca Mountain. Presence of post-bomb tritium in matrix water away from fracture zones further indicates that parts of the fast-flow water that moves through fractures have been diverted laterally into nonwelded units. Experimental data show that different lithologic units require specific water-extraction methods for stable-isotope analyses of hydrogen and oxygen to ensure accurate characterization. Vacuum-distillation and compression-extraction methods both can yield accurate data but must be used with specific lithologies. Column experiments demonstrate that percolating water can exchange with pore water of the core as well as water held in zeolite minerals in the core. Exchange rates range from days to months. Pore-water samples from core, therefore, reflect the most recently infiltrated water but do not reflect percolating water of the distant past

Fe-Catalyzed Oxidative Cleavage of Unsaturated Fatty Acids

NARCIS (Netherlands)

Spannring, P.

2013-01-01

The oxidative cleavage of unsaturated fatty acids into aldehydes or carboxylic acids gives access to valuable products. The products can be used as chemical building blocks, as emulsifiers or in the paint or polymer industry. Ozonolysis is applied industrially to cleave the fatty acid oleic acid

Quasi‐steady centrifuge method for unsaturated hydraulic properties

Science.gov (United States)

Caputo, Maria C.; Nimmo, John R.

2005-01-01

We have developed the quasi‐steady centrifuge (QSC) method as a variation of the steady state centrifuge method that can be implemented simply and inexpensively with greater versatility in terms of sample size and other features. It achieves these advantages by somewhat relaxing the criterion for steadiness of flow through the sample. This compromise entails an increase in measurement uncertainty but to a degree that is tolerable in most applications. We have tested this new approach with an easily constructed apparatus to establish a quasi‐steady flow of water in unsaturated porous rock samples spinning in a centrifuge, obtaining measurements of unsaturated hydraulic conductivity and water retention that agree with results of other methods. The QSC method is adaptable to essentially any centrifuge suitable for hydrogeologic applications, over a wide range of sizes and operating speeds. The simplified apparatus and greater adaptability of this method expands the potential for exploring situations that are common in nature but have been the subject of few laboratory investigations.

Quasi-steady centrifuge method for unsaturated hydraulic properties

Science.gov (United States)

Caputo, Maria C.; Nimmo, John R.

2005-11-01

We have developed the quasi-steady centrifuge (QSC) method as a variation of the steady state centrifuge method that can be implemented simply and inexpensively with greater versatility in terms of sample size and other features. It achieves these advantages by somewhat relaxing the criterion for steadiness of flow through the sample. This compromise entails an increase in measurement uncertainty but to a degree that is tolerable in most applications. We have tested this new approach with an easily constructed apparatus to establish a quasi-steady flow of water in unsaturated porous rock samples spinning in a centrifuge, obtaining measurements of unsaturated hydraulic conductivity and water retention that agree with results of other methods. The QSC method is adaptable to essentially any centrifuge suitable for hydrogeologic applications, over a wide range of sizes and operating speeds. The simplified apparatus and greater adaptability of this method expands the potential for exploring situations that are common in nature but have been the subject of few laboratory investigations.

Thermal conductivity measurements in unsaturated hydrate-bearing sediments

Science.gov (United States)

Dai, Sheng; Cha, Jong-Ho; Rosenbaum, Eilis J.; Zhang, Wu; Seol, Yongkoo

2015-08-01

Current database on the thermal properties of hydrate-bearing sediments remains limited and has not been able to capture their consequential changes during gas production where vigorous phase changes occur in this unsaturated system. This study uses the transient plane source (TPS) technique to measure the thermal conductivity of methane hydrate-bearing sediments with various hydrate/water/gas saturations. We propose a simplified method to obtain thermal properties from single-sided TPS signatures. Results reveal that both volume fraction and distribution of the pore constituents govern the thermal conductivity of unsaturated specimens. Thermal conductivity hysteresis is observed due to water redistribution and fabric change caused by hydrate formation and dissociation. Measured thermal conductivity increases evidently when hydrate saturation Sh > 30-40%, shifting upward from the geometric mean model prediction to a Pythagorean mixing model. These observations envisage a significant drop in sediment thermal conductivity when residual hydrate/water saturation falls below ~40%, hindering further gas production.

Simulation of groundwater flows in unsaturated porous media

International Nuclear Information System (INIS)

Musy, A.

1976-01-01

Groundwater flow in unsaturated porous media is caused by a potential gradient where the total potential consists of the sum of a gravitational and a suction component. The partial differential equations which result from the general analysis of groundwater flow in unsaturated soil are solved by succesive approximations with the finite-element method. General boundary and initial conditions, linear or curvilinear shaped elements (isoparametric elements) and steady-state or transient flow can be introduced into the numerical computer program. The results of this mathematical model are compared with experimental data established in the laboratory with a physical groundwater model. This is a rectangular testing tank of dimension 3 x 1.5 x 0.15 m and contains a silty clay loam. The variation of the bulk density and the volumetric moisture of the soil as a function of time and space are measured by gamma absorption from a 137 Cs source with 300 mCi intensity

The use of polynuclear aromatic hydrocarbon (PAH) alkyl homologues in determining petroleum source identification and weathering

International Nuclear Information System (INIS)

Brown, J.S.; Boehm, P.D.; Sauer, T.C.; Wong, W.M.C.

1993-01-01

Techniques utilizing double ratio plots of selected polynuclear aromatic hydrocarbon (PAH) alkyl homologues were used to identify and distinguish crude oils and refined petroleum products from each other and to distinguish petroleum sources in complex pollutant regimes. Petroleum samples were fractionated by high performance liquid chromatography (HPLC) into saturated and aromatic (PAH) hydrocarbon fractions. The saturated hydrocarbon fractions were then analyzed by gas chromatography/flame ionization detection (GC/FID) to obtain a resolved/unresolved alkane fingerprint of each oil. The aromatic fractions of the oils were analyzed by gas chromatography/mass spectrometry (GC/MS) for PAH and selected alkyl homologues. Comparisons of the saturated hydrocarbon fingerprints indicated that some oils were indistinguishable based on the alkane fingerprint alone. Another double ratio plot of the alkyl chrysenes and alkyl dibenzothiophenes was effective in establishing the weathering of oil in environmental samples which were processed using the same analytical techniques, since the dibenzothiophenes are degraded more rapidly than the chrysenes. The application of selected ratios in oil spill source identification in complex environmental samples from Suisin Bay California and Boston Harbor are discussed. The use of ratios to measure the extent of weathering in oil spill samples from Prince William Sound and the Gulf of Alaska is examined

Unsaturated Fatty Acids Supplementation Reduces Blood Lead Level in Rats

Science.gov (United States)

Skoczyńska, Anna; Wojakowska, Anna; Nowacki, Dorian; Bobak, Łukasz; Turczyn, Barbara; Smyk, Beata; Szuba, Andrzej; Trziszka, Tadeusz

2015-01-01

Some dietary factors could inhibit lead toxicity. The aim of this study was to evaluate the effect of dietary compounds rich in unsaturated fatty acids (FA) on blood lead level, lipid metabolism, and vascular reactivity in rats. Serum metallothionein and organs' lead level were evaluated with the aim of assessing the possible mechanism of unsaturated FA impact on blood lead level. For three months, male Wistar rats that were receiving drinking water with (100 ppm Pb) or without lead acetate were supplemented per os daily with virgin olive oil or linseed oil (0.2 mL/kg b.w.) or egg derived lecithin fraction: “super lecithin” (50 g/kg b.w.). Mesenteric artery was stimulated ex vivo by norepinephrine (NE) administered at six different doses. Lecithin supplementation slightly reduced pressor responses of artery to NE. Lead administered to rats attenuated the beneficial effect of unsaturated FA on lipid metabolism and vascular reactivity to adrenergic stimulation. On the other hand, the super lecithin and linseed oil that were characterized by low omega-6 to omega-3 ratio (about 1) reduced the blood lead concentration. This effect was observed in lead poisoned rats (p < 0.0001) and also in rats nonpoisoned with lead (p < 0.05). PMID:26075218

Visualization of microscale phase displacement proceses in retention and outflow experiments: nonuniquensess of unsaturated flow properties

DEFF Research Database (Denmark)

Mortensen, Annette Pia; Glass, R.J.; Hollenbeck, K.J.

2001-01-01

-scale heterogeneities. Because the mixture of these microscale processes yields macroscale effective behavior, measured unsaturated flow properties are also a function of these controls. Such results suggest limitations on the current definitions and uniqueness of unsaturated hydraulic properties....

Damping Effect of an Unsaturated-Saturated System on Tempospatial Variations of Pressure Head and Specific Flux

Science.gov (United States)

Yang, C.; Zhang, Y. K.; Liang, X.

2014-12-01

Damping effect of an unsaturated-saturated system on tempospatialvariations of pressurehead and specificflux was investigated. The variance and covariance of both pressure head and specific flux in such a system due to a white noise infiltration were obtained by solving the moment equations of water flow in the system and verified with Monte Carlo simulations. It was found that both the pressure head and specific flux in this case are temporally non-stationary. The variance is zero at early time due to a deterministic initial condition used, then increases with time, and approaches anasymptotic limit at late time.Both pressure head and specific flux arealso non-stationary in space since the variance decreases from source to sink. The unsaturated-saturated systembehavesasa noise filterand it damps both the pressure head and specific flux, i.e., reduces their variations and enhances their correlation. The effect is stronger in upper unsaturated zone than in lower unsaturated zone and saturated zone. As a noise filter, the unsaturated-saturated system is mainly a low pass filter, filtering out the high frequency components in the time series of hydrological variables. The damping effect is much stronger in the saturated zone than in the saturated zone.

A mountain-scale model for characterizing unsaturated flow and transport in fractured tuffs of Yucca Mountain

International Nuclear Information System (INIS)

Wu, Yu-Shu; Lu, Guoping; Zhang, Keni; Bodvarsson, G.S.

2003-01-01

This paper presents a large-scale modeling study characterizing fluid flow and tracer transport in the unsaturated zone of Yucca Mountain, Nevada, the proposed underground repository site for storing high-level radioactive waste. The modeling study is conducted using a three-dimensional numerical model, which incorporates a wide variety of field data and takes into account the coupled processes of flow and transport in Yucca Mountain's highly heterogeneous, unsaturated, fractured porous rock. The modeling approach is based on a dual-continuum formulation. Using different conceptual models of unsaturated flow, various scenarios of current and future climate conditions and their effects on the unsaturated zone are evaluated to aid in the assessment of the repository's system performance. These models are calibrated against field-measured data. Model-predicted flow and transport processes under current and future climates are discussed

Introduction of damage in an elasto-plastic model for unsaturated geo-materials

International Nuclear Information System (INIS)

Le Pense, S.; Pouya, A.; Gatmiri, B.

2012-01-01

Document available in extended abstract form only. During the excavation of nuclear waste repository galleries, the surrounding soil is suspected to undergo structural changes as well as modification of its stress state. The desaturation due to ventilation of galleries during this stage makes it necessary to consider the unsaturated state of the host geo-material. The decompression occurring after the excavation leads to a modification of the stress state. The purpose of our work is to develop a mechanical model to simulate the non-linear stress-strain behaviour of geo-materials which will have to contain radioactivity of nuclear waste for a very long time. Two irreversible phenomena can explain the non-linear behaviour of geo-materials. Plasticity leads to irrecoverable strains. Damage, linked to the appearance and extension of microcracks, results in a deterioration of elastic and hydraulic properties. We will present here the bases of a new model coupling damage and plasticity for the stress-strain behaviour of unsaturated geo-materials. This model should be thermodynamically consistent and use only a reasonable number of parameters. Based on the work of Houlsby, (Houlsby 1997), we choose to use as constitutive variables for unsaturated soils Bishop's stress and suction. This choice as the advantage to allow for continuity at the transition between saturated and unsaturated states. Damage is taken into account by defining a damaged constitutive stress, which is similar to the effective stress principle defined by Kachanov (Kachanov 1958). A simple damage criterion is proposed and an associative flow rule is assumed. We choose to follow the principle of strain equivalence defined by Lemaitre (Lemaitre 1996). This leads to the following elasticity law giving the damaged constitutive stress as a function of elastic strain. If non-linear elasticity is considered, a pressure-dependent bulk modulus and a constant shear modulus can be chosen in order to fit

Modeling field scale unsaturated flow and transport processes

International Nuclear Information System (INIS)

Gelhar, L.W.; Celia, M.A.; McLaughlin, D.

1994-08-01

The scales of concern in subsurface transport of contaminants from low-level radioactive waste disposal facilities are in the range of 1 to 1,000 m. Natural geologic materials generally show very substantial spatial variability in hydraulic properties over this range of scales. Such heterogeneity can significantly influence the migration of contaminants. It is also envisioned that complex earth structures will be constructed to isolate the waste and minimize infiltration of water into the facility. The flow of water and gases through such facilities must also be a concern. A stochastic theory describing unsaturated flow and contamination transport in naturally heterogeneous soils has been enhanced by adopting a more realistic characterization of soil variability. The enhanced theory is used to predict field-scale effective properties and variances of tension and moisture content. Applications illustrate the important effects of small-scale heterogeneity on large-scale anisotropy and hysteresis and demonstrate the feasibility of simulating two-dimensional flow systems at time and space scales of interest in radioactive waste disposal investigations. Numerical algorithms for predicting field scale unsaturated flow and contaminant transport have been improved by requiring them to respect fundamental physical principles such as mass conservation. These algorithms are able to provide realistic simulations of systems with very dry initial conditions and high degrees of heterogeneity. Numerical simulation of the movement of water and air in unsaturated soils has demonstrated the importance of air pathways for contaminant transport. The stochastic flow and transport theory has been used to develop a systematic approach to performance assessment and site characterization. Hypothesis-testing techniques have been used to determine whether model predictions are consistent with observed data

Thermo-mechanical constitutive modeling of unsaturated clays based on the critical state concepts

OpenAIRE

Tourchi, Saeed; Hamidi, Amir

2015-01-01

A thermo-mechanical constitutive model for unsaturated clays is constructed based on the existing model for saturated clays originally proposed by the authors. The saturated clays model was formulated in the framework of critical state soil mechanics and modified Cam-clay model. The existing model has been generalized to simulate the experimentally observed behavior of unsaturated clays by introducing Bishop's stress and suction as independent stress parameters and modifying the hardening rul...

Structural Analysis of Unsaturated Glycosphingolipids Using Shotgun Ozone-Induced Dissociation Mass Spectrometry

Science.gov (United States)

Barrientos, Rodell C.; Vu, Ngoc; Zhang, Qibin

2017-08-01

Glycosphingolipids are essential biomolecules widely distributed across biological kingdoms yet remain relatively underexplored owing to both compositional and structural complexity. While the glycan head group has been the subject of most studies, there is paucity of reports on the lipid moiety, particularly the location of unsaturation. In this paper, ozone-induced dissociation mass spectrometry (OzID-MS) implemented in a traveling wave-based quadrupole time-of-flight (Q-ToF) mass spectrometer was applied to study unsaturated glycosphingolipids using shotgun approach. Resulting high resolution mass spectra facilitated the unambiguous identification of diagnostic OzID product ions. Using [M+Na]+ adducts of authentic standards, we observed that the long chain base and fatty acyl unsaturation had distinct reactivity with ozone. The reactivity of unsaturation in the fatty acyl chain was about 8-fold higher than that in the long chain base, which enables their straightforward differentiation. Influence of the head group, fatty acyl hydroxylation, and length of fatty acyl chain on the oxidative cleavage of double bonds was also observed. Application of this technique to bovine brain galactocerebrosides revealed co-isolated isobaric and regioisomeric species, which otherwise would be incompletely identified using contemporary collision-induced dissociation (CID) alone. These results highlight the potential of OzID-MS in glycosphingolipids research, which not only provides complementary structural information to existing CID technique but also facilitates de novo structural determination of these complex biomolecules. [Figure not available: see fulltext.

Estimate of dispersion in an unsaturated aquifer

Science.gov (United States)

Stephenson, D.; De Jesus, A. S. M.

1985-10-01

The Nuclear Development Corporation of South Africa (Pty) Ltd. (NUCOR) is constructing a low-level radioactive waste disposal site near Springbok in Namaqualand, an arid region to the west of South Africa. A groundwater model was developed which required site-specific data and this work describes procedures developed to assess the dispersivity of the soil in the vicinity of the proposed site. Preliminary laboratory tests, carried out using a sodium chloride solution, indicated the order of magnitude of the dispersivity for saturated soil at various levels. This enabled site tests to be designed. The site tests were done by injecting a pulse of scandium-46 into a hole and monitoring the displacement of the radioactive cloud as it moved down under gravity and spread laterally. A mathematical model was developed to predict the behaviour of the cloud and calibration of the model yielded vertical and horizontal dispersivities. The dispersion of radioactivity at the cloud front was assumed to occur in unsaturated medium while the continuously injected water behind the radioactivity was assumed to disperse in a saturated medium. Thus monitoring the concentration of both yielded approximate values for the effective dispersivities in unsaturated and saturated media.

Saturated and unsaturated salt transport in peat from a constructed fen

Science.gov (United States)

Simhayov, Reuven B.; Weber, Tobias K. D.; Price, Jonathan S.

2018-02-01

The underlying processes governing solute transport in peat from an experimentally constructed fen peatland were analyzed by performing saturated and unsaturated solute breakthrough experiments using Na+ and Cl- as reactive and non-reactive solutes, respectively. We tested the performance of three solute transport models, including the classical equilibrium convection-dispersion equation (CDE), a chemical non-equilibrium one-site adsorption model (OSA) and a model to account for physical non-equilibrium, the mobile-immobile (MIM) phases. The selection was motivated by the fact that the applicability of the MIM in peat soils finds a wide consensus. However, results from inverse modeling and a robust statistical evaluation of this peat provide evidence that the measured breakthrough of the conservative tracer, Cl-, could be simulated well using the CDE. Furthermore, the very high Damköhler number (which approaches infinity) suggests instantaneous equilibration between the mobile and immobile phases underscoring the redundancy of the MIM approach for this particular peat. Scanning electron microscope images of the peat show the typical multi-pore size distribution structures have been homogenized sufficiently by decomposition, such that physical non-equilibrium solute transport no longer governs the transport process. This result is corroborated by the fact the soil hydraulic properties were adequately described using a unimodal van Genuchten-Mualem model between saturation and a pressure head of ˜ -1000 cm of water. Hence, MIM was not the most suitable choice, and the long tailing of the Na+ breakthrough curve was caused by chemical non-equilibrium. Successful description was possible using the OSA model. To test our results for the unsaturated case, we conducted an unsaturated steady-state evaporation experiment to drive Na+ and Cl- transport. Using the parameterized transport models from the saturated experiments, we could numerically simulate the unsaturated

Development and validation of mechanical model for saturated/unsaturated bentonite buffer

International Nuclear Information System (INIS)

Yamamoto, S.; Komine, H.; Kato, S.

2010-01-01

Document available in extended abstract form only. Development and validation of mechanical models for bentonite buffer and backfill materials are one of important subjects to appropriately evaluate long term behaviour or condition of the EBS in radioactive waste disposal. The Barcelona Basic Model (BBM), which is one of extensions of the modified Cam-Clay model for unsaturated and expansive soil, has been developed and widely applied to several problems by using the coupled THM code, Code B right. Advantage of the model is that mechanical characteristics of buffer and backfill materials under not only saturated condition but also unsaturated one are taken account as well as swelling characteristics due to wetting. In this study the BBM is compared with already existing experimental data and already developed another model in terms of swelling characteristics of Japanese bentonite Kunigel-V1, and is validated in terms of consolidation characteristics based on newly performed controlled-suction oedometer tests for the Kunigel-V1 bentonite. Komine et al. (2003) have proposed a model (set of equations) for predicting swelling characteristics based on the diffuse double layer concept and the van der Waals force concept etc. They performed a lot of swelling deformation tests of bentonite and sand-bentonite mixture to confirm the applicability of the model. The BBM well agrees with the model proposed by Komine et al. and the experimental data in terms of swelling characteristics. Compression index and swelling index depending on suction are introduced in the BBM. Controlled-suction consolidation tests (oedometer tests) were performed to confirm the applicability of the suction dependent indexes to unsaturated bentonite. Compacted bentonite with initial dry density of 1.0 Mg/m 3 was tested. Constant suction, 80 kPa, 280 kPa and 480 kPa was applied and kept during the consolidation tests. Applicability of the BBM to consolidation and swelling behaviour of saturated and

Continuum model for water movement in an unsaturated fractured rock mass

International Nuclear Information System (INIS)

Peters, R.R.; Klavetter, E.A.

1988-01-01

The movement of fluids in a fractured, porous medium has been the subject of considerable study. This paper presents a continuum model that may be used to evaluate the isothermal movement of water in an unsaturated, fractured, porous medium under slowly changing conditions. This continuum model was developed for use in evaluating the unsaturated zone at the Yucca Mountain site as a potential repository for high-level nuclear waste. Thus its development has been influenced by the conditions thought to be present at Yucca Mountain. A macroscopic approach and a microscopic approach are used to develop a continuum model to evaluate water movement in a fractured rock mass. Both approaches assume that the pressure head in the fractures and the matrix are identical in a plane perpendicular to flow. Both approaches lead to a single-flow equation for a fractured rock mass. The two approaches are used to calculate unsaturated hydrologic properties, i.e., relative permeability and saturation as a function of pressure head, for several types of tuff underlying Yucca Mountain, using the best available hydrologic data for the matrix and the fractures. Rock mass properties calculated by both approaches are similar

Synthesis and study of novel silicon-based unsaturated polymers

Energy Technology Data Exchange (ETDEWEB)

Lin, Jibing [Iowa State Univ., Ames, IA (United States)

1995-06-19

Novel unsaturated polymers have been synthesized and studied as precursors to silicon carbide and third order nonlinear optical materials. X ray structures were obtained. Kinetic and mechanistic studies of the unique thermal isomerization of dimethylenedisilacyclobutane to a carbene were conducted.

A Preliminary Design of a Calibration Chamber for Evaluating the Stability of Unsaturated Soil Slope

Science.gov (United States)

Hsu, H.-H.

2012-04-01

The unsaturated soil slopes, which have ground water tables and are easily failure caused by heavy rainfalls, are widely distributed in the arid and semi-arid areas. For analyzing the stability of slope, in situ tests are the direct methods to obtain the test site characteristics. The cone penetration test (CPT) is a popular in situ test method. Some of the CPT empirical equations established from calibration chamber tests. The CPT performed in calibration chamber was commonly used clean quartz sand as testing material in the past. The silty sand is observed in many actual slopes. Because silty sand is relatively compressible than quartz sand, it is not suitable to apply the correlations between soil properties and CPT results built from quartz sand to silty sand. The experience on CPT calibration in silty sand has been limited. CPT calibration tests were mostly performed in dry or saturated soils. The condition around cone tip during penetration is assumed to be fully drained or fully undrained, yet it was observed to be partially drained for unsaturated soils. Because of the suction matrix has a great effect on the characteristics of unsaturated soils, they are much sensitive to the water content than saturated soils. The design of an unsaturated calibration chamber is in progress. The air pressure is supplied from the top plate and the pore water pressure is provided through the high air entry value ceramic disks located at the bottom plate of chamber cell. To boost and uniform distribute the unsaturated effect, four perforated burettes are installed onto the ceramic disks and stretch upwards to the midheight of specimen. This paper describes design concepts, illustrates this unsaturated calibration chamber, and presents the preliminary test results.

Time-lapse gravity data for monitoring and modeling artificial recharge through a thick unsaturated zone

Science.gov (United States)

Kennedy, Jeffrey R.; Ferre, Ty P.A.; Creutzfeldt, Benjamin

2016-01-01

Groundwater-level measurements in monitoring wells or piezometers are the most common, and often the only, hydrologic measurements made at artificial recharge facilities. Measurements of gravity change over time provide an additional source of information about changes in groundwater storage, infiltration, and for model calibration. We demonstrate that for an artificial recharge facility with a deep groundwater table, gravity data are more sensitive to movement of water through the unsaturated zone than are groundwater levels. Groundwater levels have a delayed response to infiltration, change in a similar manner at many potential monitoring locations, and are heavily influenced by high-frequency noise induced by pumping; in contrast, gravity changes start immediately at the onset of infiltration and are sensitive to water in the unsaturated zone. Continuous gravity data can determine infiltration rate, and the estimate is only minimally affected by uncertainty in water-content change. Gravity data are also useful for constraining parameters in a coupled groundwater-unsaturated zone model (Modflow-NWT model with the Unsaturated Zone Flow (UZF) package).

Study of interaction in systems of MoCl/sub 5/-MeCl/sub 2/ (Me - Sn, Zn, Cd, Hg) - a solvent

Energy Technology Data Exchange (ETDEWEB)

Golub, A M; Trachevskii, V V; Ul' ko, N V [Kievskij Gosudarstvennyj Univ. (Ukrainian SSR)

1978-04-01

Interaction of Mo(5) with dichlorides of tin, zinc, cadmium and mercury in organic solvents was studied by preparative methods, by electron, epr, infrared spectrometry and by conductometry. A polynuclear diamagnetic compound with Mo(5):Sn(2) ratio of 2:1 formed in acetone. A coordination polynuclear compound of (MoOCl/sub 3/)/sub 2/xSnCl/sub 2/x2CH/sub 3/CN was isolated from acetonitrile. It is shown that formation of solvate-chloride and solvate complexes of Mo(5) in solvents depends both on the solvating capacity of the solvent and on stability of the MeCl/sup -3/ (Me is Sn, Zn, Cd, Hg) chloride complex, which grows in the Zn < Sn < Cd < Hg series.

MODELING COUPLED PROCESSES OF MULTIPHASE FLOW AND HEAT TRANSFER IN UNSATURATED FRACTURED ROCK

International Nuclear Information System (INIS)

Y. Wu; S. Mukhopadhyay; K. Zhang; G.S. Bodvarsson

2006-01-01

A mountain-scale, thermal-hydrologic (TH) numerical model is developed for investigating unsaturated flow behavior in response to decay heat from the radioactive waste repository at Yucca Mountain, Nevada, USA. The TH model, consisting of three-dimensional (3-D) representations of the unsaturated zone, is based on the current repository design, drift layout, and thermal loading scenario under estimated current and future climate conditions. More specifically, the TH model implements the current geological framework and hydrogeological conceptual models, and incorporates the most updated, best-estimated input parameters. This mountain-scale TH model simulates the coupled TH processes related to mountain-scale multiphase fluid flow, and evaluates the impact of radioactive waste heat on the hydrogeological system, including thermally perturbed liquid saturation, gas- and liquid-phase fluxes, and water and rock temperature elevations, as well as the changes in water flux driven by evaporation/condensation processes and drainage between drifts. For a better description of the ambient geothermal condition of the unsaturated zone system, the TH model is first calibrated against measured borehole temperature data. The ambient temperature calibration provides the necessary surface and water table boundary as well as initial conditions. Then, the TH model is used to obtain scientific understanding of TH processes in the Yucca Mountain unsaturated zone under the designed schedule of repository thermal load

Comparison of strongly heat-driven flow codes for unsaturated media

International Nuclear Information System (INIS)

Updegraff, C.D.

1989-08-01

Under the sponsorship of the US Nuclear Regulatory Commission, Sandia National Laboratories (SNL) is developing a performance assessment methodology for the analysis of long-term disposal of high-level radioactive waste (HLW) in unsaturated welded tuff. As part of this effort, SNL evaluated existing strongly heat-driven flow computer codes for simulating ground-water flow in unsaturated media. The three codes tested, NORIA, PETROS, and TOUGH, were compared against a suite of problems for which analytical and numerical solutions or experimental results exist. The problems were selected to test the abilities of the codes to simulate situations ranging from simple, uncoupled processes, such as two-phase flow or heat transfer, to fully coupled processes, such as vaporization caused by high temperatures. In general, all three codes were found to be difficult to use because of (1) built-in time stepping criteria, (2) the treatment of boundary conditions, and (3) handling of evaporation/condensation problems. A drawback of the study was that adequate problems related to expected repository conditions were not available in the literature. Nevertheless, the results of this study suggest the need for thorough investigations of the impact of heat on the flow field in the vicinity of an unsaturated HLW repository. Recommendations are to develop a new flow code combining the best features of these three codes and eliminating the worst ones. 19 refs., 49 figs

Dsc cure kinetics of an unsaturated polyester resin using empirical kinetic model

International Nuclear Information System (INIS)

Abdullah, I.

2015-01-01

In this paper, the kinetics of curing of unsaturated polyester resin initiated with benzoyl peroxide was studied. In case of unsaturated polyester (UP) resin, isothermal test alone could not predict correctly the curing time of UP resin. Therefore, isothermal kinetic analysis through isoconventional adjustment was used to correctly predict the curing time and temperature of UP resin. Isothermal kinetic analysis through isoconversional adjustment indicated that 97% of UP resin cures in 33 min at 120 degree C. Curing of UP resin through microwaves was also studied and found that 67% of UP resin cures in 1 min at 120 degree C. The crosslinking reaction of UP resin is so fast at 120 degree C that it becomes impossible to predict correctly the curing time of UP resin using isothermal test and the burial of C=C bonds in microgels makes it impossible to be fully cured by microwaves at 120 degree C. The rheological behaviour of unsaturated polyester resin was also studied to observe the change in viscosity with respect to time and temperature. (author)

Treatability and scale-up protocols for polynuclear aromatic hydrocarbon bioremediation of manufactured-gas-plant soils. Final report, September 1987-July 1991

International Nuclear Information System (INIS)

Blackburn, J.W.; DiGrazia, P.M.; Sanseverino, J.

1991-07-01

The report describes activities to develop a framework to reliably scale-up and apply challenging bioremediation processes to polynuclear aromatic hydrocarbons in Manufactured Gas Plant (MGP) soils. It includes: a discussion of the accuracy needed for competitive application of bioremediation; a framework and examples for treatability and scale-up protocols for selection, design and application of these processes; both batch and continuous testing protocols for developing predictive rate data; and special predictive relationships that may be used in process selection/scale-up. The work, coupled with subsequent work (as recommended) to develop an MGP soil desorption/diffusion protocol and new scale-up methods, and with subsequent scale-up testing should lead to the capability for improved selection of MGP sites for bioremediation and improved performance, success, and reliability of field applications. With this greater predictive reliability, bioremediation will be used more often in the field on the most favorable applications and its cost advantages over other remediation options will be realized

Determination of Matric Suction and Saturation Degree for Unsaturated Soils, Comparative Study - Numerical Method versus Analytical Method

Science.gov (United States)

Chiorean, Vasile-Florin

2017-10-01

Matric suction is a soil parameter which influences the behaviour of unsaturated soils in both terms of shear strength and permeability. It is a necessary aspect to know the variation of matric suction in unsaturated soil zone for solving geotechnical issues like unsaturated soil slopes stability or bearing capacity for unsaturated foundation ground. Mathematical expression of the dependency between soil moisture content and it’s matric suction (soil water characteristic curve) has a powerful character of nonlinearity. This paper presents two methods to determine the variation of matric suction along the depth included between groundwater level and soil level. First method is an analytical approach to emphasize one direction steady state unsaturated infiltration phenomenon that occurs between the groundwater level and the soil level. There were simulated three different situations in terms of border conditions: precipitations (inflow conditions on ground surface), evaporation (outflow conditions on ground surface), and perfect equilibrium (no flow on ground surface). Numerical method is finite element method used for steady state, two-dimensional, unsaturated infiltration calculus. Regarding boundary conditions there were simulated identical situations as in analytical approach. For both methods, was adopted the equation proposed by van Genuchten-Mualen (1980) for mathematical expression of soil water characteristic curve. Also for the unsaturated soil permeability prediction model was adopted the equation proposed by van Genuchten-Mualen. The fitting parameters of these models were adopted according to RETC 6.02 software in function of soil type. The analyses were performed in both methods for three major soil types: clay, silt and sand. For each soil type were concluded analyses for three situations in terms of border conditions applied on soil surface: inflow, outflow, and no flow. The obtained results are presented in order to highlight the differences

Triangles and squares for a unique molecular crystal structure. Unsupported two-coordinate lithium cations and CC agostic interactions in cyclopropyllithium derivatives

Energy Technology Data Exchange (ETDEWEB)

Dufrois, Quentin; Daran, Jean-Claude; Vendier, Laure; Dinoi, Chiara; Etienne, Michel [Laboratoire de Chimie de Coordination du CNRS (LCC), Toulouse (France); Universite de Toulouse, UPS, INPT, LCC, Toulouse (France)

2018-02-12

Understanding and controlling the aggregation state is germane to alkyllithium chemistry. Lewis base-free alkyllithium compounds normally form tetrahedral tetramers or octahedral hexamers in the solid state with the lithium cations being three-coordinate. We report that the unsupported cyclopropyl derivative 1-(trimethylsilyl)cyclopropyllithium [{μ-c-C(SiMe_3)C_2H_4}Li]{sub 4} (1), synthesized by the reduction of 1-(phenylthio)-1-(trimethylsilyl)cyclopropane, crystallizes as a tetramer in the space group I-4 with the two-coordinate lithium atoms forming a square. CC agostic interactions complete the coordination sphere around each lithium. The aggregate is preserved in hydrocarbon solution. Furthermore, CC agostic interactions compete intra- and intermolecularly with Lewis base donation as in the unsaturated dimer of 1-(phenylthio)cyclopropyllithium [Li(thf){sub 2}{μ-c-C(SPh)C_2H_4}{sub 2}Li (thf)] (3) which is also fully characterized. (copyright 2018 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Unsaturated Zone and Saturated Zone Transport Properties (U0100)

Energy Technology Data Exchange (ETDEWEB)

J. Conca

2000-12-20

This Analysis/Model Report (AMR) summarizes transport properties for the lower unsaturated zone hydrogeologic units and the saturated zone at Yucca Mountain and provides a summary of data from the Busted Butte Unsaturated Zone Transport Test (UZTT). The purpose of this report is to summarize the sorption and transport knowledge relevant to flow and transport in the units below Yucca Mountain and to provide backup documentation for the sorption parameters decided upon for each rock type. Because of the complexity of processes such as sorption, and because of the lack of direct data for many conditions that may be relevant for Yucca Mountain, data from systems outside of Yucca Mountain are also included. The data reported in this AMR will be used in Total System Performance Assessment (TSPA) calculations and as general scientific support for various Process Model Reports (PMRs) requiring knowledge of the transport properties of different materials. This report provides, but is not limited to, sorption coefficients and other relevant thermodynamic and transport properties for the radioisotopes of concern, especially neptunium (Np), plutonium (Pu), Uranium (U), technetium (Tc), iodine (I), and selenium (Se). The unsaturated-zone (UZ) transport properties in the vitric Calico Hills (CHv) are discussed, as are colloidal transport data based on the Busted Butte UZTT, the saturated tuff, and alluvium. These values were determined through expert elicitation, direct measurements, and data analysis. The transport parameters include information on interactions of the fractures and matrix. In addition, core matrix permeability data from the Busted Butte UZTT are summarized by both percent alteration and dispersion.

Unsaturated Zone and Saturated Zone Transport Properties (U0100)

International Nuclear Information System (INIS)

Conca, J.

2000-01-01

This Analysis/Model Report (AMR) summarizes transport properties for the lower unsaturated zone hydrogeologic units and the saturated zone at Yucca Mountain and provides a summary of data from the Busted Butte Unsaturated Zone Transport Test (UZTT). The purpose of this report is to summarize the sorption and transport knowledge relevant to flow and transport in the units below Yucca Mountain and to provide backup documentation for the sorption parameters decided upon for each rock type. Because of the complexity of processes such as sorption, and because of the lack of direct data for many conditions that may be relevant for Yucca Mountain, data from systems outside of Yucca Mountain are also included. The data reported in this AMR will be used in Total System Performance Assessment (TSPA) calculations and as general scientific support for various Process Model Reports (PMRs) requiring knowledge of the transport properties of different materials. This report provides, but is not limited to, sorption coefficients and other relevant thermodynamic and transport properties for the radioisotopes of concern, especially neptunium (Np), plutonium (Pu), Uranium (U), technetium (Tc), iodine (I), and selenium (Se). The unsaturated-zone (UZ) transport properties in the vitric Calico Hills (CHv) are discussed, as are colloidal transport data based on the Busted Butte UZTT, the saturated tuff, and alluvium. These values were determined through expert elicitation, direct measurements, and data analysis. The transport parameters include information on interactions of the fractures and matrix. In addition, core matrix permeability data from the Busted Butte UZTT are summarized by both percent alteration and dispersion

The transport and behaviour of isoproturon in unsaturated chalk cores

Science.gov (United States)

Besien, T. J.; Williams, R. J.; Johnson, A. C.

2000-04-01

A batch sorption study, a microcosm degradation study, and two separate column leaching studies were used to investigate the transport and fate of isoproturon in unsaturated chalk. The column leaching studies used undisturbed core material obtained from the field by dry percussion drilling. Each column leaching study used 25 cm long, 10 cm wide unsaturated chalk cores through which a pulse of isoproturon and bromide was eluted. The cores were set-up to simulate conditions in the unsaturated zone of the UK Chalk aquifer by applying a suction of 1 kPa (0.1 m H 2O) to the base of each column, and eluting at a rate corresponding to an average recharge rate through the unsaturated Chalk. A dye tracer indicated that the flow was through the matrix under these conditions. The results from the first column study showed high recovery rates for both isoproturon (73-92%) and bromide (93-96%), and that isoproturon was retarded by a factor of about 1.23 relative to bromide. In the second column study, two of the four columns were eluted with non-sterile groundwater in place of the sterile groundwater used on all other columns, and this study showed high recovery rates for bromide (85-92%) and lower recovery rates for isoproturon (66-79% — sterile groundwater, 48-61% — non-sterile groundwater). The enhanced degradation in the columns eluted with non-sterile groundwater indicated that groundwater microorganisms had increased the degradation rate within these columns. Overall, the reduced isoproturon recovery in the second column study was attributed to increased microbial degradation as a result of the longer study duration (162 vs. 105 days). The breakthrough curves (BTCs) for bromide had a characteristic convection-dispersion shape and were accurately simulated with the minimum of calibration using a simple convection-dispersion model (LEACHP). However, the isoproturon BTCs had an unusual shape and could not be accurately simulated.

Pore-water extraction from unsaturated tuff by triaxial and one-dimensional compression methods, Nevada Test Site, Nevada

International Nuclear Information System (INIS)

Mower, T.E.; Higgins, J.D.; Yang, In C.; Peters, C.A.

1994-01-01

The hydrologic system in the unsaturated tuff at Yucca Mountain, Nevada, is being evaluated for the US Department of Energy by the Yucca Mountain Project Branch of the US Geological Survey as a potential site for a high-level radioactive-waste repository. Part of this investigation includes a hydrochemical study that is being made to assess characteristics of the hydrologic system such as: traveltime, direction of flow, recharge and source relations, and types and magnitudes of chemical reactions in the unsaturated tuff. In addition, this hydrochemical information will be used in the study of the dispersive and corrosive effects of unsaturated-zone water on the radioactive-waste storage canisters. This report describes the design and validation of laboratory experimental procedures for extracting representative samples of uncontaminated pore water from welded and nonwelded, unsaturated tuffs from the Nevada Test Site

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Compounds

Science.gov (United States)

George, C.; Passananti, M.; Kong, L.; Shang, J.; Perrier, S.; Jianmin, C.; Donaldson, D. J.

2016-12-01

The atmospheric formation of organosulfur derivatives through reaction with SO2 is generally mediated by oxidants such as O3, OH; recently we have proposed a direct reaction between SO2 and unsaturated compounds as another possible pathway for organosulfate formation in the troposphere. For the first time it was shown recently that a heterogeneous reaction between SO2 and oleic acid (OA; an unsaturated fatty acid) takes place and leads efficiently to the formation of organosulfur products. Here, we demonstrate that this reaction proceeds on various unsaturated compounds, and may therefore have a general environmental impact. We used different experimental strategies i.e., a coated flow tube (CFT), an aerosol flow tube (AFT) and a DRIFT (diffuse reflectance infrared Fourier transform) cell. The reaction products were analyzed by means of liquid chromatography coupled to a high resolution mass spectrometer (LC-HR-MS). We report indeed that SO2 reacts with large variety of C=C unsaturations and that even in the presence of ozone, SO2 reacts with OA leading to organosulfur products. A strong enhancement in product formation is observed under actinic illumination, increases the atmospheric significance of this chemical pathway. This is probably due to the chromophoric nature of the SO2 adduct with C=C bonds, and means that the contribution of this direct addition of SO2 could be in excess of 5%. The detection in atmospheric aerosols of organosulfur compounds with the same chemical formulae as the products identified here seems to confirm the importance of this reaction in the atmosphere.

Conceptual Model and Numerical Approaches for Unsaturated Zone Flow and Transport

International Nuclear Information System (INIS)

H.H. Liu

2004-01-01

The purpose of this model report is to document the conceptual and numerical models used for modeling unsaturated zone (UZ) fluid (water and air) flow and solute transport processes. This work was planned in ''Technical Work Plan for: Unsaturated Zone Flow Model and Analysis Report Integration'' (BSC 2004 [DIRS 169654], Sections 1.2.5, 2.1.1, 2.1.2 and 2.2.1). The conceptual and numerical modeling approaches described in this report are mainly used for models of UZ flow and transport in fractured, unsaturated rock under ambient conditions. Developments of these models are documented in the following model reports: (1) UZ Flow Model and Submodels; (2) Radionuclide Transport Models under Ambient Conditions. Conceptual models for flow and transport in unsaturated, fractured media are discussed in terms of their applicability to the UZ at Yucca Mountain. The rationale for selecting the conceptual models used for modeling of UZ flow and transport is documented. Numerical approaches for incorporating these conceptual models are evaluated in terms of their representation of the selected conceptual models and computational efficiency; and the rationales for selecting the numerical approaches used for modeling of UZ flow and transport are discussed. This report also documents activities to validate the active fracture model (AFM) based on experimental observations and theoretical developments. The AFM is a conceptual model that describes the fracture-matrix interaction in the UZ of Yucca Mountain. These validation activities are documented in Section 7 of this report regarding use of an independent line of evidence to provide additional confidence in the use of the AFM in the UZ models. The AFM has been used in UZ flow and transport models under both ambient and thermally disturbed conditions. Developments of these models are documented

Modification of unsaturated polyester resins using nano-size core ...

African Journals Online (AJOL)

Modification of unsaturated polyester resins using nano-size core-shell particles. MO Munyati, PA Lovell. Abstract. No Abstract Available Journal of Science and Technology Special Edition 2004: 24-31. Full Text: EMAIL FULL TEXT EMAIL FULL TEXT · DOWNLOAD FULL TEXT DOWNLOAD FULL TEXT.

Numerical modeling of isothermal and nonisothermal flow in unsaturated fractured rock: A review

International Nuclear Information System (INIS)

Pruess, K.; Wang, J.S.Y.

1986-01-01

The tuff formations at and near the Nevada Test Site are comprised of fractured-porous material, with hydrologic properties quite different from those encountered in most previous unsaturated flow studies dealing with soils. In the vicinity of the waste packages, flow is driven by high temperatures (exceeding 100 0 C) and large temperature gradients. The approximations developed in soil science for weakly nonisothermal flow are not applicable to this situation, and a multiphase description of flow is required, similar to approaches used in modeling of geothermal reservoirs and thermally enhance oil recovery. The conventional approach to unsaturated flow is applicable, however, to a variety of problems relating to natural (undisturbed) and far-field flow conditions. This paper reviews recent work on numerical modeling of unsaturated flow undertaken in the context of nuclear waste isolation studies. Concepts and applications of broader interest are summarized, and important issues are identified that have not been adequately explored. 84 refs, 8 figs

Method of polymerizing ethylenically unsaturated materials by irradiation and composition for use therein

International Nuclear Information System (INIS)

Nemcek, J.; Heap, N.

1976-01-01

This patent concerns photopolymerizable compositions consisting essentially of at least one polymerizable ethylenically unsaturated material and a photosensitive catalyst comprising (a) from 0.5 to 5 percent based on the ethylenically unsaturated material of at least one photosensitizer having the structure Ph(CO)C 2 A(CO)Ph, where Ph is phenyl, halogen-substituted phenyl, phenylene or halogen-substituted phenylene and A is a cyclic hydrocarbyl group, a halogen-substituted cyclic hydrocarbyl group, or a group of the formula X(NR)COCONRY, where X and Y each is hydrogen, a hydrocarbyl, or a halogen-substituted hydrocarbyl group, and (b) from 1 to 5 percent by weight based on the ethylenically unsaturated material of a reducing agent capable of reducing the photosensitizer when the photosensitizer is in an excited state. Also described is a process of preparing polymeric materials by irradiating the foregoing polymerizable composition at a wavelength capable of exciting the photosensitizer to an excited state

Review of Upscaling Methods for Describing Unsaturated Flow

Energy Technology Data Exchange (ETDEWEB)

Wood, Brian D.

2000-09-26

Representing samll-scale features can be a challenge when one wants to model unsaturated flow in large domains. In this report, the various upscaling techniques are reviewed. The following upscaling methods have been identified from the literature: stochastic methods, renormalization methods, volume averaging and homogenization methods. In addition, a final technique, full resolution numerical modeling, is also discussed.

Numerical convergence improvements for porflow unsaturated flow simulations

Energy Technology Data Exchange (ETDEWEB)

Flach, Greg [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2017-08-14

Section 3.6 of SRNL (2016) discusses various PORFLOW code improvements to increase modeling efficiency, in preparation for the next E-Area Performance Assessment (WSRC 2008) revision. This memorandum documents interaction with Analytic & Computational Research, Inc. (http://www.acricfd.com/default.htm) to improve numerical convergence efficiency using PORFLOW version 6.42 for unsaturated flow simulations.

Role of the unsaturated zone in radioactive and hazardous waste disposal

International Nuclear Information System (INIS)

Mercer, J.W.; Marine, I.W.; Rao, P.S.C.

1983-01-01

The problems of hazardous and low-level radioactive waste disposal caused by the physical and chemical processes active in the unsaturated zone are explored in this book. The focus is on the use of laboratory analyses, field observations, and numerical and analytical calculations to create a clear picture of both problems and potential solutions. Topics include policy modeling, statistical techniques, liners, and field applications. Contents include: Modeling of Moisture Movement through Layered Trench Covers; Role of Partially Saturated Soil in Liner Design for Hazardous Waste Disposal Sites; Field Experiments to Determine Saturated Hydraulic Conductivity in the Vadose Zone; Role of Desaturation on Transport through Fractured Rock; Nuclear Waste Isolation in the Unsaturated Zone of Arid Regions

The measurement of unsaturated hydraulic conductivity from one-step outflow method

International Nuclear Information System (INIS)

Lee, S. H.; Hwang, J. H.; Lee, J. M.; Kim, C. R.

2003-01-01

One of the most important parts in constructing radioactive waste repository may be its safety aspect. The fundamental function of the repository is to isolate completely and forever the radioactive wastes disposed of in it. However, since either normally or abnormally nuclides are to be released from the repository with a certain causes. The hydraulic conductivity is related to transportation of nuclide in soil. However, hydraulic characteristics research in unsaturated soil is not enough at present time. A fast and easy procedure for estimating unsaturated flow parameters is presented. The estimation is based on direct measurement of the retention characteristics combined with inverse estimation of the hydraulic conductivity characteristics from one-step outflow experiment

Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

DEFF Research Database (Denmark)

Binning, Philip John; Postma, Diederik Jan; Russel, T.F.

2007-01-01

Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed at...... parameters; for example, the time to approach steady state depends exponentially on the distance between the soil surface and the subsurface reactive zone. Copyright 2007 by the American Geophysical Union....... at depth in the unsaturated zone, a pressure gradient is created between the reactive zone and the ground surface, causing a substantial advective air flow into the subsurface. To determine the balance between advective and diffusive transport, a one-dimensional multicomponent unsaturated zone gas...

Solid-State NMR Spectroscopy Proves the Presence of Penta-coordinated Sc Sites in MIL-100(Sc).

Science.gov (United States)

Giovine, Raynald; Volkringer, Christophe; Ashbrook, Sharon E; Trébosc, Julien; McKay, David; Loiseau, Thierry; Amoureux, Jean-Paul; Lafon, Olivier; Pourpoint, Frédérique

2017-07-18

Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45 Sc NMR experiment allows their specific observation in activated Sc 3 BTB 2 (H 3 BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO 5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO 5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13 C- 45 Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fourier transform infrared imaging showing reduced unsaturated lipid content in the hippocampus of a mouse model of Alzheimer's disease.

Science.gov (United States)

Leskovjan, Andreana C; Kretlow, Ariane; Miller, Lisa M

2010-04-01

Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer's disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier transform infrared imaging (FTIRI) to visualize the unsaturated lipid content in specific regions of the hippocampus in the PSAPP mouse model of AD as a function of plaque formation. Specifically, the unsaturated lipid content was imaged using the olefinic =CH stretching mode at 3012 cm(-1). The axonal, dendritic, and somatic layers of the hippocampus were examined in the mice at 13, 24, 40, and 56 weeks old. Results showed that lipid unsaturation in the axonal layer was significantly increased with normal aging in control (CNT) mice (p avoiding progression of the disease.

Unsaturated zone flow modeling for GWTT-95

International Nuclear Information System (INIS)

Ho, C.K.; Altman, S.J.; McKenna, S.A.; Arnold, B.W.

1995-01-01

In accordance with the Nuclear Regulatory Commission regulation regarding groundwater travel times at geologic repositories, various models of unsaturated flow in fractured tuff have been developed and implemented to assess groundwater travel times at the potential repository at Yucca Mountain, Nevada. Kaplan used one-dimensional models to describe the uncertainty and sensitivity of travel times to various processes at Yucca Mountain. Robey and Arnold et al. used a two-dimensional equivalent continuum model (ECM) with inter- and intra-unit heterogeneity in an attempt to assess fast-flow paths through the unsaturated, fractured tuff at Yucca Mountain (GWTT-94). However, significant flow through the fractures in previous models was not simulated due to the characteristics of the ECM, which requires the matrix to be nearly saturated before flow through the fractures is initiated. In the current study (GWTT-95), four two-dimensional cross-sections at Yucca Mountain are simulated using both the ECM and dual-permeability (DK) models. The properties of both the fracture and matrix domains are geostatistically simulated, yielding completely heterogeneous continua. Then, simulations of flow through the four cross-sections are performed using spatially nonuniform infiltration boundary conditions. Steady-state groundwater travel times from the potential repository to the water table are calculated

Effect Of Intraruminal Infussion Of Saturated And Unsaturated Fatty ...

African Journals Online (AJOL)

This study describes the effect of intraruminal infusion of diferent proportions of palmitic (saturated fatty acid) and linolenic (unsaturated fatty acid) on rumen degradability of organic matter fraction of Pennisetium purpureum, total volatile fatty acid and total methane productions in West African Dwarf sheep. Five combination ...

NaturAnalogs for the Unsaturated Zone

Energy Technology Data Exchange (ETDEWEB)

A. Simmons; A. Unger; M. Murrell

2000-03-08

The purpose of this Analysis/Model Report (AMR) is to document natural and anthropogenic (human-induced) analog sites and processes that are applicable to flow and transport processes expected to occur at the potential Yucca Mountain repository in order to build increased confidence in modeling processes of Unsaturated Zone (UZ) flow and transport. This AMR was prepared in accordance with ''AMR Development Plan for U0135, Natural Analogs for the UZ'' (CRWMS 1999a). Knowledge from analog sites and processes is used as corroborating information to test and build confidence in flow and transport models of Yucca Mountain, Nevada. This AMR supports the Unsaturated Zone (UZ) Flow and Transport Process Model Report (PMR) and the Yucca Mountain Site Description. The objectives of this AMR are to test and build confidence in the representation of UZ processes in numerical models utilized in the UZ Flow and Transport Model. This is accomplished by: (1) applying data from Boxy Canyon, Idaho in simulations of UZ flow using the same methodologies incorporated in the Yucca Mountain UZ Flow and Transport Model to assess the fracture-matrix interaction conceptual model; (2) Providing a preliminary basis for analysis of radionuclide transport at Pena Blanca, Mexico as an analog of radionuclide transport at Yucca Mountain; and (3) Synthesizing existing information from natural analog studies to provide corroborating evidence for representation of ambient and thermally coupled UZ flow and transport processes in the UZ Model.

Natural Analogs for the Unsaturated Zone

International Nuclear Information System (INIS)

Simmons, A.; Unger, A.; Murrell, M.

2000-01-01

The purpose of this Analysis/Model Report (AMR) is to document natural and anthropogenic (human-induced) analog sites and processes that are applicable to flow and transport processes expected to occur at the potential Yucca Mountain repository in order to build increased confidence in modeling processes of Unsaturated Zone (UZ) flow and transport. This AMR was prepared in accordance with ''AMR Development Plan for U0135, Natural Analogs for the UZ'' (CRWMS 1999a). Knowledge from analog sites and processes is used as corroborating information to test and build confidence in flow and transport models of Yucca Mountain, Nevada. This AMR supports the Unsaturated Zone (UZ) Flow and Transport Process Model Report (PMR) and the Yucca Mountain Site Description. The objectives of this AMR are to test and build confidence in the representation of UZ processes in numerical models utilized in the UZ Flow and Transport Model. This is accomplished by: (1) applying data from Boxy Canyon, Idaho in simulations of UZ flow using the same methodologies incorporated in the Yucca Mountain UZ Flow and Transport Model to assess the fracture-matrix interaction conceptual model; (2) Providing a preliminary basis for analysis of radionuclide transport at Pena Blanca, Mexico as an analog of radionuclide transport at Yucca Mountain; and (3) Synthesizing existing information from natural analog studies to provide corroborating evidence for representation of ambient and thermally coupled UZ flow and transport processes in the UZ Model

Changes of the water isotopic composition in unsaturated soils

International Nuclear Information System (INIS)

Feurdean, Victor; Feurdean, Lucia

2001-01-01

Based on the spatial and temporal variations of the stable isotope content in precipitation - as input in subsurface - and the mixing processes, the deuterium content in the water that moves in unsaturated zones was used to determine the most conducive season to recharge, the mechanisms for infiltration of snow or rain precipitation in humid, semi-arid or arid conditions, the episodic cycles of infiltration water mixing with the already present soil water and water vapor and whether infiltration water is or is not from local precipitation. Oscillations in the isotopic profiles of soil moisture can be used to estimate the following aspects: where piston or diffusive flow is the dominant mechanisms of water infiltration; the average velocities of the water movement in vadose zone; the influence of vegetation cover, soil type and slope exposure on the dynamics of water movement in soil; the conditions required for infiltration such as: the matrix, gravity, pressure and osmotic potentials during drainage in unsaturated soil. (authors)

Unsaturated transport of inorganic cations in undisturbed soil columns

International Nuclear Information System (INIS)

Jardine, P.M.; Jacobs, G.K.

1990-01-01

The unsaturated transport of Sr, Co, and Ca were studied in undisturbed soil columns (14 x 40 cm) of saprolitic shale to evaluate the significance of time dependent mass transfer and multispecies competitive exchange during transport. Observed breakthrough curves (BTCs) for Sr and Co were delayed relative to nonreactive Br BTC indicating that the former tracers were adsorbed by the soil. Effluent concentrations of Sr and Co were modeled with the classical convective dispersive (CD) equation and nonequilibrium mass transfer considerations did not appear necessary. Cation exchange equilibria relationships obtained from both shake batch and miscible displacement methods adequately described the thermodynamic processes which were prevalent during transport. These results suggest that the preferential transport of a reactive tracer is negligible for the realistic unsaturated conditions used in the study, and that the massive saprolite within the soil is a chemically active constituent during transport of reactive solutes. The implications of these findings for modeling in-situ subsurface contaminant transport are discussed. 7 refs., 9 figs

AN ACTIVE FRACTURE MODEL FOR UNSATURATED FLOW AND TRANSPORT

International Nuclear Information System (INIS)

HUI-HAI LIU, GUDMUNDUR S. BODVARSSON AND CHRISTINE DOUGHTY

1999-01-01

Fracture/matrix (F/M) interaction is a key factor affecting flow and transport in unsaturated fractured rocks. In classic continuum approaches (Warren and Root, 1963), it is assumed that flow occurs through all the connected fractures and is uniformly distributed over the entire fracture area, which generally gives a relatively large F/M interaction. However, fractures seem to have limited interaction with the surrounding matrix at Yucca Mountain, Nevada, as suggested by geochemical nonequilibrium between the perched water (resulting mainly from fracture flow) and pore water in the rock matrix. Because of the importance of the F/M interaction and related issues, there is a critical need to develop new approaches to accurately consider the interaction reduction inferred from field data at the Yucca Mountain site. Motivated by this consideration, they have developed an active fracture model based on the hypothesis that not all connected fractures actively conduct water in unsaturated fractured rocks

Analysis of gaseous-phase stable and radioactive isotopes in the unsaturated zone, Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Yang, I.C.; Haas, H.H.; Weeks, E.P.; Thorstenson, D.C.

1985-01-01

The Nevada Nuclear Waste Storage Investigations Project of the US Department of Energy provides that agency with data for evaluating volcanic tuff beneath Yucca Mountain, Nevada, to determine its suitability for a potential repository of high-level radioactive waste. Thickness of the unsaturated zone, which consists of fractured, welded and nonwelded tuff, is about 1640 to 2460 feet (500 to 750 meters). One question to be resolved is an estimate of minimum ground-water traveltime from the disturbed zone of the potentail repository to the accessible environment. Another issue is the potential for diffusive or convective gaseous transport of radionuclides from an underground facility in the unsaturated zone to the accessible environment. Gas samples were collected at intervals to a depth of 1200 feet from the unsaturated zone at Yucca Mountain, Nevada. Samples were analyzed for major atmospheric gases; carbon dioxide in the samples was analyzed for carbon-14 activity and for delta 13 C; water vapor in the samples was analyzed for deuterium and oxygen-18. These data could provide insight into the nature of unsaturated zone transport processes. 15 refs., 4 figs., 4 tabs

Binuclear and tetranuclear Mn(II) clusters in coordination polymers derived from semirigid tetracarboxylate and N‑donor ligands: syntheses, new topology structures and magnetism

Energy Technology Data Exchange (ETDEWEB)

Li, Xiao-Ling [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Liu, Guang-Zhen, E-mail: gzliuly@126.com [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Xin, Ling-Yun [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); Wang, Li-Ya [College of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented Porous Materials, Luoyang Normal University, Luoyang 471934 (China); College of Chemistry and Pharmacy Engineering, Nanyang Normal University, Nanyang, Henan 473061 (China)

2017-02-15

Two topologically new Mn(II) coordination polymers, namely ([Mn{sub 2}(H{sub 4}ipca)(4,4′-bpy){sub 1.5}(CH{sub 3}CH{sub 2}OH){sub 0.5}(H{sub 2}O){sub 1.5}]·0.5CH{sub 3}CH{sub 2}OH·2.5H{sub 2}O){sub n} (1) and (Mn{sub 4}(H{sub 4}ipca){sub 2}(bze)(H{sub 2}O){sub 4}){sub n} (2) were prepared by the solvothermal reactions of Mn(II) acetate with 5-(2’,3’-dicarboxylphenoxy)isophthalic acid (H{sub 4}ipca) in the presence of different N-donor coligands (4,4′-bpy=4,4′-bipyridyl and bze=1, 4-bis(1-imidazoly)benzene). The single crystal X-ray diffractions reveal that two complexes display 3D metal-organic frameworks with binuclear and tetranuclear Mn(II) units, respectively. Complex 1 features a (3,4,6)-connected porous framework based on dinuclear Mn(II) unit with the (4.5{sup 2}){sub 2}(4{sup 2}.6{sup 8}.8{sup 3}.9{sup 2})(5{sup 2}.8.9{sup 2}.10) new topology, and complex 2 possesses a (3,8)-connected network based on tetranuclear Mn(II) unit with the (4{sup 2}.6){sub 2}(4{sup 4}.6{sup 14}.7{sup 7}.8{sup 2}.9) new topology. Magnetic analyses indicate that both two compounds show weak antiferromagnetic interactions within binuclear and tetranuclear Mn(II) units. - Graphical abstract: Two topologically new Mn(II) metal-organic frameworks with dinuclear and tetranuclear Mn(II) units respectively were assembled by using 5-(2′,3′-Dicarboxylphenoxy)isophthalic acid and N-donor ancillary coligands. Magnetic analysis revealed the existence of dominant antiferromagnetic interactions within the polynuclear Mn(II) units. - Highlights: • Mixed ligand strategy produces two topologically new MOFs with dinuclear and tetranuclear Mn(II) respectively. • Magnetic fitting gives weak antiferromagnetic interactions within the polynuclear Mn(II) units.

Beaded Fiber Mats of PVA Containing Unsaturated Heteropoly Salt

Institute of Scientific and Technical Information of China (English)

Guo Cheng YANG; Yan PAN; Jian GONG; Chang Lu SHAO; Shang Bin WEN; Chen SHAO; Lun Yu QU

2004-01-01

Poly(vinyl alcohol) (PVA) fiber mats containing unsaturated heteropoly salt was prepared for the first time. IR, X-ray diffraction and SEM photographs characterized the beaded fiber mats.The viscoelasticity and the conductivity of the solution were the key factors that influence the formation of the beaded fiber mats.

The synthesis of some unsaturated 4-substituted-g-lactones

Directory of Open Access Journals (Sweden)

SUREN HUSINEC

2000-02-01

Full Text Available The synthesis of conjugated and nonconjugated unsaturated 4-substituted lactones of type 1 and 2 are described. The type 1 lactone was prepared by a two step procedure employing Bredereck's reagent. The type 2 lactone was synthesised by combining the Claisen-Ireland rearrangement and selenolactonisation.

Effect of water content on dispersion of transferred solute in unsaturated porous media

Energy Technology Data Exchange (ETDEWEB)

Latrille, C. [CEA Saclay, DEN/DANS/DPC/SECR/L3MR, 91191 Gif sur Yvette (France)

2013-07-01

Estimating contaminant migration in the context of waste disposal and/or environmental remediation of polluted soils requires a complete understanding of the underlying transport processes. In unsaturated porous media, water content impacts directly on porous solute transfer. Depending on the spatial distribution of water content, the flow pathway is more complex than in water saturated media. Dispersivity is consequently dependent on water content. Non-reactive tracer experiments performed using unsaturated sand columns confirm the dependence of dispersivity with pore velocity; moreover, a power law relationship between dispersivity and water content is evidenced. (authors)

CAPILLARY BARRIERS IN UNSATURATED FRACTURED ROCKS OF YUCCA MOUNTAIN, NEVADA

International Nuclear Information System (INIS)

Wu, Y.S.; Zhang, W.; Pan, L.; Hinds, J.; Bodvarsson, G.

2000-01-01

This work presents modeling studies investigating the effects of capillary barriers on fluid-flow and tracer-transport processes in the unsaturated zone of Yucca Mountain, Nevada, a potential site for storing high-level radioactive waste. These studies are designed to identify factors controlling the formation of capillary barriers and to estimate their effects on the extent of possible large-scale lateral flow in unsaturated fracture rocks. The modeling approach is based on a continuum formulation of coupled multiphase fluid and tracer transport through fractured porous rock. Flow processes in fractured porous rock are described using a dual-continuum concept. In addition, approximate analytical solutions are developed and used for assessing capillary-barrier effects in fractured rocks. This study indicates that under the current hydrogeologic conceptualization of Yucca Mountain, strong capillary-barrier effects exist for significantly diverting moisture flow

Quantifying the Effects of Biofilm on the Hydraulic Properties of Unsaturated Soils

Science.gov (United States)

Volk, E.; Iden, S.; Furman, A.; Durner, W.; Rosenzweig, R.

2017-12-01

Quantifying the effects of biofilms on hydraulic properties of unsaturated soils is necessary for predicting water and solute flow in soil with extensive microbial presence. This can be relevant to bioremediation processes, soil aquifer treatment and effluent irrigation. Previous works showed a reduction in the hydraulic conductivity and an increase in water content due to the addition of biofilm analogue materials. The objective of this research is to quantify soil hydraulic properties of unsaturated soil (water retention and hydraulic conductivity) using real soil biofilm. In this work, Hamra soil was incubated with Luria Broth (LB) and biofilm-producing bacteria (Pseudomonas Putida F1). Hydraulic conductivity and water retention were measured by the evaporation method, Dewpoint method and a constant head permeameter. Biofilm was quantified using viable counts and the deficit of TOC. The results show that the presence of biofilms increases soil retention in the `dry' range of the curve and reduces the hydraulic conductivity (see figure). This research shows that biofilms may have a non-negligible effect on flow and transport in unsaturated soils. These findings contribute to modeling water flow in biofilm amended soil.

Flow and transport in unsaturated fractured rock: Effects of multiscale heterogeneity of hydrogeologic properties

International Nuclear Information System (INIS)

Zhou, Quanlin; Liu, Hui-Hai; Bodvarsson, Gudmundur S.; Oldenburg, Curtis M.

2002-01-01

The heterogeneity of hydrogeologic properties at different scales may have different effects on flow and transport processes in a subsurface system. A model for the unsaturated zone of Yucca Mountain, Nevada, is developed to represent complex heterogeneity at two different scales: (1) layer scale corresponding to geologic layering and (2) local scale. The layer-scale hydrogeologic properties are obtained using inverse modeling, based on the available measurements collected from the Yucca Mountain site. Calibration results show a significant lateral and vertical variability in matrix and fracture properties. Hydrogeologic property distributions in a two-dimensional, vertical cross section of the site are generated by combining the average layer-scale matrix and fracture properties with local-scale perturbations generated using a stochastic simulation method. The unsaturated water flow and conservative (nonsorbing) tracer transport through the cross section are simulated for different sets of matrix and fracture property fields. Comparison of simulation results indicates that the local-scale heterogeneity of matrix and fracture properties has a considerable effect on unsaturated flow processes, leading to fast flow paths in fractures and the matrix. These paths shorten the travel time of a conservative tracer from the source (repository) horizon in the unsaturated zone to the water table for small fractions of total released tracer mass. As a result, the local-scale heterogeneity also has a noticeable effect on global tracer transport processes, characterized by an average breakthrough curve at the water table, especially at the early arrival time of tracer mass. However, the effect is not significant at the later time after 20 percent tracer mass reaches the water table. The simulation results also verify that matrix diffusion plays an important role in overall solute transport processes in the unsaturated zone at Yucca Mountain

Consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates.

Science.gov (United States)

Vero, S E; Ibrahim, T G; Creamer, R E; Grant, J; Healy, M G; Henry, T; Kramers, G; Richards, K G; Fenton, O

2014-12-01

The true efficacy of a programme of agricultural mitigation measures within a catchment to improve water quality can be determined only after a certain hydrologic time lag period (subsequent to implementation) has elapsed. As the biophysical response to policy is not synchronous, accurate estimates of total time lag (unsaturated and saturated) become critical to manage the expectations of policy makers. The estimation of the vertical unsaturated zone component of time lag is vital as it indicates early trends (initial breakthrough), bulk (centre of mass) and total (Exit) travel times. Typically, estimation of time lag through the unsaturated zone is poor, due to the lack of site specific soil physical data, or by assuming saturated conditions. Numerical models (e.g. Hydrus 1D) enable estimates of time lag with varied levels of input data. The current study examines the consequences of varied soil hydraulic and meteorological complexity on unsaturated zone time lag estimates using simulated and actual soil profiles. Results indicated that: greater temporal resolution (from daily to hourly) of meteorological data was more critical as the saturated hydraulic conductivity of the soil decreased; high clay content soils failed to converge reflecting prevalence of lateral component as a contaminant pathway; elucidation of soil hydraulic properties was influenced by the complexity of soil physical data employed (textural menu, ROSETTA, full and partial soil water characteristic curves), which consequently affected time lag ranges; as the importance of the unsaturated zone increases with respect to total travel times the requirements for high complexity/resolution input data become greater. The methodology presented herein demonstrates that decisions made regarding input data and landscape position will have consequences for the estimated range of vertical travel times. Insufficiencies or inaccuracies regarding such input data can therefore mislead policy makers regarding

Estimation of folate binding capacity (unsaturated and total) in normal human serum and in β-thalassaemia

International Nuclear Information System (INIS)

Moulopoulos, S.; Mantzos, J.; Gyftaki, E.; Kesse-Elias, M.; Alevizou-Terzaki, V.; Souli-Tsimili, E.

1978-01-01

A method is described for measuring the total serum folate binding capacity (TBC) after treating the serum with urea at pH5.5, the unsaturated serum folate binding capacity (UBC) being determined without treatment with urea. The method was applied to 50 normal controls and 20 patients with homozygous β-thalassaemia. The results show an increase in folate binding capacity after treating the serum with urea in all cases studied. There is no correlation between serum folic acid level and total or unsaturated folate binding capacity or per cent saturation. The method described is a simple and rapid one for screening the different groups studied for saturated and unsaturated specific folate-binding proteins. (author)

Migrations of 60-Co and 137-Cs in Saturated and unsaturated Soil at Serpong Nuclear Research Center

International Nuclear Information System (INIS)

Lubis, E; Untara

1996-01-01

The migrations of 60-Co and 137-Cs in saturated and unsaturated soil at Serpong Nuclear Research Center was investigated. The objectives of this investigation are to find the geological and hydrological parameters, especially for estimating the migrations of radionuclides in porous media with advection-dispersion equations. The result showed that the porosity (η) and density (ρ ) of saturated soil are 27.6% and 1.35 g/cm3, and in the unsaturated soil are 18.9% and 1.41 g/cm3. The coefficients distributions (Kd) of 60-Co and 137-Cs in saturated and unsaturated soil are 1.6 - 8.9 and 3.2 - 7.7 respectively. The hydrodinamic coefficients (Dx) and dispersivity (αx) of C0-60 in saturated and unsaturated soil are 0.85 cm2/second and 2.4 x 10-3 cm, and for 137-Cs are 0.91 cm2/second and 2.54 x 10E3 cm

A simple method to assess unsaturated zone time lag in the travel time from ground surface to receptor.

Science.gov (United States)

Sousa, Marcelo R; Jones, Jon P; Frind, Emil O; Rudolph, David L

2013-01-01

In contaminant travel from ground surface to groundwater receptors, the time taken in travelling through the unsaturated zone is known as the unsaturated zone time lag. Depending on the situation, this time lag may or may not be significant within the context of the overall problem. A method is presented for assessing the importance of the unsaturated zone in the travel time from source to receptor in terms of estimates of both the absolute and the relative advective times. A choice of different techniques for both unsaturated and saturated travel time estimation is provided. This method may be useful for practitioners to decide whether to incorporate unsaturated processes in conceptual and numerical models and can also be used to roughly estimate the total travel time between points near ground surface and a groundwater receptor. This method was applied to a field site located in a glacial aquifer system in Ontario, Canada. Advective travel times were estimated using techniques with different levels of sophistication. The application of the proposed method indicates that the time lag in the unsaturated zone is significant at this field site and should be taken into account. For this case, sophisticated and simplified techniques lead to similar assessments when the same knowledge of the hydraulic conductivity field is assumed. When there is significant uncertainty regarding the hydraulic conductivity, simplified calculations did not lead to a conclusive decision. Copyright © 2012 Elsevier B.V. All rights reserved.

Transient Point Infiltration In The Unsaturated Zone

Science.gov (United States)

Buecker-Gittel, M.; Mohrlok, U.

The risk assessment of leaking sewer pipes gets more and more important due to urban groundwater management and environmental as well as health safety. This requires the quantification and balancing of transport and transformation processes based on the water flow in the unsaturated zone. The water flow from a single sewer leakage could be described as a point infiltration with time varying hydraulic conditions externally and internally. External variations are caused by the discharge in the sewer pipe as well as the state of the leakage itself. Internal variations are the results of microbiological clogging effects associated with the transformation processes. Technical as well as small scale laboratory experiments were conducted in order to investigate the water transport from an transient point infiltration. From the technical scale experiment there was evidence that the water flow takes place under transient conditions when sewage infiltrates into an unsaturated soil. Whereas the small scale experiments investigated the hydraulics of the water transport and the associated so- lute and particle transport in unsaturated soils in detail. The small scale experiment was a two-dimensional representation of such a point infiltration source where the distributed water transport could be measured by several tensiometers in the soil as well as by a selective measurement of the discharge at the bottom of the experimental setup. Several series of experiments were conducted varying the boundary and initial con- ditions in order to derive the important parameters controlling the infiltration of pure water from the point source. The results showed that there is a significant difference between the infiltration rate in the point source and the discharge rate at the bottom, that could be explained by storage processes due to an outflow resistance at the bottom. This effect is overlayn by a decreasing water content decreases over time correlated with a decreasing infiltration

Antiprotozoal Activity of α,β-Unsaturated δ-Lactones: Promising ...

African Journals Online (AJOL)

The parasite resistance and side effects of drugs used to treat protozoal diseases have led to the search for new therapies, both natural and synthetic. Studies have shown that various α,β-unsaturated δ-lactones displayed high antiprotozoal activity and thus are promising compounds for new drug discovery and ...

Unsaturated aldehydes as alkene equivalents in the Diels-Alder reaction

DEFF Research Database (Denmark)

Taarning, Esben; Madsen, Robert

2008-01-01

A one-pot procedure is described for using alpha,beta-unsaturated aldehydes as olefin equivalents in the Diels-Alder reaction. The method combines the normal electron demand cycloaddition with aldehyde dienophiles and the rhodium-catalyzed decarbonylation of aldehydes to afford cyclohexenes...

ENGINEERING ISSUE: IN SITU BIOREMEDIATION OF CONTAMINATED UNSATURATED SUBSURFACE SOILS

Science.gov (United States)

An emerging technology for the remediation of unsaturated subsurface soils involves the use of microorganisms to degrade contaminants which are present in such soils. Understanding the processes which drive in situ bioremediation, as well as the effectiveness and efficiency of th...

Solid waste leach characteristics and contaminant-sediment interactions Volume 2: Contaminant transport under unsaturated moisture contents

International Nuclear Information System (INIS)

Lindenmeier, C.W.; Serne, R.J.; Conca, J.L.

1995-09-01

The objectives of this report and subsequent volumes include describing progress on (1) development and optimization of experimental methods to quantify the release of contaminants from solid wastes and their subsequent interactions with unsaturated sediments and (2) the creation of empirical data that become input parameters to performance assessment (PA) analyses for future Hanford Site disposal units and baseline risk assessments for inactive and existing solid waste disposal units. For this report, efforts focused on developing methodologies to evaluate contaminant transport in Trench 8 (W-5 Burial Ground) sediments under unsaturated (vadose zone) conditions. To accomplish this task, a series of flow-through column tests were run using standard saturated column systems, Wierenga unsaturated column systems (both commercial and modified), and the Unsaturated Flow Apparatus (UFA). The reactants investigated were 85 Sr, 236 U, and 238 U as reactive tracers, and tritium as a non-reactive tracer. Results indicate that for moderately unsaturated conditions (volumetric water contents >50 % of saturation), the Wierenga system performed reasonably well such that long water residence times (50-147 h) were achieved, and reasonably good steady-state flow conditions were maintained. The major drawbacks in using this system for reactive tracer work included (1) the inability to achieve reproducible and constant moisture content below 50% of saturation, (2) the four to six month time required to complete a single test, and (3) the propensity for mechanical failure resulting from laboratory power outages during the prolonged testing period

Stereoselective synthesis of unsaturated α-amino acids.

Science.gov (United States)

Fanelli, Roberto; Jeanne-Julien, Louis; René, Adeline; Martinez, Jean; Cavelier, Florine

2015-06-01

Stereoselective synthesis of unsaturated α-amino acids was performed by asymmetric alkylation. Two methods were investigated and their enantiomeric excess measured and compared. The first route consisted of an enantioselective approach induced by the Corey-Lygo catalyst under chiral phase transfer conditions while the second one involved the hydroxypinanone chiral auxiliary, both implicating Schiff bases as substrate. In all cases, the use of a prochiral Schiff base gave higher enantiomeric excess and yield in the final desired amino acid.

Review of Upscaling Methods for Describing Unsaturated Flow

Energy Technology Data Exchange (ETDEWEB)

BD Wood

2000-09-26

The representation of small-scale features can be a challenge when attempting to model unsaturated flow in large domains. Upscaling methods offer the possibility of reducing the amount of resolution required to adequately simulate such a problem. In this report, the various upscaling techniques that are discussed in the literature are reviewed. The following upscaling methods have been identified from the literature: (1) stochastic methods, (2) renormalization methods, and (3) volume averaging and homogenization methods; in addition, a final technique, full resolution numerical modeling, is also discussed. Each of these techniques has its advantages and disadvantages. The trade-off is a reduction in accuracy in favor of a method that is easier to employ. For practical applications, the most reasonable approach appears to be one in which any of the upscaling methods identified above maybe suitable for upscaling in regions where the variations in the parameter fields are small. For regions where the subsurface structure is more complex, only the homogenization and volume averaging methods are probably suitable. With the continual increases in computational capacity, fill-resolution numerical modeling may in many instances provide a tractable means of solving the flow problem in unsaturated systems.

Measurement of unsaturated hydraulic properties and evaluation of property-transfer models for deep sedimentary interbeds, Idaho National Laboratory, Idaho

Science.gov (United States)

Perkins, Kimberlie; Johnson, Brittany D.; Mirus, Benjamin B.

2014-01-01

Operations at the Idaho National Laboratory (INL) have the potential to contaminate the underlying Eastern Snake River Plain (ESRP) aquifer. Methods to quantitatively characterize unsaturated flow and recharge to the ESRP aquifer are needed to inform water-resources management decisions at INL. In particular, hydraulic properties are needed to parameterize distributed hydrologic models of unsaturated flow and transport at INL, but these properties are often difficult and costly to obtain for large areas. The unsaturated zone overlying the ESRP aquifer consists of alternating sequences of thick fractured volcanic rocks that can rapidly transmit water flow and thinner sedimentary interbeds that transmit water much more slowly. Consequently, the sedimentary interbeds are of considerable interest because they primarily restrict the vertical movement of water through the unsaturated zone. Previous efforts by the U.S. Geological Survey (USGS) have included extensive laboratory characterization of the sedimentary interbeds and regression analyses to develop property-transfer models, which relate readily available physical properties of the sedimentary interbeds (bulk density, median particle diameter, and uniformity coefficient) to water retention and unsaturated hydraulic conductivity curves.

(Bio-)remediation of VCHC contaminants in a Technosol under unsaturated conditions.

Science.gov (United States)

Baumgarten, W; Fleige, H; Peth, S; Horn, R

2013-07-01

The remediation of dense non-aqueous phase liquids has always been a concern of both public and scientific interest groups. In this research work a modified physical concept of (bio)remediation of a volatile chlorinated hydrocarbon (VCHC) contamination was elaborated under laboratory conditions and modeled with HYDRUS-2D. In field dechlorination is influenced by both physicochemical and hydraulic properties of the substrate, e.g. texture, pore size distribution, pore liquid characteristics, e.g. viscosity, pH, surface tension, and dependent on the degree of saturation of the vadose zone. Undisturbed soil cores (100 cm³) were sampled from a Spolic Technosol. Considering hydraulic properties and functions, unsaturated percolation was performed with vertically and horizontally structured samples. VCHC concentrations were calculated prior, during, and after each percolation cycle. According to laboratory findings, microemulsion showed the most efficient results with regard to flow behavior in the unsaturated porous media and its accessibility for bacteria as nutrient. The efficiency of VCHC remediation could be increased by the application of a modified pump-and-treat system: the injection of bacteria Dehalococcoides ethanogenes with microemulsion, and extraction at a constant matric potential level of -6 kPa. Achieved data was used for HYDRUS-2D simulations, modeling in situ conditions, demonstrating the practical relevance (field scale) of performed unsaturated percolation (core scale), and in order to exclude capillary barrier effects.

Low temperature irradiation of vitrifiable mixtures of unsaturated monomers

International Nuclear Information System (INIS)

Kaetsu, I.; Ito, A.; Hayashi, K.

1975-01-01

A specific mixture containing at least one polymerizable unsaturated monomer which is not vitrifiable by itself can advantageously be polymerized by irradiating the mixture at a temperature not higher than 100 0 C above glass transition temperature of the mixture with an ionizing radiation and/or a light. 12 claims, 6 drawings, figures

Movement of pentachlorophenol in unsaturated soil by electrokinetics

Energy Technology Data Exchange (ETDEWEB)

Harbottle, M.; Sills, G. [Dept. of Engineering Science, Oxford (United Kingdom); Jackman, S. [Dept. of Engineering Science, Oxford (United Kingdom)]|[NERC Centre for Ecology and Hydrology, Oxford (United Kingdom); Thompson, I. [NERC Centre for Ecology and Hydrology, Oxford (United Kingdom)

2001-07-01

Electrokinetic experiments have been performed on unsaturated natural soil specimens artificially contaminated with pentachlorophenol. Movement of pentachlorophenol within the soil mass has been demonstrated, but no contaminant was discovered in any effluent fluids. The results indicate that it may be possible to improve the bioavailability of the pollutant to degradative microorganisms using electrokinetics, by moving the chemical and microbes relative to each others. (orig.)

Screening of Chlorinated Paraffins and Unsaturated Analogues in Commercial Mixtures: Confirmation of Their Occurrences in the Atmosphere.

Science.gov (United States)

Li, Tong; Gao, Shixiong; Ben, Yujie; Zhang, Hong; Kang, Qiyue; Wan, Yi

2018-02-20

Characterizing the detailed compositions of chlorinated paraffins (CPs) commercial mixtures is crucial to understand their environmental sources, fates, and potential risks. In this study, dichloromethane (DCM)-enhanced UPLC-ESI-QTOFMS analysis combined with characteristic isotope chlorine peaks is applied to screen all CPs and their structural analogues in the three most commonly produced CP commercial mixtures (CP-42, CP-52, and CP-70). Mass fractions of total short-chain CPs (SCCPs), medium-chain CPs (MCCPs) and long-chain CPs (LCCPs) ranged from 0.64 to 31.9%, 0.64 to 21.8%, and 0.04 to 43.9%, respectively, in the three commercial mixtures. 113 unsaturated SCCPs, MCCPs, and LCCPs were identified in the commercial mixtures. The detailed mass percentages of saturated and unsaturated CPs with carbon numbers of 10-30, chlorine numbers of 5-28, and unsaturated degrees of 0-7 were characterized in all commercial mixtures. Occurrences of the predominant saturated and unsaturated CPs were further confirmed in air samples collected in Guangdong Province, one of the major CP production areas in China, over one year. The profiles of the detected compounds indicated that LCCPs in air samples might come mainly from the production and usage of CP-52, and unsaturated C 24-29 -LCCPs were specifically originated from CP-70 used in the area.

Electrokinetic remediation of anionic contamination from unsaturated soil: Field application

International Nuclear Information System (INIS)

Lindgren, E.R.; Mattson, E.D.

1995-01-01

Electrokinetic remediation is an in situ technique under development at Sandia National Laboratories for removal of ionic contaminants from soil. While to date most other studies of this technique have focused on saturated soils, usually clays, the work at Sandia has been to extend the process to unsaturated sandy soils typical of arid regions. The impetus for this study is a chromate plume located beneath an old Sandia chemical waste landfill. Working in unsaturated soils is complicated by moisture control requirements, both to prevent undesired hydraulic transport of contamination outside the treatment zone and to optimize soil properties for efficient electrokinetic remediation. Two field tests will be discussed. First, a field test in clean soil is in progress to demonstrate moisture control with the Sandia electrode system. The second field demonstration, planned to begin the Fall of 1995, involves chromate removal from a in a chemical waste landfill

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Directory of Open Access Journals (Sweden)

Katherine M. Byrd

2015-04-01

Full Text Available The conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

Synthesis and investigation of new heteronuclear [Zn-La] coordination compounds based on unsaturated lanthanum complex with N,N'-tetraethyl-N''-trichloacetylphosphortriamide

International Nuclear Information System (INIS)

Amyirkhanov, O.V.; Sliva, T.Yu.; Moroz, O.V.; Trush, Je.A.; Frits'kij, Yi.O.

2011-01-01

New heteronuclear [Zn-La] coordination compounds, perspective luminescent materials, with general formulas [Zn(Ve)La(X) 2 (Ac)] ({Zn-La;Ve;X}) and [Zn(Vp)La(X) 2 (Ac)] ({Zn-La;Vp;X}) have been synthesized HX=CCl 3 C(O)NHP(O)[N(C 2 H 5 ) 2 ] 2 - N,N'-tetraethyl-N''-trichloracetylphosphortriamide, H 2 Ve and H 2 Vp are products of the condensation of 1,2-diaminoethane and 1,3-diaminopropane with o-vanillin, respectively). The composition of [Zn-La] complexes has been determined, and the coordination mode of a phosphorylated ligand has been suggested by element analysis, IR- and 1 H, 31 P NMR-spectroscopy.

Relating shear strength of unsaturated soils with capillary water retention curve

Directory of Open Access Journals (Sweden)

Zhou Annan

2016-01-01

Full Text Available This paper proposes a new water retention model for unsaturated soils, which takes into account capillary condensation of adsorbed water. In the proposed water retention model, the degree of saturation of a soil is separated into that based on capillary water and that based on adsorbed water. Through the analysis of a partially saturated two-cylinder system, a new shear strength criterion for unsaturated soils is proposed, in which only the degree of saturation based on capillary water contributes to the variation of shear strength with suction. The proposed shear strength criterion is justified against thermodynamic principles. The proposed strength criterion is compared against existing criteria in the literature, which shows that it provides a much improved prediction of the experimental data, for a wide range of suction values.

Total fatty acid content of the plasma membrane of Saccharomyces cerevisiae is more responsible for ethanol tolerance than the degree of unsaturation.

Science.gov (United States)

Kim, Hyun-Soo; Kim, Na-Rae; Choi, Wonja

2011-03-01

The effect of change in unsaturated fatty acid composition on ethanol tolerance in Saccharomyces cerevisiae overexpressing ScOLE1 (∆9 fatty acid desaturase gene of S. cerevisiae), CaFAD2 (∆12 fatty acid desaturase gene of Candida albicans), or CaFAD3 (ω3 fatty acid desaturase gene of C. albicans) was examined. ScOLE1 over-expression increased the total unsaturated fatty acid content and enhanced ethanol tolerance, compared with a control strain. In contrast, overexpression of CaFAD2 and CaFAD3, which led to production of linoleic acid (18:2) and α-linolenic acid (18:3), respectively, neither changed total unsaturated fatty acids nor enhanced ethanol tolerance. The total unsaturated fatty acid content rather than the degree of unsaturation is thus an important factor for ethanol tolerance.

Study of reactive solutes transport and PAH migration in unsaturated soils

International Nuclear Information System (INIS)

Gujisaite, V.; Simonnot, M.O.; Gujisaite, V.; Morel, J.L.; Ouvrard, S.; Simonnot, M.O.; Gaudet, J.P.

2005-01-01

Experimental studies about solute transport in soil have most of the time been conducted under saturated conditions, whereas studies with unsaturated media are usually limited to hydrodynamic analysis. Those are mainly concerning the prediction of water flow, which is the main vector for the transport of contaminants in soil. Only a few studies have made the link between unsaturated flow and physical, chemical and biological interactions, which are controlling the availability of pollutants. However, the presence of a gaseous phase in soil can modify not only the movement of soil solution, but also chemical interactions and exchanges between soil aggregates and solution. Study of reactive solute transport in the vadose zone seems thus to be a necessary stage to predict contaminant fate in natural soils, for risk assessment as well as for the design of effective processes for the remediation of contaminated soils. This question is the main objective of the present work developed in the frame of our French Scientific Interest Group Industrial Wastelands called 'GISFI' (www.gisfi.prd.fr), based around a scientific and technological project dedicated to acquisition of knowledge for sustainable requalification of degraded sites polluted by past industrial activities. We will focus here on Polycyclic Aromatic Hydrocarbons (PAH), which are among the most widely discussed environmental contaminants because of their toxicity for human health and ecosystems. They are present in large quantities in soils polluted by former industrial activities, especially in relation to the coal extraction, exploitation and treatment. An experimental system has been specifically designed at the laboratory scale to carry out experiments under controlled conditions, with an unsaturated steady-state flow. The first experiments are performed on model soils, in order to investigate unsaturated steady-state flow in relation to interactions mechanisms. We have thus chosen to use a sandy

Three-dimensional saturated-unsaturated flow with axial symmetry to a partially penetrating well in a compressible unconfined aquifer

Science.gov (United States)

Tartakovsky, Guzel D.; Neuman, Shlomo P.

2007-01-01

A new analytical solution is presented for the delayed response process characterizing flow to a partially penetrating well in an unconfined aquifer. The new solution generalizes that of Neuman (1972, 1974) by accounting for unsaturated flow above the water table. Three-dimensional, axially symmetric flow in the unsaturated zone is described by a linearized version of Richards' equation in which hydraulic conductivity and water content vary exponentially with incremental capillary pressure head relative to its air entry value (defining the interface between the saturated and unsaturated zones). Unsaturated soil properties are characterized by an exponent κ having the dimension of inverse length or, equivalently, a dimensionless exponent κD = κb, where b is initial saturated thickness. Our treatment of the unsaturated zone is similar to that of Kroszynski and Dagan (1975), who, however, have ignored internal (artesian) aquifer storage. According to Kroszynski and Dagan, aquifers that are not excessively shallow have values of κD (their parameter a) much greater than 10. We find that in such typical cases, unsaturated flow has little impact on early and late dimensionless time drawdown a short distance below the water table. Unsaturated flow causes drawdown to increase slightly at intermediate dimensionless time values that represent transition from an early artesian-dominated to a late water-table-dominated flow regime. Delayed drainage from the unsaturated zone becomes less and less important as κD increases; as κD → ∞, this effect dies out, and drawdown is controlled entirely by delayed decline in the water table as in the model of Neuman. The unsaturated zone has a major impact on drawdown at intermediate time and a significant impact at early and late times, in the atypical case of κD ≤ 1, becoming the dominant factor as κD approaches zero (the soil water retention capacity becomes very large and/or saturated thickness becomes insignificant). Our

Development of sugar palm yarn/glass fibre reinforced unsaturated polyester hybrid composites

Science.gov (United States)

Nurazzi, N. Mohd; Khalina, A.; Sapuan, S. Mohd; Rahmah, M.

2018-04-01

This study investigates the effect of fibre hybridization for sugar palm yarn fibre with glass fibre reinforced with unsaturated polyester composites. In this work, unsaturated polyester resin are reinforced with fibre at a ratio of 70:30 wt% and 60:40 wt%. The hybrid composites were characterized in terms of physical (density and water absorption), mechanical (tensile, flexural and compression) and thermal properties through thermal gravimetry analysis (TGA). Density determination showed that density increased with higher wt% of glass fibre. The inherently higher density of glass fibre increased the density of hybrid composite. Resistance to water absorption is improved upon the incorporation of glass fibre and the hybrid composites were found to reach equilibrium absorption at days 4 and 5. As for mechanical performance, the highest tensile strength, tensile modulus, flexural strength, flexural modulus and compression strength were obtained from 40 wt% of fibres reinforcement with ratio of 50:50 wt% of sugar palm yarn fibre and glass fibre reinforced unsaturated polyester composites. The increase of glass fibre loading had a synergistic effect on the mechanical properties to the composites structure due to its superior strength and modulus. The thermal stability of hybrid composites was improved by the increase of onset temperature and the reduction of residues upon increase in temperature.

Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation

DEFF Research Database (Denmark)

Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan

2001-01-01

The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase in the inc......The oxidation of pyrite (FeS2) contained in unsaturated aquifer sediment was studied by sediment incubation in gas impermeable polymer laminate bags. Reaction progress was followed over a period of nearly 2 months by monitoring the gas composition within the laminate bag. The gas phase...... in the incubation bags became depleted in O2 and enriched in CO2 and N2 and was interpreted as due to pyrite oxidation in combination with calcite dissolution. Sediment incubation provides a new method to estimate low rates of pyrite oxidation in unsaturated zone aquifer sediments. Oxidation rates of up to 9.4â10......-10 mol FeS2/gâs are measured, and the rates are only weakly correlated with the sediment pyrite content. The reactivity of pyrite, including the inhibition by FeOOH layers formed on its surface, apparently has a major effect on the rate of oxidation. The code PHREEQC 2.0 was used to calculate...

Biodiesel unsaturation degree effects on diesel engine NOx emissions and cotton wick flame temperature

Directory of Open Access Journals (Sweden)

Abdullah Mohd Fareez Edzuan

2017-01-01

Full Text Available As compared with conventional diesel fuel, biodiesel has better lubricity and lower particulate matter (PM emissions however nitrogen oxides (NOx emissions generally increase in biodiesel-fuelled diesel engine. Strict regulation on NOx emissions is being implemented in current Euro 6 standard and it is expected to be tighter in next standard, thus increase of NOx cannot be accepted. In this study, biodiesel unsaturation degree effects on NOx emissions are investigated. Canola, palm and coconut oils are selected as the feedstock based on their unsaturation degree. Biodiesel blends of B20 were used to fuel a single cylinder diesel engine and exhaust emissions were sampled directly at exhaust tailpipe with a flue gas analyser. Biodiesel flame temperature was measured from a cotton wick burned in simple atmospheric conditions using a thermocouple. Fourier transform infrared (FTIR spectrometer was also used to identify the functional groups presence in the biodiesel blends. Oxygen content in biodiesel may promote complete combustion as the NOx emissions and flame temperatures were increased while the carbon monoxide (CO emissions were decreased for all biodiesel blends. It is interesting to note that the NOx emissions and flame temperatures were directly proportional with biodiesel unsaturation degree. It might be suggested that apart from excess oxygen and free radical formation, higher NOx emissions can also be caused by the elevated flame temperatures due to the presence of double bonds in unsaturated biodiesel.

Multimodel analysis of anisotropic diffusive tracer-gas transport in a deep arid unsaturated zone

Science.gov (United States)

Green, Christopher T.; Walvoord, Michelle Ann; Andraski, Brian J.; Striegl, Robert G.; Stonestrom, David A.

2015-01-01

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

SYNTHESIS OF 2,3-UNSATURATED FURANIC HEX- AND PENT ...

African Journals Online (AJOL)

a

[12] and reduction in two steps of 3-(2-furyl)-acrolein[13] in good yields. The reaction of alcohols 2a-e with glucal 1, carried out in presence of boron trifluoride [7]. (method A), ferric chloride [11] (method B) and CAN [10] (method C), afforded the corresponding 2,3-unsaturated glucopyranosides 3a-e (Table 1). Table 1.

Modelling of the partial oxidation of {alpha}, {beta}-unsaturated aldehydes on Mo-V-oxides based catalysts

Energy Technology Data Exchange (ETDEWEB)

Boehnke, H.; Petzoldt, J.C.; Stein, B.; Weimer, C.; Gaube, J.W. [Technische Univ. Darmstadt (Germany). Inst. fuer Chemische Technologie

1998-12-31

A kinetic model based on the Mars-van Krevelen mechanism that allows to describe the microkinetics of the heterogeneously catalysed partial oxidation of {alpha}, {beta}-unsaturated aldehydes is presented. This conversion is represented by a network, composed of the oxidation of the {alpha}, {beta}-unsaturated aldehyde towards the {alpha}, {beta}-unsaturated carboxylic acid and the consecutive oxidation of the acid as well as the parallel reaction of the aldehyde to products of deeper oxidation. The reaction steps of aldehyde respectively acid oxidation and catalyst reoxidation have been investigated separately in transient experiments. The combination of steady state and transient experiments has led to an improved understanding of the interaction of the catalyst with the aldehyde and the carboxylic acids as well as to a support of the kinetic model assumptions. (orig.)

Moditored unsaturated soil transport processes as a support for large scale soil and water management

Science.gov (United States)

Vanclooster, Marnik

2010-05-01

The current societal demand for sustainable soil and water management is very large. The drivers of global and climate change exert many pressures on the soil and water ecosystems, endangering appropriate ecosystem functioning. The unsaturated soil transport processes play a key role in soil-water system functioning as it controls the fluxes of water and nutrients from the soil to plants (the pedo-biosphere link), the infiltration flux of precipitated water to groundwater and the evaporative flux, and hence the feed back from the soil to the climate system. Yet, unsaturated soil transport processes are difficult to quantify since they are affected by huge variability of the governing properties at different space-time scales and the intrinsic non-linearity of the transport processes. The incompatibility of the scales between the scale at which processes reasonably can be characterized, the scale at which the theoretical process correctly can be described and the scale at which the soil and water system need to be managed, calls for further development of scaling procedures in unsaturated zone science. It also calls for a better integration of theoretical and modelling approaches to elucidate transport processes at the appropriate scales, compatible with the sustainable soil and water management objective. Moditoring science, i.e the interdisciplinary research domain where modelling and monitoring science are linked, is currently evolving significantly in the unsaturated zone hydrology area. In this presentation, a review of current moditoring strategies/techniques will be given and illustrated for solving large scale soil and water management problems. This will also allow identifying research needs in the interdisciplinary domain of modelling and monitoring and to improve the integration of unsaturated zone science in solving soil and water management issues. A focus will be given on examples of large scale soil and water management problems in Europe.

Production of highly unsaturated fatty acids using agro-processing by-products

CSIR Research Space (South Africa)

Jacobs, A

2008-11-01

Full Text Available The South African agro-processing industry generates millions of tons of cereal derived by-products annually. The by-products from biofuel production are expected to increase these volumes dramatically. Highly unsaturated fatty acids (HUFA...

Role of Unsaturated Lipid and Ergosterol in Ethanol Tolerance of Model Yeast Biomembranes

KAUST Repository

Vanegas, Juan M.

2012-02-07

We present a combined atomic force microscopy and fluorescence microscopy study of the behavior of a ternary supported lipid bilayer system containing a saturated lipid (DPPC), an unsaturated lipid (DOPC), and ergosterol in the presence of high ethanol (20 vol %). We find that the fluorescent probe Texas Red DHPE preferentially partitions into the ethanol-induced interdigitated phase, which allows the use of fluorescence imaging to investigate the phase behavior of the system. Atomic force microscopy and fluorescence images of samples with the same lipid mixture show good agreement in sample morphology and area fractions of the observed phases. Using area fractions obtained from fluorescence images over a broad range of compositions, we constructed a phase diagram of the DPPC/DOPC/ergosterol system at 20 vol % ethanol. The phase diagram clearly shows that increasing unsaturated lipid and/or ergosterol protects the membrane by preventing the formation of the interdigitated phase. This result supports the hypothesis that yeast cells increase ergosterol and unsaturated lipid content to prevent interdigitation and maintain an optimal membrane thickness as ethanol concentration increases during anaerobic fermentations. Changes in plasma membrane composition provide an important survival factor for yeast cells to deter ethanol toxicity.

Role of Unsaturated Lipid and Ergosterol in Ethanol Tolerance of Model Yeast Biomembranes

KAUST Repository

Vanegas, Juan  M.; Contreras, Maria F.; Faller, Roland; Longo, Marjorie  L.

2012-01-01

We present a combined atomic force microscopy and fluorescence microscopy study of the behavior of a ternary supported lipid bilayer system containing a saturated lipid (DPPC), an unsaturated lipid (DOPC), and ergosterol in the presence of high ethanol (20 vol %). We find that the fluorescent probe Texas Red DHPE preferentially partitions into the ethanol-induced interdigitated phase, which allows the use of fluorescence imaging to investigate the phase behavior of the system. Atomic force microscopy and fluorescence images of samples with the same lipid mixture show good agreement in sample morphology and area fractions of the observed phases. Using area fractions obtained from fluorescence images over a broad range of compositions, we constructed a phase diagram of the DPPC/DOPC/ergosterol system at 20 vol % ethanol. The phase diagram clearly shows that increasing unsaturated lipid and/or ergosterol protects the membrane by preventing the formation of the interdigitated phase. This result supports the hypothesis that yeast cells increase ergosterol and unsaturated lipid content to prevent interdigitation and maintain an optimal membrane thickness as ethanol concentration increases during anaerobic fermentations. Changes in plasma membrane composition provide an important survival factor for yeast cells to deter ethanol toxicity.

Lithological Effects on Evaporation and Direct Infiltration Through the Unsaturated Zone in Damascus Oasis (Syria)

International Nuclear Information System (INIS)

Abou zakhem, B.

2004-01-01

Soil water movement is directly affected by the lithology and texture of soil profile. The objective of this study is to determine water movement mechanism through the unsaturated zone, by estimating the direct infiltration rate and evaporation process in Damascus Oasis, using isotope techniques. Two soil profiles were drilled using a hand-auger. Soil samples were subjected to granulometry, mineralogy, chemical and isotopic analysis. Isotopic measurements indicate that the evaporation front is located at shallow depth between 0 and 2 m. Variations in isotopic content indicate to the alternation of wet and dry periods corresponding to infiltration and evaporation processes respectively. Results show considerable difference in isotopic content between the unsaturated zone and the groundwater, which is mainly attributed to limited recharge of the aquifer through the unsaturated. Whereas the indirect groundwater recharge is considered to be more predominant. Chloride concentration correspond to stable isotopes in the unsaturated zone, it increases proportionally with the evaporation rate. Using chemical balance of Chloride, it was possible to estimate the effective recharge average rate which is ranging between 1.8 mm/y and 0.45 mm/y. The calculated mean evaporation rate according to Barnes and Allison model is 18.1 mm/y at water table level of 3 m depth. This rate decreases to 2.4 mm/y at 6 m depth. (author)

Method of coupling 1-D unsaturated flow with 3-D saturated flow on large scale

Directory of Open Access Journals (Sweden)

Yan Zhu

2011-12-01

Full Text Available A coupled unsaturated-saturated water flow numerical model was developed. The water flow in the unsaturated zone is considered the one-dimensional vertical flow, which changes in the horizontal direction according to the groundwater table and the atmospheric boundary conditions. The groundwater flow is treated as the three-dimensional water flow. The recharge flux to groundwater from soil water is considered the bottom flux for the numerical simulation in the unsaturated zone, and the upper flux for the groundwater simulation. It connects and unites the two separated water flow systems. The soil water equation is solved based on the assumed groundwater table and the subsequent predicted recharge flux. Then, the groundwater equation is solved with the predicted recharge flux as the upper boundary condition. Iteration continues until the discrepancy between the assumed and calculated groundwater nodal heads have a certain accuracy. Illustrative examples with different water flow scenarios regarding the Dirichlet boundary condition, the Neumann boundary condition, the atmospheric boundary condition, and the source or sink term were calculated by the coupled model. The results are compared with those of other models, including Hydrus-1D, SWMS-2D, and FEFLOW, which demonstrate that the coupled model is effective and accurate and can significantly reduce the computational time for the large number of nodes in saturated-unsaturated water flow simulation.

Particle tracking for unsaturated-zone groundwater travel time analysis at Yucca Mountain

International Nuclear Information System (INIS)

Arnold, B.W.; Skinner, L.H.; Zieman, N.B.

1995-01-01

A particle tracking code developed to link numerical modeling of groundwater flow in the unsaturated zone to the analysis of groundwater travel times was used to produce preliminary estimates of the distribution of groundwater-travel time from a potential repository at Yucca Mountain, Nevada to the water table. Compliance with 10CFR960 requires the demonstration that pre-waste-emplacement groundwater travel time from the disturbed zone to the accessible environment is expected to exceed 1,000 years along any path of likely and significant radionuclide travel. The use of multiple particles and multiple realizations of the geology and parameter distributions in the unsaturated zone allows a probabilistic analysis of groundwater travel times that may be applied for evaluating compliance

Barriers to bacterial motility on unsaturated surfaces

DEFF Research Database (Denmark)

Dechesne, Arnaud; Smets, Barth F.

2013-01-01

Our knowledge of the spatial organization and spatial dynamics of microbial populations in soil at a scale close to that of the microorganisms is scarce. While passive dispersal via water ow or soil biota is probably a major dispersal route, it is reasonable to consider that active dispersal also...... and their isogenic mutants unable to express various type of motility we aimed to quantify the physical limits of bacterial motility. Our results demonstrate how hydration controls bacterial motility under unsaturated conditions. They can form the base of improved biodegradation models that include microbial...

Transport of elemental mercury in the unsaturated zone from a waste disposal site in an arid region

Science.gov (United States)

Walvoord, Michelle Ann; Andraski, Brian J.; Krabbenhoft, D.P.; Striegl, Robert G.

2008-01-01

Mercury contained in buried landfill waste may be released via upward emission to the atmosphere or downward leaching to groundwater. Data from the US Geological Survey’s Amargosa Desert Research Site (ADRS) in arid southwestern Nevada reveal another potential pathway of Hg release: long-distance (102 m) lateral migration of elemental Hg (Hg0) through the unsaturated zone. Gas collected from multiple depths from two instrumented boreholes that sample the entire 110-m unsaturated zone thickness and are located 100 and 160 m away from the closest waste burial trench exhibit gaseous Hg concentrations of up to 33 and 11 ng m−3, respectively. The vertical distribution of gaseous Hg in the borehole closest to the disposal site shows distinct subsurface peaks in concentration at depths of 1.5 and 24 m that cannot be explained by radial diffusive transport through a heterogeneous layered unsaturated zone. The inability of current models to explain gaseous Hg distribution at the ADRS highlights the need to advance the understanding of gas-phase contaminant transport in unsaturated zones to attain a comprehensive model of landfill Hg release.

Monte Carlo simulation of nonlinear reactive contaminant transport in unsaturated porous media

International Nuclear Information System (INIS)

Giacobbo, F.; Patelli, E.

2007-01-01

In the current proposed solutions of radioactive waste repositories, the protective function against the radionuclide water-driven transport back to the biosphere is to be provided by an integrated system of engineered and natural geologic barriers. The occurrence of several nonlinear interactions during the radionuclide migration process may render burdensome the classical analytical-numerical approaches. Moreover, the heterogeneity of the barriers' media forces approximations to the classical analytical-numerical models, thus reducing their fidelity to reality. In an attempt to overcome these difficulties, in the present paper we adopt a Monte Carlo simulation approach, previously developed on the basis of the Kolmogorov-Dmitriev theory of branching stochastic processes. The approach is here extended for describing transport through unsaturated porous media under transient flow conditions and in presence of nonlinear interchange phenomena between the liquid and solid phases. This generalization entails the determination of the functional dependence of the parameters of the proposed transport model from the water content and from the contaminant concentration, which change in space and time during the water infiltration process. The corresponding Monte Carlo simulation approach is verified with respect to a case of nonreactive transport under transient unsaturated flow and to a case of nonlinear reactive transport under stationary saturated flow. Numerical applications regarding linear and nonlinear reactive transport under transient unsaturated flow are reported

The Role of Surface Infiltration in Hydromechanical Coupling Effects in an Unsaturated Porous Medium of Semi-Infinite Extent

Directory of Open Access Journals (Sweden)

L. Z. Wu

2017-01-01

Full Text Available Rainfall infiltration into an unsaturated region of the earth’s surface is a pervasive natural phenomenon. During the rainfall-induced seepage process, the soil skeleton can deform and the permeability can change with the water content in the unsaturated porous medium. A coupled water infiltration and deformation formulation is used to examine a problem related to the mechanics of a two-dimensional region of semi-infinite extent. The van Genuchten model is used to represent the soil-water characteristic curve. The model, incorporating coupled infiltration and deformation, was developed to resolve the coupled problem in a semi-infinite domain based on numerical methods. The numerical solution is verified by the analytical solution when the coupled effects in an unsaturated medium of semi-infinite extent are considered. The computational results show that a numerical procedure can be employed to examine the semi-infinite unsaturated seepage incorporating coupled water infiltration and deformation. The analysis indicates that the coupling effect is significantly influenced by the boundary conditions of the problem and varies with the duration of water infiltration.

Effects from Unsaturated Zone Flow during Oscillatory Hydraulic Testing

Science.gov (United States)

Lim, D.; Zhou, Y.; Cardiff, M. A.; Barrash, W.

2014-12-01

In analyzing pumping tests on unconfined aquifers, the impact of the unsaturated zone is often neglected. Instead, desaturation at the water table is often treated as a free-surface boundary, which is simple and allows for relatively fast computation. Richards' equation models, which account for unsaturated flow, can be compared with saturated flow models to validate the use of Darcy's Law. In this presentation, we examine the appropriateness of using fast linear steady-periodic models based on linearized water table conditions in order to simulate oscillatory pumping tests in phreatic aquifers. We compare oscillatory pumping test models including: 1) a 2-D radially-symmetric phreatic aquifer model with a partially penetrating well, simulated using both Darcy's Law and Richards' Equation in COMSOL; and 2) a linear phase-domain numerical model developed in MATLAB. Both COMSOL and MATLAB models are calibrated to match oscillatory pumping test data collected in the summer of 2013 at the Boise Hydrogeophysical Research Site (BHRS), and we examine the effect of model type on the associated parameter estimates. The results of this research will aid unconfined aquifer characterization efforts and help to constrain the impact of the simplifying physical assumptions often employed during test analysis.

Estimating the timing and location of shallow rainfall-induced landslides using a model for transient, unsaturated infiltration

Science.gov (United States)

Baum, Rex L.; Godt, Jonathan W.; Savage, William Z.

2010-01-01

Shallow rainfall-induced landslides commonly occur under conditions of transient infiltration into initially unsaturated soils. In an effort to predict the timing and location of such landslides, we developed a model of the infiltration process using a two-layer system that consists of an unsaturated zone above a saturated zone and implemented this model in a geographic information system (GIS) framework. The model links analytical solutions for transient, unsaturated, vertical infiltration above the water table to pressure-diffusion solutions for pressure changes below the water table. The solutions are coupled through a transient water table that rises as water accumulates at the base of the unsaturated zone. This scheme, though limited to simplified soil-water characteristics and moist initial conditions, greatly improves computational efficiency over numerical models in spatially distributed modeling applications. Pore pressures computed by these coupled models are subsequently used in one-dimensional slope-stability computations to estimate the timing and locations of slope failures. Applied over a digital landscape near Seattle, Washington, for an hourly rainfall history known to trigger shallow landslides, the model computes a factor of safety for each grid cell at any time during a rainstorm. The unsaturated layer attenuates and delays the rainfall-induced pore-pressure response of the model at depth, consistent with observations at an instrumented hillside near Edmonds, Washington. This attenuation results in realistic estimates of timing for the onset of slope instability (7 h earlier than observed landslides, on average). By considering the spatial distribution of physical properties, the model predicts the primary source areas of landslides.

New Class of Solutions for Water Infiltration Problems in Unsaturated Soils

DEFF Research Database (Denmark)

Barari, Amin; Omidvar, M; Momeni, M

2010-01-01

This paper presents the results of approximate analytical solutions to Richards’ equation, which governs the problem of unsaturated flow in porous media. The existing methods generally fall within the category of numerical and analytical methods, often having many restrictions for practical situa...

Geochemical modelling of hydrogen gas migration in an unsaturated bentonite buffer

NARCIS (Netherlands)

Sedighi, M.; Thomas, H.R.; Al Masum, S.; Vardon, P.J.; Nicholson, D.; Chen, Q.

2014-01-01

This paper presents an investigation of the transport and fate of hydrogen gas through compacted bentonite buffer. Various geochemical reactions that may occur in the multiphase and multicomponent system of the unsaturated bentonite buffer are considered. A reactive gas transport model, developed

Design of dry barriers for containment of contaminants in unsaturated soils

International Nuclear Information System (INIS)

Morris, C.E.; Thomson, B.M.; Stormont, J.C.

1997-01-01

A dry barrier is a region of very dry conditions in unsaturated soil that prevents vertical migration of water created by circulating dry air through the formation. Dry soil creates a barrier to vertical water movement by decreasing the soil's hydraulic conductivity, a concept also used in capillary barriers. A dry barrier may be a viable method for providing containment of a contaminant plume in a setting with a thick unsaturated zone and dry climate. The principal factors which determine the feasibility of a dry barrier include: (1) an and environment, (2) thick vadose zone, and (3) the ability to circulate air through the vadose zone. This study investigated the technical and economic considerations associated with creating a dry barrier to provide containment of a hypothetical 1 ha aqueous contaminant plume. The concept appears to be competitive with other interim containment methods such as ground freezing

Development of methods to evaluate uranium distribution coefficients in unsaturated media

International Nuclear Information System (INIS)

Sautman, M.T.; Simonson, S.A.

1993-01-01

To date, batch sorption and dynamic column experiments have been performed for many elements as part of site characterization programs. These experiments were often conducted with samples having relatively high liquid/solid ratios (in some cases the solid volume was much smaller than the solution volume). The development of methods for measuring sorption parameters at low liquid/solid ratios was undertaken to attempt to judge whether or not results of saturated experiments are valid for use in performance assessments of sites located in unsaturated rocks. The amount of hydrologic saturation can affect the ionic strength, pH, and redox potential which can in turn affect sorption. In addition, the presence of the gas phase may affect the amount of wetting occurring on the solid's surface. This paper describes experimental procedures which were developed to evaluate the sorption of uranium by silica sand at predetermined levels of unsaturation

Steady state method to determine unsaturated hydraulic conductivity at the ambient water potential

Science.gov (United States)

HUbbell, Joel M.

2014-08-19

The present invention relates to a new laboratory apparatus for measuring the unsaturated hydraulic conductivity at a single water potential. One or more embodiments of the invented apparatus can be used over a wide range of water potential values within the tensiometric range, requires minimal laboratory preparation, and operates unattended for extended periods with minimal supervision. The present invention relates to a new laboratory apparatus for measuring the unsaturated hydraulic conductivity at a single water potential. One or more embodiments of the invented apparatus can be used over a wide range of water potential values within the tensiometric range, requires minimal laboratory preparation, and operates unattended for extended periods with minimal supervision.

Studies of reaction difference between γ-ray and glow discharge on hydrogenation of unsaturated fatty acid esters

International Nuclear Information System (INIS)

Sakoda, Tatsuya; Nieda, Hiroshi; Kitahara, Kazuta; Ando, Kiyomi

2000-01-01

Hydrogenation of unsaturated fatty acid esters using an inductively coupled plasma at low pressure was performed, and electron temperature and density were measured using a double-probe in order to investigate the reaction difference between γ-ray and glow discharge on hydrogenation. In this experiment, unsaturated fatty acid esters were partly hydrogenated by the hydrogen plasma that had electron temperature of 3.5 eV, which was more efficient than γ-ray irradiation method. As a result, it was found that the plasma can effectively supply electrons that had the optimum energy for hydrogenation at the interface of fatty acids as well as excited atoms and ions. Also, the plasma generated at low pressure would be possible to convert unsaturated fatty acids into saturated fatty acids without breaking the starting monomer. (author)

Towards the blackbox computation of magnetic exchange coupling parameters in polynuclear transition-metal complexes: theory, implementation, and application.

Science.gov (United States)

Phillips, Jordan J; Peralta, Juan E

2013-05-07

We present a method for calculating magnetic coupling parameters from a single spin-configuration via analytic derivatives of the electronic energy with respect to the local spin direction. This method does not introduce new approximations beyond those found in the Heisenberg-Dirac Hamiltonian and a standard Kohn-Sham Density Functional Theory calculation, and in the limit of an ideal Heisenberg system it reproduces the coupling as determined from spin-projected energy-differences. Our method employs a generalized perturbative approach to constrained density functional theory, where exact expressions for the energy to second order in the constraints are obtained by analytic derivatives from coupled-perturbed theory. When the relative angle between magnetization vectors of metal atoms enters as a constraint, this allows us to calculate all the magnetic exchange couplings of a system from derivatives with respect to local spin directions from the high-spin configuration. Because of the favorable computational scaling of our method with respect to the number of spin-centers, as compared to the broken-symmetry energy-differences approach, this opens the possibility for the blackbox exploration of magnetic properties in large polynuclear transition-metal complexes. In this work we outline the motivation, theory, and implementation of this method, and present results for several model systems and transition-metal complexes with a variety of density functional approximations and Hartree-Fock.

Going greener: Synthesis of fully biobased unsaturated polyesters for styrene crosslinked resins with enhanced thermomechanical properties

Directory of Open Access Journals (Sweden)

C. S. M. F. Costa

2017-11-01

Full Text Available The main goal of this work was the development of fully biobased unsaturated polyesters (UPs that upon crosslinking with unsaturated monomers (UM could lead to greener unsaturated polyester resins (UPRs with similar thermomechanical properties to commercial fossil based UPR. After the successful synthesis of the biobased UPs, those were crosslinked with styrene (Sty, the most commonly used monomer, and the influence of the chemical structure of the UPs on the thermomechanical characteristics of UPRs were evaluated. The properties were compared with those of a commercial resin (Resipur 9837©. The BioUPRs presented high gel contents and contact angles that are similar to the commercial resin. The thermomechanical properties were evaluated by dynamic mechanical thermal analysis (DMTA and it was found that the UPR synthesized using propylene glycol (PG, succinic acid (SuAc and itaconic acid (ItAc presented very close thermomechanical properties compared to the commercial resin.

A free boundary problem describing the saturated-unsaturated flow in a porous medium

Directory of Open Access Journals (Sweden)

Gabriela Marinoschi

2004-01-01

Full Text Available This paper presents a functional approach to a nonlinear model describing the complete physical process of water infiltration into an unsaturated soil, including the saturation occurrence and the advance of the wetting front. The model introduced in this paper involves a multivalued operator covering the simultaneous saturated and unsaturated flow behaviors and enhances the study of the displacement of the free boundary between these two flow regimes. The model resides in Richards' equation written in pressure form with an initial condition and boundary conditions which in this work express the inflow due to the rain on the soil surface on the one hand, and characterize a certain permeability corresponding to the underground boundary, on the other hand. Existence, uniqueness, and regularity results for the transformed model in diffusive form, that is, for the moisture of the soil, and the existence of the weak solution for the pressure form are proved in the 3D case. The main part of the paper focuses on the existence of the free boundary between the saturated and unsaturated parts of the soil, and this is proved, in the 1D case, for certain stronger assumptions on the initial data and boundary conditions.

The Unsaturated Hydromechanical Coupling Model of Rock Slope Considering Rainfall Infiltration Using DDA

Directory of Open Access Journals (Sweden)

Xianshan Liu

2017-01-01

Full Text Available Water flow and hydromechanical coupling process in fractured rocks is more different from that in general porous media because of heterogeneous spatial fractures and possible fracture-dominated flow; a saturated-unsaturated hydromechanical coupling model using a discontinuous deformation analysis (DDA similar to FEM and DEM was employed to analyze water movement in saturated-unsaturated deformed rocks, in which the Van-Genuchten model differently treated the rock and fractures permeable properties to describe the constitutive relationships. The calibrating results for the dam foundation indicated the validation and feasibility of the proposed model and are also in good agreement with the calculations based on DEM still demonstrating its superiority. And then, the rainfall infiltration in a reservoir rock slope was detailedly investigated to describe the water pressure on the fault surface and inside the rocks, displacement, and stress distribution under hydromechanical coupling conditions and uncoupling conditions. It was observed that greater rainfall intensity and longer rainfall time resulted in lower stability of the rock slope, and larger difference was very obvious between the hydromechanical coupling condition and uncoupling condition, demonstrating that rainfall intensity, rainfall time, and hydromechanical coupling effect had great influence on the saturated-unsaturated water flow behavior and mechanical response of the fractured rock slopes.

Full-field dye concentration measurement within saturated/unsaturated thin slabs of porous media

International Nuclear Information System (INIS)

Norton, D.L.; Glass, R.J.

1993-01-01

This paper presents a full-field dye concentration measurement technique that extends our experimental capabilities to the measurement of transient dye concentration fields within steady state flow fields under unsaturated or saturated conditions. Simple light absorption theory provides a basis for translating images into high resolution dye concentration fields. A series of dye pulse experiments that demonstrate the combined use of the full-field saturation and dye concentration techniques was conducted at four different degrees of saturation. Each of these experimental sequences was evaluated with respect to mass balance, the results being within 5% of the known dye mass input. An image windowing technique allowed us to see increased dispersion due to decreasing moisture content, tailing of concentration at the rear of the dye pulse and slight velocity changes of the dispersive front due to changes in moisture content. The exceptional resolution of dye concentration in space and time provided by this laboratory technique allows systematic experimentation for examining basic processes affecting solute transport within saturated/unsaturated porous media. Future challenges for this work will be to use these techniques to analyze more complex systems involving heterogeneities, scaling laws, and detailed investigations of the relationship between transverse and longitudinal dispersion in unsaturated media

Preferential flow occurs in unsaturated conditions

Science.gov (United States)

Nimmo, John R.

2012-01-01

Because it commonly generates high-speed, high-volume flow with minimal exposure to solid earth materials, preferential flow in the unsaturated zone is a dominant influence in many problems of infiltration, recharge, contaminant transport, and ecohydrology. By definition, preferential flow occurs in a portion of a medium – that is, a preferred part, whether a pathway, pore, or macroscopic subvolume. There are many possible classification schemes, but usual consideration of preferential flow includes macropore or fracture flow, funneled flow determined by macroscale heterogeneities, and fingered flow determined by hydraulic instability rather than intrinsic heterogeneity. That preferential flow is spatially concentrated associates it with other characteristics that are typical, although not defining: it tends to be unusually fast, to transport high fluxes, and to occur with hydraulic disequilibrium within the medium. It also has a tendency to occur in association with large conduits and high water content, although these are less universal than is commonly assumed. Predictive unsaturated-zone flow models in common use employ several different criteria for when and where preferential flow occurs, almost always requiring a nearly saturated medium. A threshold to be exceeded may be specified in terms of the following (i) water content; (ii) matric potential, typically a value high enough to cause capillary filling in a macropore of minimum size; (iii) infiltration capacity or other indication of incipient surface ponding; or (iv) other conditions related to total filling of certain pores. Yet preferential flow does occur without meeting these criteria. My purpose in this commentary is to point out important exceptions and implications of ignoring them. Some of these pertain mainly to macropore flow, others to fingered or funneled flow, and others to combined or undifferentiated flow modes.

The Effect of Intra-Ruminal Infusion of Saturated and Unsaturated ...

African Journals Online (AJOL)

This study investigated the effect of different proportional combinations of a saturated fatty acid (Palmitic acid, PA) and unsaturated fatty acid (Linolenic acid, LA) on rumen outflow rate (r) in West African dwarf (WAD) sheep. A 5x5 Latin square experimental model of five sheep and five combination proportions of palmitic and ...

Accumulation of macular xanthophylls in unsaturated membrane domains.

Science.gov (United States)

Wisniewska, Anna; Subczynski, Witold K

2006-05-15

The distribution of macular xanthophylls, lutein and zeaxanthin, between domains formed in membranes made from an equimolar ternary mixture of dioleoylphosphatidylcholine/sphingomyelin/cholesterol, called a raft-forming mixture, was investigated. In these membranes, two domains are formed: the raft domain enriched in saturated lipids and cholesterol (detergent-resistant membranes, DRM), and the bulk domain enriched in unsaturated lipids (detergent-soluble membranes, DSM). These membrane domains have been separated using cold Triton X-100 extraction from membranes containing 1 mol% of either lutein or zeaxanthin. The results indicated that xanthophylls are substantially excluded from DRM and remain concentrated in DSM. Concentrations of xanthophylls in DRM and DSM calculated as the mole ratio of either xanthophyll to phospholipid were 0.005 and 0.03, respectively, and calculated as the mole ratio of either xanthophyll to total lipid (phospholipid + cholesterol) were 0.003 and 0.025, respectively. Thus, xanthophylls are over eight times more concentrated in DSM than in DRM. No significant difference in the distribution of lutein and zeaxanthin was found. It was also demonstrated using saturation-recovery EPR that at 1 mol%, neither lutein nor zeaxanthin affect the formation of membrane domains. The location of xanthophylls in domains formed from unsaturated lipids is ideal if they are to act as a lipid antioxidant, which is the most accepted mechanism through which lutein and zeaxanthin protect the retina from age-related macular diseases.

An exploration of unsaturated zone during in-situ heating test in sedimentary soft rocks

International Nuclear Information System (INIS)

Kubota, Kenji; Suzuki, Koichi; Ikenoya, Takafumi; Takakura, Nozomu; Tani, Kazuo

2011-01-01

In-situ heating test has been conducted to evaluate the influence of high temperature in an underground facility at a depth of 50 m. Resistivity monitoring is thought to be effective to map the extent of the high temperature and unsaturated zone. So we have conducted resistivity tomography during the heating test. As a result, the resistivity of the rock mass around the heating well was decreased and this area was gradually expanded from the heated area during the heating. This suggests that high temperature zone is detected by resistivity tomography. The results also suggested that resistivity was increased by unsaturation of rock mass around the heating well. (author)

Reduction of , -Unsaturated Ketones Using a Zn/NiCl System in ...

African Journals Online (AJOL)

NJD

Reduction of , -Unsaturated Ketones Using a Zn/NiCl. 2. System in Aqueous Media in the Presence of Anionic and. Cationic Surfactants. Hocine Ilikti*, Tayeb Benabdallah, Kamel Bentayeb, Adil A. Othman and Zoubir Derriche. Organic Chemistry and Electrochemistry Laboratory, Department of Chemistry, Faculty of Science, ...

Elastoplastic model for unsaturated, quasi-saturated and fully saturated fine soils

Directory of Open Access Journals (Sweden)

Lai Ba Tien

2016-01-01

Full Text Available In unsaturated soils, the gaseous phase is commonly assumed to be continuous. This assumption is no more valid at high saturation ratio. In that case, air bubbles and pockets can be trapped in the porous network by the liquid phase and the gas phase becomes discontinuous. This trapped air reduces the apparent compressibility of the pore fluid and affect the mechanical behavior of the soil. Although it is trapped in the pores, its dissolution can take place. Dissolved air can migrate through the pore space, either by following the flow of the fluid or by diffusion. In this context, this paper present a hydro mechanical model that separately considers the kinematics and the mechanical behavior of each fluid species (eg liquid water, dissolved air, gaseous air and the solid matrix. This new model was implemented in a C++ code. Some numerical simulations are performed to demonstrate the ability of this model to reproduce a continuous transition of unsaturated to saturated states.

Generation of dense plume fingers in saturated-unsaturated homogeneous porous media

Science.gov (United States)

Cremer, Clemens J. M.; Graf, Thomas

2015-02-01

Flow under variable-density conditions is widespread, occurring in geothermal reservoirs, at waste disposal sites or due to saltwater intrusion. The migration of dense plumes typically results in the formation of vertical plume fingers which are known to be triggered by material heterogeneity or by variations in source concentration that causes the density variation. Using a numerical groundwater model, six perturbation methods are tested under saturated and unsaturated flow conditions to mimic heterogeneity and concentration variations on the pore scale in order to realistically generate dense fingers. A laboratory-scale sand tank experiment is numerically simulated, and the perturbation methods are evaluated by comparing plume fingers obtained from the laboratory experiment with numerically simulated fingers. Dense plume fingering for saturated flow can best be reproduced with a spatially random, time-constant perturbation of the solute source. For unsaturated flow, a spatially and temporally random noise of solute concentration or a random conductivity field adequately simulate plume fingering.

Prediction of unsaturated flow and water backfill during infiltration in layered soils

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Cui, Guotao; Zhu, Jianting

2018-02-01

We develop a new analytical infiltration model to determine water flow dynamics around layer interfaces during infiltration process in layered soils. The model mainly involves the analytical solutions to quadratic equations to determine the flux rates around the interfaces. Active water content profile behind the wetting front is developed based on the solution of steady state flow to dynamically update active parameters in sharp wetting front infiltration equations and to predict unsaturated flow in coarse layers before the front reaches an impeding fine layer. The effect of water backfill to saturate the coarse layers after the wetting front encounters the impeding fine layer is analytically expressed based on the active water content profiles. Comparison to the numerical solutions of the Richards equation shows that the new model can well capture water dynamics in relation to the arrangement of soil layers. The steady state active water content profile can be used to predict the saturation state of all layers when the wetting front first passes through these layers during the unsteady infiltration process. Water backfill effect may occur when the unsaturated wetting front encounters a fine layer underlying a coarse layer. Sensitivity analysis shows that saturated hydraulic conductivity is the parameter dictating the occurrence of unsaturated flow and water backfill and can be used to represent the coarseness of soil layers. Water backfill effect occurs in coarse layers between upper and lower fine layers when the lower layer is not significantly coarser than the upper layer.

Solutes transport in unsaturated double-porosity medium. Modelling by homogenization and applications

International Nuclear Information System (INIS)

Tran Ngoc, T.D.

2008-07-01

This Ph.D thesis presents the development of the solute transport models in unsaturated double-porosity medium, by using the asymptotic homogenization method. The obtained macroscopic models concern diffusion, diffusion-convection and dispersion-convection, according to the transport regime which is characterized by the non-dimensional numbers. The models consist of two coupled equations that show the local non-equilibrium of concentrations. The double-porosity transport models were numerically implemented using the code COMSOL Multiphysics (finite elements method), and compared with the solution of the same problem at the fine scale. The implementation allows solving the coupled equations in the macro- and micro-porosity domains (two-scale computations). The calculations of the dispersion tensor as a solution of the local boundary value problems, were also conducted. It was shown that the dispersivity depends on the saturation, the physical properties of the macro-porosity domain and the internal structure of the double-porosity medium. Finally, two series of experiments were performed on a physical model of double-porosity that is composed of a periodic assemblage of sintered clay spheres in Hostun sand HN38. The first experiment was a drainage experiment, which was conducted in order to validate the unsaturated flow model. The second series was a dispersion experiment in permanent unsaturated water flow condition (water content measured by gamma ray attenuation technique). A good agreement between the numerical simulations and the experimental observations allows the validation of the developed models. (author)

In-situ arsenic removal during groundwater recharge through unsaturated alluvium

Science.gov (United States)

O'Leary, David; Izbicki, John; T.J. Kim,; Clark Ajawani,; Suarez, Donald; Barnes, Thomas; Thomas Kulp,; Burgess, Matthew K.; Tseng, Iwen

2015-01-01

OBJECTIVES The purpose of this study was to determine the feasibility and sustainability of in-situ removal of arsenic from water infiltrated through unsaturated alluvium. BACKGROUND Arsenic is naturally present in aquifers throughout the southwestern United States and elsewhere. In January 2006, the U.S. Environmental Protection Agency (EPA) lowered the Maximum Contaminant Level (MCL) for arsenic from 50 to 10 micrograms per liter (g/L). This raised concerns about naturally-occurring arsenic in groundwater. Although commercially available systems using sorbent iron or aluminum oxide resins are available to treat high-arsenic water, these systems are expensive to build and operate, and may generate hazardous waste. Iron and aluminum oxides occur naturally on the surfaces of mineral grains that compose alluvial aquifers. In areas where alluvial deposits are unsaturated, these oxides may sorb arsenic in the same manner as commercial resins, potentially providing an effective low-cost alternative to commercially engineered treatment systems. APPROACH The Antelope Valley within the Mojave Desert of southern California contains a shallow water-table aquifer with arsenic concentrations of 5 g/L, and a deeper aquifer with arsenic concentrations of 30 g/L. Water was pumped from the deep aquifer into a pond and infiltrated through an 80 m-thick unsaturated zone as part of field-scale and laboratory experiments to treat high-arsenic groundwater and recharge the shallow water table aquifer at the site. The field-scale recharge experiment included the following steps: 1) construction of a recharge pond 2) test drilling for sample collection and instrument installation adjacent to the pond 3) monitoring downward migration of water infiltrated from the pond 4) monitoring changes in selected trace-element concentrations as water infiltrated through the unsaturated zone Data from instruments within the borehole adjacent to the pond were supplemented with borehole and

Supplementation with bypass fat in silvopastoral systems diminishes the ratio of milk saturated/unsaturated fatty acids.

Science.gov (United States)

Mahecha, L; Angulo, J; Salazar, B; Cerón, M; Gallo, J; Molina, C H; Molina, E J; Suárez, J F; Lopera, J J; Olivera, M

2008-04-01

This study was conducted to evaluate if supplementing bypass fat to cows under silvopastoral systems, increases the concentration of unsaturated fatty acids in milk, thus improving the saturated/ unsaturated ratio without a negative effect on total milk yield in fat or protein. Two concentrations of two different sources of bypass fat were evaluated for 40 days, each in a group of 24 multiparous Lucerna (Colombian breed) cows. A cross-over design of 8 Latin squares 3 x 3 was used. The variables submitted to analysis were body condition, daily milk production and milk composition. Body condition, milk yield and milk quality were not different but there was a significant decrease in the amount of saturated fatty acid in both experiments while the unsaturated fat increased significantly in experiment 1 and remained stable in experiment 2. Results, such as these have as far as we know, not been reported previously and they provide an approach for the improvement of milk as a "functional food".

Freezing process in unsaturated packed beds; Fuhowa ryushi sonai ni okeru suibun toketsu

Energy Technology Data Exchange (ETDEWEB)

Akahori, M; Aoki, K; Hattori, M [Nagaoka University of Technology, Niigata (Japan); Tani, T [Oji Paper Co. Ltd., Tokyo (Japan)

1998-04-25

The freezing process in unsaturated packed beds has been investigated experimentally and theoretically. Water transport to the frozen front plays an important part on freezing. The rate of the absorption of water into frozen layer depended on the freezing heat flux and the water saturation at the freezing front. As a result, ice content in the frozen layer was related to the rate of the absorption of water and the freezing heat flux. A one-dimensional freezing model in unsaturated packed beds has been presented, accounting for the water transport. The predicted water saturation and temperature distributions in the body and the thickness of frozen layer were compared with the experimental results using a porous bed composed of glass beads. 12 refs., 10 figs., 1 tab.

Effect of Structure Change on Radiation Crosslinking of Unsaturated Polyesters

International Nuclear Information System (INIS)

Ranogajec, F.

2006-01-01

During the course of crosslinking of unsaturated polyesters reacting system, that was liquid prior to reaction, gels, and becomes solid. Crosslinking reaction begins to be controlled by the change of the physical state of the system at an early stage of reaction. The kinetics can not be studied by the usual kinetical methods. In-source 60 C o gamma rays induced crosslinking of unsaturated polyester with styrene was followed directly and continuously by measuring electrical conductivity change. The results of extraction analysis proved good correlation between the change of electrical conductivity and the extent of curing. The gel content was inversely proportional to conductivity and free styrene content directly proportional to conductivity. DC-electrical conductivity has shown high sensitivity toward structural changes and enabled us to detect liquid-liquid transitions in unsaturated polyester. The upper liquid-liquid transition (T l ρ) is less known transition caused by a stepwise decrease of intramolecular short-range local order that remains above the glass and lower liquid-liquid transitions. The local order is based on secondary valent interactions and is enhanced by hydrogen bonding. The linear temperature dependence of the viscosity and dc electrical conductivity of unsaturated polyesters showed a change of slope caused by the (T l ρ). Those changes were the result of the diminishing of the local order (which includes several bond lengths) caused by breaking of the intramolecular interactions. The intramolecular nature of the (T l ρ) in the polyesters under consideration was proved by its insensitivity to crosslinking and dilution with solvents. In the corresponding temperature range, DSC thermograms shoved expected endothermic changes. The structure changes related to the (T l ρ) in the investigated polyesters were determined by 1 H NMR and NIR spectroscopy. The proton NMR indicated that the stepwise change in hydrogen bonding occurred in the

Effects of crude oil on water and tracer movement in the unsaturated and saturated zones.

Science.gov (United States)

Delin, Geoffrey N; Herkelrath, William N

2017-05-01

A tracer test was conducted to aid in the investigation of water movement and solute transport at a crude-oil spill site near Bemidji, Minnesota. Time of travel was measured using breakthrough curves for rhodamine WT and bromide tracers moving from the soil surface through oil-contaminated and oil-free unsaturated zones to the saturated zone. Results indicate that the rates of tracer movement were similar in the oil-free unsaturated and saturated zones compared to the oily zones. These results are somewhat surprising given the oil contamination in the unsaturated and saturated zones. Rhodamine tracer breakthrough in the unsaturated and saturated zones in general was delayed in comparison to bromide tracer breakthrough. Peak tracer concentrations for the lysimeters and wells in the oily zone were much greater than at the corresponding depths in the oil-free zone. Water and tracer movement in the oily zone was complicated by soil hydrophobicity and decreased oil saturations toward the periphery of the oil. Preferential flow resulted in reduced tracer interaction with the soil, adsorption, and dispersion and faster tracer movement in the oily zone than expected. Tracers were freely transported through the oily zone to the water table. Recharge calculations support the idea that the oil does not substantially affect recharge in the oily zone. This is an important result indicating that previous model-based assumptions of decreased recharge beneath the oil were incorrect. Results have important implications for modeling the fate and transport of dissolved contaminants at hydrocarbon spill sites. Published by Elsevier B.V.

Thermodynamics of U(VI) and Eu(III) complexation by unsaturated carboxylates

Energy Technology Data Exchange (ETDEWEB)

Rawat, Neetika; Bhattacharyya, A. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tomar, B.S., E-mail: bstomar@barc.gov.in [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Ghanty, T.K. [Theoretical Chemistry Section, Bhabha Atomic Research Centre, Mumbai 400085 (India); Manchanda, V.K. [Radiochemistry Division, Bhabha Atomic Research Centre, Mumbai 400085 (India)

2011-05-10

Highlights: {yields} {Delta}H and log K determined for U(VI) and Eu(III) complexes with maleate and fumarate. {yields} log K and coordination environment of Eu(III) complexes has been studied by TRFS. {yields} Higher log K of U(VI) complexes than Eu(III) complexes is due to higher entropy. {yields} Plot of log K vs log K{sub P} suggest charge polarization in fumarate complexes. {yields} Ab initio calculations support charge polarization in fumarate complexes. - Abstract: The thermodynamic parameters ({Delta}G, {Delta}H and {Delta}S) of complexation of U(VI) and Eu(III) by unsaturated dicarboxylic acids, namely, maleic and fumaric acid, has been determined by potentiometric and microcalorimetric titrations at fixed ionic strength (I = 1.0 M) and temperature (298 K). The results show formation of 1:1 complexes by both the ligands with Eu(III). In the case of U(VI), maleate forms both 1:1 and 1:2 complexes, while only 1:1 complex was formed with fumarate. The fluorescence emission spectra of Eu(III)-dicarboxylate solutions at varying ligand to metal ratio were also used to obtain their stability constants. In addition, the fluorescence lifetimes reveal higher dehydration of Eu(III)-maleate compared to Eu(III)-fumarate which corroborates the {Delta}S values. The thermodynamic quantities suggest charge polarization effects in the case of U(VI) and Eu(III) complexes of fumarate, which is further corroborated by theoretical calculations. For the same ligand, U(VI) complexes were found to be more stable which was mainly due to higher entropy term.

Stable and radioactive isotopes in the study of the unsaturated soil zone

International Nuclear Information System (INIS)

1985-11-01

This publication brings together the main results with conclusions and recommendations on the usefulness of studies of the oxygen 18, deuterium and tritium in water in the unsaturated zone. A separate abstract was prepared for each of the 9 papers

Processing of Unsaturated Organic Acid Aerosols by Ozone

Science.gov (United States)

Aloisio, S.; Donaldson, D. J.; Eliason, T. L.; Cziczo, D.; Vaida, V.

2002-05-01

We present results of in-situ studies of the oxidative "processing" of organic aerosols composed of unsaturated organic compounds. Aerosol samples of 2-octenoic acid and undecylenic acid were exposed to approx. 10 mbar ozone in a room temperature, atmospheric pressure flow tube reactor. In-situ spectroscopic probing of the reaction mixture, as well as GC-MS analysis of the flow tube effluent, shows evidence of efficient oxidation of double bonds in the organic species, with production of gas-phase and aerosol phase ozonolysis products.

The investigation formation of complexes of Fe(III) and Fe(II) in the water solution of imidazole at 298 K

International Nuclear Information System (INIS)

Radjabov, U.R.; Yusupov, Z.N.; Sharipov, I.Kh.

2001-01-01

C H lm=0.1 mol/l, C F e(II)=1·10 - 4 m ol/l and iron sterns: 0.10, 0.25, 0.50 and 1.00 mol/l. It is established that in the investigated systems form at different on composition mono-, polynuclear, homo-- and heterovalent coordination compounds. In aids of the oxidation function accurate the composition, defined the constants formation and domination sphere of complex forms

Chemical and Isotopes study of pollutants transport through unsaturated zone in Damascus oasis (Syria)

International Nuclear Information System (INIS)

Abou Zakhem, B.; Hafez, R.

2011-08-01

The primary objectives of this study were to determine the hydrochemical and isotopic characteristics of groundwater and to study vertical transport processes for trace elements through the unsaturated zone, from the surface water into the groundwater system. A third objective is to identifying the importance of the unsaturated zone in protecting groundwater from contamination. Distribution of trace elements, including Cu, Pb, Cr, Cd, Zn and As in the soil with depth were studied. Mineralogy was investigated using X-Ray diffraction techniques and granulometry in three drilled soil profile (KA, KB and KS) in Damascus Oasis, which indicated that the soil consists mainly of calcite, a mineral that has the ability to bind some of the trace elements. Measurement of nitrate concentrations in groundwater permitted an investigation of the urban, industrial and agricultural pollution in the Oasis, in particular, in the eastern part of Damascus city and in the north of Oasis where the irrigation by treated wastewater is applied. Depending on the chemical characteristics of the studied trace elements and soil conditions, these elements have high concentrations in the upper part of the soil (20-30 cm depth), due to absorption by clay minerals and organic matter. These high concentrations represent pollution by leather industries (tannery) in the area. The trace element concentrations decrease towards the east in parallel with river flow direction. The lower part of profiles show low trace element concentrations, below the international permitted limit. The low concentrations of trace elements in groundwater which are also below the international limit, indicates no pollution is presented. The isotopic composition of shallow groundwater indicates the underground recharge, originated from the Anti-Lebanon Mountain, is more significant than the direct recharge through unsaturated zone. It is concluded the unsaturated zone and the decrease of groundwater levels have played an

Effects of thermal vapor diffusion on seasonal dynamics of water in the unsaturated zone

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Milly, Paul C.D.

1996-01-01

The response of water in the unsaturated zone to seasonal changes of temperature (T) is determined analytically using the theory of nonisothermal water transport in porous media, and the solutions are tested against field observations of moisture potential and bomb fallout isotopic (36Cl and 3H) concentrations. Seasonally varying land surface temperatures and the resulting subsurface temperature gradients induce thermal vapor diffusion. The annual mean vertical temperature gradient is close to zero; however, the annual mean thermal vapor flux is downward, because the temperature‐dependent vapor diffusion coefficient is larger, on average, during downward diffusion (occurring at high T) than during upward diffusion (low T). The annual mean thermal vapor flux is shown to decay exponentially with depth; the depth (about 1 m) at which it decays to e−1of its surface value is one half of the corresponding decay depth for the amplitude of seasonal temperature changes. This depth‐dependent annual mean flux is effectively a source of water, which must be balanced by a flux divergence associated with other transport processes. In a relatively humid environment the liquid fluxes greatly exceed the thermal vapor fluxes, so such a balance is readily achieved without measurable effect on the dynamics of water in the unsaturated zone. However, if the mean vertical water flux through the unsaturated zone is very small (theoretical prediction is supported by long‐term field measurements in the Chihuahuan Desert. The analysis also makes predictions, confirmed by the field observations, regarding the seasonal variations of matric potential at a given depth. The conceptual model of unsaturated zone water transport developed here implies the possibility of near‐surface trapping of any aqueous constituent introduced at the surface.

Novel α, β-Unsaturated Sophoridinic Derivatives: Design, Synthesis, Molecular Docking and Anti-Cancer Activities

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Yiming Xu

2017-11-01

Full Text Available Using sophoridine 1 and chalcone 3 as the lead compounds, a series of novel α, β-unsaturated sophoridinic derivatives were designed, synthesized, and evaluated for their in vitro cytotoxicity. Structure-activity relationship (SAR analysis indicated that introduction of α, β-unsaturated ketone moiety and heterocyclic group might significantly enhance anticancer activity. Among the compounds, 2f and 2m exhibited potential effects against HepG-2 and CNE-2 human cancer cell lines. Furthermore, molecular docking studies were performed to understand possible docking sites of the molecules on the target proteins and the mode of binding. This work provides a theoretical basis for structural optimizations and exploring anticancer pathways of this kind of compound.

Predicting unsaturated zone nitrogen mass balances in agricultural settings of the United States

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Nolan, Bernard T.; Puckett, Larry J.; Ma, Liwang; Green, Christopher T.; Bayless, E. Randall; Malone, Robert W.

2009-01-01

Unsaturated zone N fate and transport were evaluated at four sites to identify the predominant pathways of N cycling: an almond [Prunus dulcis (Mill.) D.A. Webb] orchard and cornfield (Zea mays L.) in the lower Merced River study basin, California; and corn–soybean [Glycine max (L.) Merr.] rotations in study basins at Maple Creek, Nebraska, and at Morgan Creek, Maryland. We used inverse modeling with a new version of the Root Zone Water Quality Model (RZWQM2) to estimate soil hydraulic and nitrogen transformation parameters throughout the unsaturated zone; previous versions were limited to 3-m depth and relied on manual calibration. The overall goal of the modeling was to derive unsaturated zone N mass balances for the four sites. RZWQM2 showed promise for deeper simulation profiles. Relative root mean square error (RRMSE) values for predicted and observed nitrate concentrations in lysimeters were 0.40 and 0.52 for California (6.5 m depth) and Nebraska (10 m), respectively, and index of agreement (d) values were 0.60 and 0.71 (d varies between 0 and 1, with higher values indicating better agreement). For the shallow simulation profile (1 m) in Maryland, RRMSE and d for nitrate were 0.22 and 0.86, respectively. Except for Nebraska, predictions of average nitrate concentration at the bottom of the simulation profile agreed reasonably well with measured concentrations in monitoring wells. The largest additions of N were predicted to come from inorganic fertilizer (153–195 kg N ha−1 yr−1 in California) and N fixation (99 and 131 kg N ha−1 yr−1 in Maryland and Nebraska, respectively). Predicted N losses occurred primarily through plant uptake (144–237 kg N ha−1 yr−1) and deep seepage out of the profile (56–102 kg N ha−1 yr−1). Large reservoirs of organic N (up to 17,500 kg N ha−1 m−1 at Nebraska) were predicted to reside in the unsaturated zone, which has implications for potential future transfer of nitrate to groundwater.

Dissipative particle dynamics simulation of fluid motion through an unsaturated fracture and fracture junction

International Nuclear Information System (INIS)

Liu Moubin; Meakin, Paul; Huang Hai

2007-01-01

Multiphase fluid motion in unsaturated fractures and fracture networks involves complicated fluid dynamics, which is difficult to model using grid-based continuum methods. In this paper, the application of dissipative particle dynamics (DPD), a relatively new mesoscale method to simulate fluid motion in unsaturated fractures is described. Unlike the conventional DPD method that employs a purely repulsive conservative (non-dissipative) particle-particle interaction to simulate the behavior of gases, we used conservative particle-particle interactions that combine short-range repulsive and long-range attractive interactions. This new conservative particle-particle interaction allows the behavior of multiphase systems consisting of gases, liquids and solids to be simulated. Our simulation results demonstrate that, for a fracture with flat parallel walls, the DPD method with the new interaction potential function is able to reproduce the hydrodynamic behavior of fully saturated flow, and various unsaturated flow modes including thin film flow, wetting and non-wetting flow. During simulations of flow through a fracture junction, the fracture junction can be fully or partially saturated depending on the wetting property of the fluid, the injection rate and the geometry of the fracture junction. Flow mode switching from a fully saturated flow to a thin film flow can also be observed in the fracture junction

Conceptualization of a hypothetical high-level nuclear waste repository site in unsaturated, fractured tuff

International Nuclear Information System (INIS)

Parsons, A.M.; Olague, N.E.; Gallegos, D.P.

1991-01-01

Under the sponsorship of the US Nuclear Regulatory Commission (NRC), Sandia National Laboratories (SNL) is developing a performance assessment methodology for the analysis of long-term disposal and isolation of high-level nuclear wastes (HLW) in alternative geologic media. As part of this exercise, SNL created a conceptualization of ground-water flow and radionuclide transport in the far field of a hypothetical HLW repository site located in unsaturated, fractured tuff formations. This study provides a foundation for the development of conceptual mathematical, and numerical models to be used in this performance assessment methodology. This conceptualization is site specific in terms of geometry, the regional ground-water flow system, stratigraphy, and structure in that these are based on information from Yucca Mountain located on the Nevada Test Site. However, in terms of processes in unsaturated, fractured, porous media, the model is generic. This report also provides a review and evaluation of previously proposed conceptual models of unsaturated and saturated flow and solute transport. This report provides a qualitative description of a hypothetical HLW repository site in fractured tuff. However, evaluation of the current knowledge of flow and transport at Yucca Mountain does not yield a single conceptual model. Instead, multiple conceptual models are possible given the existing information

Conceptualization of a hypothetical high-level nuclear waste repository site in unsaturated, fractured tuff

Energy Technology Data Exchange (ETDEWEB)

Parsons, A.M.; Olague, N.E.; Gallegos, D.P. [Sandia National Labs., Albuquerque, NM (USA)

1991-01-01

Under the sponsorship of the US Nuclear Regulatory Commission (NRC), Sandia National Laboratories (SNL) is developing a performance assessment methodology for the analysis of long-term disposal and isolation of high-level nuclear wastes (HLW) in alternative geologic media. As part of this exercise, SNL created a conceptualization of ground-water flow and radionuclide transport in the far field of a hypothetical HLW repository site located in unsaturated, fractured tuff formations. This study provides a foundation for the development of conceptual mathematical, and numerical models to be used in this performance assessment methodology. This conceptualization is site specific in terms of geometry, the regional ground-water flow system, stratigraphy, and structure in that these are based on information from Yucca Mountain located on the Nevada Test Site. However, in terms of processes in unsaturated, fractured, porous media, the model is generic. This report also provides a review and evaluation of previously proposed conceptual models of unsaturated and saturated flow and solute transport. This report provides a qualitative description of a hypothetical HLW repository site in fractured tuff. However, evaluation of the current knowledge of flow and transport at Yucca Mountain does not yield a single conceptual model. Instead, multiple conceptual models are possible given the existing information.

Graphene oxide-facilitated transport of levofloxacin and ciprofloxacin in saturated and unsaturated porous media.

Science.gov (United States)

Sun, Kaixuan; Dong, Shunan; Sun, Yuanyuan; Gao, Bin; Du, Wenchao; Xu, Hongxia; Wu, Jichun

2018-04-15

In this work, effects of graphene oxide (GO) on the co-transport of the two typical Fluoroquinolones (FQs) - levofloxacin (LEV) and ciprofloxacin (CIP) in saturated and unsaturated quartz sand media were studied. The adsorption isotherms showed that GO had much larger sorption capacities to LEV and CIP than sand with the largest Langmuir adsorption capacity of 409 mg g -1 (CIP-GO); while the sorption affinity of the two FQs onto the two adsorbents might follow the order of CIP-sand > LEV-sand > LEV-GO > CIP-GO. GO promoted the mobility of the two FQs in both saturated and unsaturated porous media due to its strong mobility and sorption capacity. The GO-bound LEV/CIP was responsible for the LEV/CIP transport in the porous media, and transport of GO-bound FQs increased with the increasing of initial GO concentration. Under unsaturated conditions, moisture showed little effect on the transport of GO-bound CIP; however, the mobility of GO-bound LEV reduced with the decreasing of moisture content, suggesting the transport of adsorbed LEV from GO to air-water interface. GO sorption reduced the antibacterial ability of the two FQs, but they were still effective in inhibiting E. coli growth. Copyright © 2018 Elsevier B.V. All rights reserved.

The Impact of Organo-Mineral Complexation on Mineral Weathering in the Soil Zone under Unsaturated Conditions

Science.gov (United States)

Michael, H. A.; Tan, F.; Yoo, K.; Imhoff, P. T.

2017-12-01

While organo-mineral complexes can protect organic matter (OM) from biodegradation, their impact on soil mineral weathering is not clear. Previous bench-scale experiments that focused on specific OM and minerals showed that the adsorption of OM to mineral surfaces accelerates the dissolution of some minerals. However, the impact of natural organo-mineral complexes on mineral dissolution under unsaturated conditions is not well known. In this study, soil samples prepared from an undisturbed forest site were used to determine mineral weathering rates under differing conditions of OM sorption to minerals. Two types of soil samples were generated: 1) soil with OM (C horizon soil from 84-100cm depth), and 2) soil without OM (the same soil as in 1) but with OM removed by heating to 350°for 24 h). Soil samples were column-packed and subjected to intermittent infiltration and drainage to mimic natural rainfall events. Each soil sample type was run in duplicate. The unsaturated condition was created by applying gas pressure to the column, and the unsaturated chemical weathering rates during each cycle were calculated from the effluent concentrations. During a single cycle, when applying the same gas pressure, soils with OM retained more moisture than OM-removed media, indicating increased water retention capacity under the impact of OM. This is consistent with the water retention data measured by evaporation experiments (HYPROP) and the dew point method (WP4C Potential Meter). Correspondingly, silicon (Si) denudation rates indicated that dissolution of silicate minerals was 2-4 times higher in OM soils, suggesting that organo-mineral complexes accelerate mineral dissolution under unsaturated conditions. When combining data from all cycles, the results showed that Si denudation rates were positively related to soil water content: denundation rate increased with increasing water content. Therefore, natural mineral chemical weathering under unsaturated conditions, while

Numerical study of damage in unsaturated Geological and Engineered barriers

International Nuclear Information System (INIS)

Arson, C.; Gatmiri, B.

2011-01-01

The theoretical framework of a damage model dedicated to non-isothermal unsaturated porous media is presented. The damage variable is a second-order tensor, and the model is formulated in independent state variables. The behavior laws are derived from a postulated expression of Helmholtz free energy. The damaged rigidities are computed by applying the Principle of Equivalent Elastic Energy (PEEE). Internal length parameters are introduced in the expressions of liquid water and vapor conductivities, to account for cracking effects on fluid flows. The damage model has been implemented in Θ-Stock Finite Element program. The mechanical aspect of the damage model is validated by simulating a triaxial compression test on a dry isothermal brittle material. Then, a sophisticated model of nuclear waste disposal, involving two non-isothermal unsaturated porous media, is reproduced. The results obtained in elasticity are in good agreement with the results presented in the corresponding reference article. A parametric study on initial damage is then performed to assess the influence of the Excavated Damaged Zone (EDZ) on the response of the nuclear waste repository during the heating phase. The trends meet the theoretical expectations. (authors)

Adaptive probabilistic collocation based Kalman filter for unsaturated flow problem

Science.gov (United States)

Man, J.; Li, W.; Zeng, L.; Wu, L.

2015-12-01

The ensemble Kalman filter (EnKF) has gained popularity in hydrological data assimilation problems. As a Monte Carlo based method, a relatively large ensemble size is usually required to guarantee the accuracy. As an alternative approach, the probabilistic collocation based Kalman filter (PCKF) employs the Polynomial Chaos to approximate the original system. In this way, the sampling error can be reduced. However, PCKF suffers from the so called "cure of dimensionality". When the system nonlinearity is strong and number of parameters is large, PCKF is even more computationally expensive than EnKF. Motivated by recent developments in uncertainty quantification, we propose a restart adaptive probabilistic collocation based Kalman filter (RAPCKF) for data assimilation in unsaturated flow problem. During the implementation of RAPCKF, the important parameters are identified and active PCE basis functions are adaptively selected. The "restart" technology is used to alleviate the inconsistency between model parameters and states. The performance of RAPCKF is tested by unsaturated flow numerical cases. It is shown that RAPCKF is more efficient than EnKF with the same computational cost. Compared with the traditional PCKF, the RAPCKF is more applicable in strongly nonlinear and high dimensional problems.

Nuclear-waste isolation in the unsaturated zone of arid regions

International Nuclear Information System (INIS)

Wollenberg, H.A.; Wang, J.S.Y.; Korbin, G.

1982-05-01

The vadose zone in arid regions is considered as a possible environment for geologic isolation of nuclear waste. There are several topographic and lithologic combinations in the vadose zone of arid regions that may lend themselves to waste isolation considerations. In some cases, topographic highs such as mesas and interbasin ranges - comprised of several rock types, may contain essentially dry or partially saturated conditions favorable for isolation. The adjacent basins, especially in the far western and southwestern US, may have no surface or subsurface hydrologic connections with systems ultimately leading to the ocean. Some rock types may have the favorable characteristics of very low permeability and contain appropriate minerals for the strong chemical retardation of radionuclides. Environments exhibiting these hydrologic and geochemical attributes are the areas underlain by tuffaceous rocks, relatively common in the Basin and Range geomorphic province. Adjacent valley areas, where tuffaceous debris makes up a significant component of valley fill alluvium, may also contain thick zones of unsaturated material, and as such also lend themselves to strong consideration as respository environments. This paper summarizes the aspects of nuclear waste isolation in unsaturated regimes in alluvial-filled valleys and tuffaceous rocks of the Basin and Range province

A borehole instrumentation program for characterization of unsaturated-zone percolation

International Nuclear Information System (INIS)

Kume, J.; Rousseau, J.P.

1994-01-01

A borehole instrumentation and monitoring program has been designed by the US Geological Survey to support site characterization of unsaturated-zone percolation at Yucca Mountain, Nye County, Nevada. This program provides a means of defining the unsaturated-zone fluid flow (liquid and gas) potential field in a setting that incorporates large-scale stratigraphic and structural features, and the influences of geothermal heat flow and atmospheric pressure changes. Data derived from this program will be used to evaluate the suitability of Yucca Mountain as a mined geologic-repository for the storage of high-level, radioactive waste. These data include in-situ temperature, pneumatic pressure, and water potential. In addition, the instrumentation program provides facilities for gas-sampling, gas-tracer diffusion testing, water-injection testing, water-level monitoring, neutron moisture-meter monitoring, temperature profiling, and in-situ recalibration of the downhole sensors. The program included testing and development of: (1) precision sensors for measurement; (2) a downhole instrumentation-station-apparatus to house the sensors, recalibrate sensors in-situ, and allow access to instrument stations for other testing purposes; and (3) surface-based support and instrumentation facilities

Natural Length Scales Shape Liquid Phase Continuity in Unsaturated Flows

Science.gov (United States)

Assouline, S.; Lehmann, P. G.; Or, D.

2015-12-01

Unsaturated flows supporting soil evaporation and internal drainage play an important role in various hydrologic and climatic processes manifested at a wide range of scales. We study inherent natural length scales that govern these flow processes and constrain the spatial range of their representation by continuum models. These inherent length scales reflect interactions between intrinsic porous medium properties that affect liquid phase continuity, and the interplay among forces that drive and resist unsaturated flow. We have defined an intrinsic length scale for hydraulic continuity based on pore size distribution that controls soil evaporation dynamics (i.e., stage 1 to stage 2 transition). This simple metric may be used to delineate upper bounds for regional evaporative losses or the depth of soil-atmosphere interactions (in the absence of plants). A similar length scale governs the dynamics of internal redistribution towards attainment of field capacity, again through its effect on hydraulic continuity in the draining porous medium. The study provides a framework for guiding numerical and mathematical models for capillary flows across different scales considering the necessary conditions for coexistence of stationarity (REV), hydraulic continuity and intrinsic capillary gradients.

Water Drainage from Unsaturated Soils in a Centrifuge Permeameter

Science.gov (United States)

Ornelas, G.; McCartney, J.; Zhang, M.

2013-12-01

This study involves an analysis of water drainage from an initially saturated silt layer in a centrifuge permeameter to evaluate the hydraulic properties of the soil layer in unsaturated conditions up to the point where the water phase becomes discontinuous. These properties include the soil water retention curve (SWRC) and the hydraulic conductivity function (HCF). The hydraulic properties of unsaturated silt are used in soil-atmosphere interaction models that take into account the role of infiltration and evaporation of water from soils due to atmospheric interaction. These models are often applied in slope stability analyses, landfill cover design, aquifer recharge analyses, and agricultural engineering. The hydraulic properties are also relevant to recent research concerning geothermal heating and cooling, as they can be used to assess the insulating effects of soil around underground heat exchangers. This study employs a high-speed geotechnical centrifuge to increase the self-weight of a compacted silt specimen atop a filter plate. Under a centrifuge acceleration of N times earth's gravity, the concept of geometric similitude indicates that the water flow process in a small-scale soil layer will be similar to those in a soil layer in the field that is N times thicker. The centrifuge acceleration also results in an increase in the hydraulic gradient across the silt specimen, which causes water to flow out of the pores following Darcy's law. The drainage test was performed until the rate of liquid water flow out of the soil layer slowed to a negligible level, which corresponds to the transition point at which further water flow can only occur due to water vapor diffusion following Fick's law. The data from the drainage test in the centrifuge were used to determine the SWRC and HCF at different depths in the silt specimen, which compared well with similar properties defined using other laboratory tests. The transition point at which liquid water flow stopped (and

Drift Scale Modeling: Study of Unsaturated Flow into a Drift Using a Stochastic Continuum Model

International Nuclear Information System (INIS)

Birkholzer, J.T.; Tsang, C.F.; Tsang, Y.W.; Wang, J.S

1996-01-01

Unsaturated flow in heterogeneous fractured porous rock was simulated using a stochastic continuum model (SCM). In this model, both the more conductive fractures and the less permeable matrix are generated within the framework of a single continuum stochastic approach, based on non-parametric indicator statistics. High-permeable fracture zones are distinguished from low-permeable matrix zones in that they have assigned a long range correlation structure in prescribed directions. The SCM was applied to study small-scale flow in the vicinity of an access tunnel, which is currently being drilled in the unsaturated fractured tuff formations at Yucca Mountain, Nevada. Extensive underground testing is underway in this tunnel to investigate the suitability of Yucca Mountain as an underground nuclear waste repository. Different flow scenarios were studied in the present paper, considering the flow conditions before and after the tunnel emplacement, and assuming steady-state net infiltration as well as episodic pulse infiltration. Although the capability of the stochastic continuum model has not yet been fully explored, it has been demonstrated that the SCM is a good alternative model feasible of describing heterogeneous flow processes in unsaturated fractured tuff at Yucca Mountain

Modeling one-dimensional unsaturated flow at the Rocky Flats Environmental Technology Site near Golden, Colorado

International Nuclear Information System (INIS)

Thompson, J.S.; Zeiler, R.M.

1995-01-01

A field investigation characterizing contamination at the Rocky Flats Plant (Rocky Flats Environmental Technology Site) near Golden, Colorado revealed unexpectedly high moisture contents in the unsaturated soil column (vadose zone) beneath several of the Plant's Waste Water Treatment Plant (WWTP) sludge drying beds. Because these beds were seldom in use, researchers had hypothesized that the water required to maintain the saturated conditions observed beneath several of the sludge drying beds was coming from sources other than the beds themselves. In an effort to substantiate this hypothesis, a one-dimensional physically-based unsaturated flow model was utilized to simulate the vertical movement of moisture from the sludge drying beds into the unsaturated soil column below. The model was run to simulate vertical flow over a two-year period and results indicated that no significant changes from initial conditions were apparent. This evidence supports the hypothesis that the high moisture contents found beneath the sludge drying beds are being fed by sources other than infiltration of sludge applied to the beds themselves. This paper presents the details of the simulation and provides further evidence of the hypothesized flow regime

Studies on the applicability of biomarkers in estimating the systematic bioavailability of polynuclear aromatic hydrocarbons from manufactured gas plant tar-contaminated soils

International Nuclear Information System (INIS)

Koganti, A.; Spina, D.A.; Rozett, K.; Ma, B.-L.; Weyand, E.; Taylor, B.B.; Mauro, D.M.

1998-01-01

The systematic bioavailability of polynuclear aromatic hydrocarbons (PAH) from ingested soils containing manufactured gas plant (MGP) tar was evaluated in mice. Soil and organic extract of each soil were incorporated into a diet and fed to mice for two weeks. 1-Hydroxypyrene levels in urine and chemical:DNA adduct levels in lungs were used as biomarkers of PAH systematic bioavailability. Estimates of PAH relative bioavailability were determined by comparing the bioavailability observed between each soil and corresponding organic extract. In all but one case, bioavailiablity estimates based on 1-hydroxypyrene levels in urine indicate that the presence of MGP tar on soil results in a considerable decrease in PAH systemic bioavailablity (9-75%). Similarly, PAH bioavailability estimates based on chemical:DNA adduct formation ranged from nondetectable to 76%. These results clearly indicate that the bioavailiablity of PAH is less than 100% when soil contaminated with MGP tar is ingested by nice. In addition, the experimental methods employed in this study appear suitable for evaluating the effects of soil on the gastrointestinal absorption and systemic bioavailability of PAH from soil containing complex organic mixtures. 44 refs., 1 fig., 5 tabs

A novel definition of the overall hyper-wiener index for unsaturated hydrocarbons.

Science.gov (United States)

Li, Xinhua; Hu, Maolin; Xiao, Hongping

2004-01-01

By replacing the distances between pairs of vertices with the relative distances, we define a novel overall hyper-Wiener index (NOR); the novel overall hyper-Wiener index extends the usefulness of the hyper-Wiener index and the overall hyper-Wiener index to unsaturated hydrocarbons.

TRPA1-dependent reversible opening of tight junction by natural compounds with an α,β-unsaturated moiety and capsaicin.

Science.gov (United States)

Kanda, Yusuke; Yamasaki, Youhei; Sasaki-Yamaguchi, Yoshie; Ida-Koga, Noriko; Kamisuki, Shinji; Sugawara, Fumio; Nagumo, Yoko; Usui, Takeo

2018-02-02

The delivery of hydrophilic macromolecules runs into difficulties such as penetration of the cell membrane lipid bilayer. Our prior experiment demonstrated that capsaicin induces the reversible opening of tight junctions (TJs) and enhances the delivery of hydrophilic macromolecules through a paracellular route. Herein, we screened paracellular permeability enhancers other than capsaicin. As TJ opening by capsaicin is associated with Ca 2+ influx, we first screened the compounds that induce Ca 2+ influx in layered MDCK II cells, and then we determined the compounds' abilities to open TJs. Our results identified several natural compounds with α,β-unsaturated moiety. A structure-activity relationship (SAR) analysis and the results of pretreatment with reducing reagent DTT suggested the importance of α,β-unsaturated moiety. We also examined the underlying mechanisms, and our findings suggest that the actin reorganization seen in capsaicin treatment is important for the reversibility of TJ opening. Furthermore, our analyses revealed that TRPA1 is involved in the Ca 2+ influx and TJ permeability increase not only by an α,β-unsaturated compound but also by capsaicin. Our results indicate that the α,β-unsaturated moiety can be a potent pharmacophore for TJ opening.

Sample size choices for XRCT scanning of highly unsaturated soil mixtures

Directory of Open Access Journals (Sweden)

Smith Jonathan C.

2016-01-01

Full Text Available Highly unsaturated soil mixtures (clay, sand and gravel are used as building materials in many parts of the world, and there is increasing interest in understanding their mechanical and hydraulic behaviour. In the laboratory, x-ray computed tomography (XRCT is becoming more widely used to investigate the microstructures of soils, however a crucial issue for such investigations is the choice of sample size, especially concerning the scanning of soil mixtures where there will be a range of particle and void sizes. In this paper we present a discussion (centred around a new set of XRCT scans on sample sizing for scanning of samples comprising soil mixtures, where a balance has to be made between realistic representation of the soil components and the desire for high resolution scanning, We also comment on the appropriateness of differing sample sizes in comparison to sample sizes used for other geotechnical testing. Void size distributions for the samples are presented and from these some hypotheses are made as to the roles of inter- and intra-aggregate voids in the mechanical behaviour of highly unsaturated soils.

Fully Biobased Unsaturated Aliphatic Polyesters from Renewable Resources : Enzymatic Synthesis, Characterization, and Properties

NARCIS (Netherlands)

Jiang, Yi; Alberda van Ekenstein, Gerhard; Woortman, Albert J. J.; Loos, Katja

2014-01-01

Fully biobased saturated and unsaturated aliphatic polyesters and oligoesters are successfully prepared by Candida antarctica lipase B (CALB)-catalyzed polycondensations of succinate, itaconate, and 1,4-butanediol. The effects of monomer substrates and polymerization methods on enzymatic

A Mass Conservative Numerical Solution for Two-Phase Flow in Porous Media With Application to Unsaturated Flow

DEFF Research Database (Denmark)

Celia, Michael A.; Binning, Philip John

1992-01-01

that the algorithm produces solutions that are essentially mass conservative and oscillation free, even in the presence of steep infiltrating fronts. When the algorithm is applied to the case of air and water flow in unsaturated soils, numerical results confirm the conditions under which Richards's equation is valid....... Numerical results also demonstrate the potential importance of air phase advection when considering contaminant transport in unsaturated soils. Comparison to several other numerical algorithms shows that the modified Picard approach offers robust, mass conservative solutions to the general equations...

Thermo-mechanical constitutive modeling of unsaturated clays based on the critical state concepts

Directory of Open Access Journals (Sweden)

Saeed Tourchi

2015-04-01

Full Text Available A thermo-mechanical constitutive model for unsaturated clays is constructed based on the existing model for saturated clays originally proposed by the authors. The saturated clays model was formulated in the framework of critical state soil mechanics and modified Cam-clay model. The existing model has been generalized to simulate the experimentally observed behavior of unsaturated clays by introducing Bishop's stress and suction as independent stress parameters and modifying the hardening rule and yield criterion to take into account the role of suction. Also, according to previous studies, an increase in temperature causes a reduction in specific volume. A reduction in suction (wetting for a given confining stress may induce an irreversible volumetric compression (collapse. Thus an increase in suction (drying raises a specific volume i.e. the movement of normal consolidation line (NCL to higher values of void ratio. However, some experimental data confirm the assumption that this reduction is dependent on the stress level of soil element. A generalized approach considering the effect of stress level on the magnitude of clays thermal dependency in compression plane is proposed in this study. The number of modeling parameters is kept to a minimum, and they all have clear physical interpretations, to facilitate the usefulness of model for practical applications. A step-by-step procedure used for parameter calibration is also described. The model is finally evaluated using a comprehensive set of experimental data for the thermo-mechanical behavior of unsaturated soils.

α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines.

Science.gov (United States)

Rigoli, Jared W; Moyer, Sara A; Pearce, Simon D; Schomaker, Jennifer M

2012-03-07

A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.

Film thinning in unsaturated superfluid 4He films during persistent flow

International Nuclear Information System (INIS)

Ekholm, D.T.; Hallock, R.B.

1979-01-01

We report measurements of the thickness of unsaturated superfluid 4 He films in persistent flow as a function of persistent current velocity. Our results are in quantitative agreement with the predictions of Kontorovich, and thus disagree with the conclusion of Rudnick and coworkers that rho/sub s//rho has an enhanced velocity dependence in these films

Permeable barrier materials for strontium immobilization: Unsaturated flow apparatus determination of hydraulic conductivity -- Column sorption experiments

International Nuclear Information System (INIS)

Moody, T.E.; Conca, J.

1996-09-01

Selected materials were tested to emulate a permeable barrier and to examine the (1) capture efficiency of these materials relating to the immobilization of strontium-90 and hexavalent chromium (Cr 6+ ) in Hanford Site groundwater; and (2) hydraulic conductivity of the barrier material relative to the surrounding area. The emplacement method investigated was a permeable reactive barrier to treat contaminated groundwater as it passes through the barrier. The hydraulic conductivity function was measured for each material, and retardation column experiments were performed for each material. Measurements determining the hydraulic conductivity at unsaturated through saturated water content were executed using the Unsaturated Flow Apparatus

The porous surface model, a novel experimental system for online quantitative observation of microbial processes under unsaturated conditions

DEFF Research Database (Denmark)

Dechesne, Arnaud; Or, D.; Gulez, Gamze

2008-01-01

Water is arguably the most important constituent of microbial microhabitats due to its control of physical and physiological processes critical to microbial activity. In natural environments, bacteria often live on unsaturated surfaces, in thin (micrometric) liquid films. Nevertheless, no experim....... The PSM constitutes a tool uniquely adapted to study the influence of liquid film geometry on microbial processes. It should therefore contribute to uncovering mechanisms of microbial adaptation to unsaturated environments.......Water is arguably the most important constituent of microbial microhabitats due to its control of physical and physiological processes critical to microbial activity. In natural environments, bacteria often live on unsaturated surfaces, in thin (micrometric) liquid films. Nevertheless......, no experimental systems are available that allow real-time observation of bacterial processes in liquid films of controlled thickness. We propose a novel, inexpensive, easily operated experimental platform, termed the porous surface model (PSM) that enables quantitative real-time microscopic observations...

COMPLEXES POLYMETALLIQUES DE LANTHANIDES (III) POUR LE DEVELOPPEMENT DE NOUVEAUX MATERIAUX LUMINESCENTS

OpenAIRE

Marchal , Claire

2008-01-01

The incorporation of f elements in highly organized polymetallic complexes is of great interest in supramolecularchemistry and allows the combination of their nanoscopic size with the magnetic or optical properties of the metal ions. However due to the difficulty in controlling the coordination environment of these ions, the assembly of lanthanide-based polynuclear architectures has lagged behind that of other systems. These factors make the rational design for the construction of supramolecu...

Natural weathering in dry disposed ash dump: Insight from chemical, mineralogical and geochemical analysis of fresh and unsaturated drilled cores.

Science.gov (United States)

Akinyemi, S A; Akinlua, A; Gitari, W M; Khuse, N; Eze, P; Akinyeye, R O; Petrik, L F

2012-07-15

Some existing alternative applications of coal fly ash such as cement manufacturing; road construction; landfill; and concrete and waste stabilisation use fresh ash directly collected from coal-fired power generating stations. Thus, if the rate of usage continues, the demand for fresh ash for various applications will exceed supply and use of weathered dry disposed ash will become necessary alternative. As a result it's imperative to understand the chemistry and pH behaviour of some metals inherent in dry disposed fly ash. The bulk chemical composition as determined by XRF analysis showed that SiO2, Al2O3 and Fe2O3 were the major oxides in fresh ash and unsaturated weathered ashes. The unsaturated weathered ashes are relatively depleted in CaO, Fe2O3, TiO2, SiO2, Na2O and P2O5 due to dissolution and hydrolysis caused by chemical interaction with ingressing CO2 from the atmosphere and infiltrating rain water. Observed accumulations of Fe2O3, TiO2, CaO, K2O, Na2O and SO3 and Zn, Zr, Sr, Pb, Ni, Cr and Co in the lower layers indicate progressive downward movement through the ash dump though at a slow rate. The bulk mineralogy of unsaturated weathered dry disposed ash, as determined by XRD analysis, revealed quartz and mullite as the major crystalline phases; while anorthite, hematite, enstatite, lime, calcite, and mica were present as minor mineral phases. Pore water chemistry revealed a low concentration of readily soluble metals in unsaturated weathered ashes in comparison with fresh ash, which shows high leachability. This suggests that over time the precipitation of transient minor secondary mineral phases; such as calcite and mica might retard residual metal release from unsaturated weathered ash. Chloride and sulphate species of the water soluble extracts of weathered ash are at equilibrium with Na+ and K+; these demonstrate progressive leaching over time and become supersaturated at the base of unsaturated weathered ash. This suggests that the ash dump does not

Optimality and Conductivity for Water Flow: From Landscapes, to Unsaturated Soils, to Plant Leaves

Energy Technology Data Exchange (ETDEWEB)

Liu, H.H.

2012-02-23

Optimality principles have been widely used in many areas. Based on an optimality principle that any flow field will tend toward a minimum in the energy dissipation rate, this work shows that there exists a unified form of conductivity relationship for three different flow systems: landscapes, unsaturated soils and plant leaves. The conductivity, the ratio of water flux to energy gradient, is a power function of water flux although the power value is system dependent. This relationship indicates that to minimize energy dissipation rate for a whole system, water flow has a small resistance (or a large conductivity) at a location of large water flux. Empirical evidence supports validity of the relationship for landscape and unsaturated soils (under gravity dominated conditions). Numerical simulation results also show that the relationship can capture the key features of hydraulic structure for a plant leaf, although more studies are needed to further confirm its validity. Especially, it is of interest that according to this relationship, hydraulic conductivity for gravity-dominated unsaturated flow, unlike that defined in the classic theories, depends on not only capillary pressure (or saturation), but also the water flux. Use of the optimality principle allows for determining useful results that are applicable to a broad range of areas involving highly non-linear processes and may not be possible to obtain from classic theories describing water flow processes.

Evolution of strain localization in variable-width three-dimensional unsaturated laboratory-scale cut slopes

Science.gov (United States)

Morse, Michael S.; Lu, Ning; Wayllace, Alexandra; Godt, Jonathan W.

2017-01-01

To experimentally validate a recently developed theory for predicting the stability of cut slopes under unsaturated conditions, the authors measured increasing strain localization in unsaturated slope cuts prior to abrupt failure. Cut slope width and moisture content were controlled and varied in a laboratory, and a sliding door that extended the height of the free face of the slope was lowered until the cut slope failed. A particle image velocimetry tool was used to quantify soil displacement in the x-y">x-y (horizontal) and x-z">x-z (vertical) planes, and strain was calculated from the displacement. Areas of maximum strain localization prior to failure were shown to coincide with the location of the eventual failure plane. Experimental failure heights agreed with the recently developed stability theory for unsaturated cut slopes (within 14.3% relative error) for a range of saturation and cut slope widths. A theoretical threshold for sidewall influence on cut slope failures was also proposed to quantify the relationship between normalized sidewall width and critical height. The proposed relationship was consistent with the cut slope experiment results, and is intended for consideration in future geotechnical experiment design. The experimental data of evolution of strain localization presented herein provide a physical basis from which future numerical models of strain localization can be validated.

Semi-analytical treatment of fracture/matrix flow in a dual-porosity simulator for unsaturated fractured rock masses

International Nuclear Information System (INIS)

Zimmerman, R.W.; Bodvarsson, G.S.

1992-04-01

A semi-analytical dual-porosity simulator for unsaturated flow in fractured rock masses has been developed. Fluid flow between the fracture network and the matrix blocks is described by analytical expressions that have been derived from approximate solutions to the imbibition equation. These expressions have been programmed into the unsaturated flow simulator, TOUGH, as a source/sink term. Flow processes are then simulated using only fracture elements in the computational grid. The modified code is used to simulate flow along single fractures, and infiltration into pervasively fractured formations

Can Electrical Resistance Tomography be used for imaging unsaturated moisture flow in cement-based materials with discrete cracks?

International Nuclear Information System (INIS)

Smyl, Danny; Rashetnia, Reza; Seppänen, Aku; Pour-Ghaz, Mohammad

2017-01-01

Previously, it has been shown that Electrical Resistance Tomography (ERT) can be used for monitoring moisture flow in undamaged cement-based materials. In this work, we investigate whether ERT could be used for imaging three-dimensional (3D) unsaturated moisture flow in cement-based materials that contain discrete cracks. Novel computational methods based on the so-called absolute imaging framework are developed and used in ERT image reconstructions, aiming at a better tolerance of the reconstructed images with respect to the complexity of the conductivity distribution in cracked material. ERT is first tested using specimens with physically simulated cracks of known geometries, and corroborated with numerical simulations of unsaturated moisture flow. Next, specimens with loading-induced cracks are imaged; here, ERT reconstructions are evaluated qualitatively based on visual observations and known properties of unsaturated moisture flow. Results indicate that ERT is a viable method of visualizing 3D unsaturated moisture flow in cement-based materials with discrete cracks. - Highlights: • 3D EIT is developed to visualize water ingress in cracked mortar. • Mortar with different size discrete cracks are used. • The EIT results are corroborated with numerical simulations. • EIT results accurately show the temporal and spatial variation of water content. • EIT is shown to be a viable method to monitor flow in cracks and matrix.

Saturated-unsaturated flow to a well with storage in a compressible unconfined aquifer

Science.gov (United States)

Mishra, Phoolendra Kumar; Neuman, Shlomo P.

2011-05-01

Mishra and Neuman (2010) developed an analytical solution for flow to a partially penetrating well of zero radius in a compressible unconfined aquifer that allows inferring its saturated and unsaturated hydraulic properties from responses recorded in the saturated and/or unsaturated zones. Their solution accounts for horizontal as well as vertical flows in each zone. It represents unsaturated zone constitutive properties in a manner that is at once mathematically tractable and sufficiently flexible to provide much improved fits to standard constitutive models. In this paper we extend the solution of [2010] to the case of a finite diameter pumping well with storage; investigate the effects of storage in the pumping well and delayed piezometer response on drawdowns in the saturated and unsaturated zones as functions of position and time; validate our solution against numerical simulations of drawdown in a synthetic aquifer having unsaturated properties described by the [1980]- [1976] model; use our solution to analyze 11 transducer-measured drawdown records from a seven-day pumping test conducted by University of Waterloo researchers at the Canadian Forces Base Borden in Ontario, Canada; validate our parameter estimates against manually-measured drawdown records in 14 other piezometers at Borden; and compare (a) our estimates of aquifer parameters with those obtained on the basis of all these records by [2008], (b) on the basis of 11 transducer-measured drawdown records by [2007], (c) our estimates of van Genuchten-Mualem parameters with those obtained on the basis of laboratory drainage data from the site by [1992], and (d) our corresponding prediction of how effective saturation varies with elevation above the initial water table under static conditions with a profile based on water contents measured in a neutron access tube at a radial distance of about 5 m from the center of the pumping well. We also use our solution to analyze 11 transducer-measured drawdown

Kinetic study of the degradation of C5 and C6 unsaturated aldehydes and alcohols by ozone

Science.gov (United States)

Kalalian, Carmen; Roth, Estelle; Chakir, Abdelkhaleq

2017-04-01

Emissions of biogenic volatile organic compounds (VOCs) are higher than those from anthropogenic sources. They are therefore likely to have a great influence on atmospheric chemistry both locally and regionally, through their impact on the HOx balance (HOx = HO + HO2), ozone production and ability to form secondary organic aerosols (SOA). Among the volatile organic compounds of biogenic origin are the family of C5 and C6 unsaturated aldehydes and alcohols. Few information exist regarding the fate of these compounds in the atmosphere especially there reaction with ozone. In this work, we studied the kinetics of the reaction of three unsaturated aldehydes (trans-2-pentenal, trans-2-hexenal and 2-methyl-2-pentenal) and three unsaturated alcohols (1-penten-3-ol, cis-2-penten-1-ol and trans-3-hexen-1-ol) with ozone O3 in a rigid atmospheric simulation chamber coupled to an FTIR spectrometer at four different temperatures (273, 298, 333 and 353 K) and at atmospheric pressure. The rate constants of the ozonolysis reaction of the unsaturated aldehydes and the unsaturated alcohols studied were determined and the following Arrhenius expression was obtained (cm3 molecule -1 s -1): k (Trans -2-pentenal)= (3.83 ± 3.71) x 10-16 exp (- (1706 ± 295) / T) k (Trans-2-hexenal)= (1.43 ± 0.67) x 10-16 exp (- (1369 ± 141) / T) k(2-Methyl-2-pentenal)= (3.62± 0.22) x 10-18 exp (- (121 ± 20) / T) k(1-penten-3-ol) = (1.42 ± 1.24) x 10-16 exp (- (642 ± 250) / T) k(Cis-2-penten-1-ol)= (3.14 ± 0.45) x 10-15 exp (- (1045 ± 40) / T) k(Trans-3-hexen-1-ol)= (6.38 ± 1.75) x 10-16 exp (- (686 ± 89) / T) The obtained data will be discussed in terms of structure-reactivity relationship and compared with the reported reactivity with OH radicals. The atmospheric implications derived from this study are discussed as well.

Investigation of isotopic signals in the unsaturated zone with the use of direct push technology and azaeotropic distillation

Directory of Open Access Journals (Sweden)

Andreas Kallioras

2012-09-01

Full Text Available This paper contributes to the investigation of the unsaturated zone, through the application of combined field and lab techniques. The results show that direct push methods, which are considered ideal for multilevel sampling of undisturbed soil in the unsaturated zone, proved to be effective also for the consequent extraction of the pore water for further isotopic determination. This ultimate goal can be achieved thank to the application of azaetropic distillation, which has the least isotopic fractionation effects on groundwater samples.

Unsaturated fatty acids lactose esters: cytotoxicity, permeability enhancement and antimicrobial activity

OpenAIRE

Lucarini, Simone; Fagioli, Laura; Campana, Raffaella; Cole, Hannah; Duranti, Andrea; Baffone, Wally; Vllasaliu, Driton; Casettari, Luca

2016-01-01

Sugar based surfactants conjugated with fatty acid chains are an emerging broad group of highly biocompatible and biodegradable compounds with established and potential future applications in the pharmaceutical, cosmetic and food industries. In this work, we investigated absorption enhancing and antimicrobial properties of disaccharide lactose, mono-esterified with unsaturated fatty acids through an enzymatic synthetic approach. After chemical and cytotoxicity characterizations, their permeab...

Solution of AntiSeepage for Mengxi River Based on Numerical Simulation of Unsaturated Seepage

Science.gov (United States)

Ji, Youjun; Zhang, Linzhi; Yue, Jiannan

2014-01-01

Lessening the leakage of surface water can reduce the waste of water resources and ground water pollution. To solve the problem that Mengxi River could not store water enduringly, geology investigation, theoretical analysis, experiment research, and numerical simulation analysis were carried out. Firstly, the seepage mathematical model was established based on unsaturated seepage theory; secondly, the experimental equipment for testing hydraulic conductivity of unsaturated soil was developed to obtain the curve of two-phase flow. The numerical simulation of leakage in natural conditions proves the previous inference and leakage mechanism of river. At last, the seepage control capacities of different impervious materials were compared by numerical simulations. According to the engineering actuality, the impervious material was selected. The impervious measure in this paper has been proved to be effectible by hydrogeological research today. PMID:24707199

Plant adaptation to frequent alterations between high and low temperatures: remodeling of membrane lipids and maintenance of unsaturation levels

OpenAIRE

Zheng, Guowei; Tian, Bo; Zhang, Fujuan; Tao, Faqing; Li, Weiqi

2011-01-01

One major strategy by which plants adapt to temperature change is to decrease the degree of unsaturation of membrane lipids under high temperature and increase it under low temperature. We hypothesize that this strategy cannot be adopted by plants in ecosystems and environments with frequent alterations between high and low temperatures, because changes in lipid unsaturation are complex and require large energy inputs. To test this hypothesis, we used a lipidomics approach to profile changes ...

Effects of Unsaturated Fat Dietary Supplements on Blood Lipids, and on Markers of Malnutrition and Inflammation in Hemodialysis Patients

DEFF Research Database (Denmark)

Ewers, Bettina; Riserus, Ulf; Marckmann, Peter

2009-01-01

OBJECTIVE: We examined the effects of commercially available unsaturated fat dietary supplements on blood lipids, and on markers of malnutrition and inflammation, in an adult population of hemodialysis (HD) patients. DESIGN: This was a restricted, randomized (equal blocks), investigator-blinded 2x6...... as assessed according to C-reactive protein serum concentrations. Adding unsaturated fat to the diet seems to be a safe and effective way to prevent and treat malnutrition in hemodialysis patients....

Approaches to large scale unsaturated flow in heterogeneous, stratified, and fractured geologic media

International Nuclear Information System (INIS)

Ababou, R.

1991-08-01

This report develops a broad review and assessment of quantitative modeling approaches and data requirements for large-scale subsurface flow in radioactive waste geologic repository. The data review includes discussions of controlled field experiments, existing contamination sites, and site-specific hydrogeologic conditions at Yucca Mountain. Local-scale constitutive models for the unsaturated hydrodynamic properties of geologic media are analyzed, with particular emphasis on the effect of structural characteristics of the medium. The report further reviews and analyzes large-scale hydrogeologic spatial variability from aquifer data, unsaturated soil data, and fracture network data gathered from the literature. Finally, various modeling strategies toward large-scale flow simulations are assessed, including direct high-resolution simulation, and coarse-scale simulation based on auxiliary hydrodynamic models such as single equivalent continuum and dual-porosity continuum. The roles of anisotropy, fracturing, and broad-band spatial variability are emphasized. 252 refs

Hydrogeology of the unsaturated zone, North Ramp area of the Exploratory Studies Facility, Yucca Mountain, Nevada

Energy Technology Data Exchange (ETDEWEB)

Rousseau, J.P.; Kwicklis, E.M.; Gillies, D.C. [eds.

1999-03-01

Yucca Mountain, in southern Nevada, is being investigated by the US Department of Energy as a potential site for a repository for high-level radioactive waste. This report documents the results of surface-based geologic, pneumatic, hydrologic, and geochemical studies conducted during 1992 to 1996 by the US Geological Survey in the vicinity of the North Ramp of the Exploratory Studies Facility (ESF) that are pertinent to understanding multiphase fluid flow within the deep unsaturated zone. Detailed stratigraphic and structural characteristics of the study area provided the hydrogeologic framework for these investigations. Shallow infiltration is not discussed in detail in this report because the focus in on three major aspects of the deep unsaturated-zone system: geologic framework, the gaseous-phase system, and the aqueous-phase system. However, because the relation between shallow infiltration and deep percolation is important to an overall understanding of the unsaturated-zone flow system, a summary of infiltration studies conducted to date at Yucca Mountain is provided in the section titled Shallow Infiltration. This report describes results of several Site Characterization Plan studies that were ongoing at the time excavation of the ESF North Ramp began and that continued as excavation proceeded.

Highly Functionalised Cyclopentanes by Radical Cyclisation of Unsaturated Bromolactones III. Preparation of Carbaaldohexofuranoses. - Determination of the Relative Configuration at C-4/C-5 of 2,3-Unsaturated heptono-1,4-lactones by Means of 1-H NMR Spectroscopy

DEFF Research Database (Denmark)

Lundt, Inge; Horneman, Anne Marie

1999-01-01

Two new carbaaldohexofuranoses, carba--D-glucofuranose and carba--L-mannofuranose have been prepared using 5,6-O-isopropylidene-D-glycero-L-galacto-heptono-1,4-lactone (6) as the starting material. The key step was a highly stereoselective intramolecular 5-exo-trig radical cyclisation of C-2......-substituted 2,3-unsaturated 7-bromo-7-deoxy-heptono-1,4-lactones promoted by tributyltin hydride. Assignment of the configuration of the unsaturated lactones was based upon NMR data of related compounds. The starting material, compound 6, was obtained by chain elongation of D-gulose, and a facile method...

Research program to develop and validate conceptual models for flow and transport through unsaturated, fractured rock

International Nuclear Information System (INIS)

Glass, R.J.; Tidwell, V.C.

1991-01-01

As part of the Yucca Mountain Project, our research program to develop and validate conceptual models for flow and transport through unsaturated fractured rock integrates fundamental physical experimentation with conceptual model formulation and mathematical modeling. Our research is directed toward developing and validating macroscopic, continuum-based models and supporting effective property models because of their widespread utility within the context of this project. Success relative to the development and validation of effective property models is predicated on a firm understanding of the basic physics governing flow through fractured media, specifically in the areas of unsaturated flow and transport in a single fracture and fracture-matrix interaction. 43 refs

Research program to develop and validate conceptual models for flow and transport through unsaturated, fractured rock

International Nuclear Information System (INIS)

Glass, R.J.; Tidwell, V.C.

1991-09-01

As part of the Yucca Mountain Project, our research program to develop and validate conceptual models for flow and transport through unsaturated fractured rock integrates fundamental physical experimentation with conceptual model formulation and mathematical modeling. Our research is directed toward developing and validating macroscopic, continuum-based models and supporting effective property models because of their widespread utility within the context of this project. Success relative to the development and validation of effective property models is predicted on a firm understanding of the basic physics governing flow through fractured media, specifically in the areas of unsaturated flow and transport in a single fracture and fracture-matrix interaction

Research program to develop and validate conceptual models for flow and transport through unsaturated, fractured rock

International Nuclear Information System (INIS)

Glass, R.J.; Tidwell, V.C.

1991-01-01

As part of the Yucca Mountain Project, our research program to develop and validate conceptual models for flow and transport through unsaturated fractured rock integrates fundamental physical experimentation with conceptual model formulation and mathematical modeling. Our research is directed toward developing and validating macroscopic, continuum-based models and supporting effective property models because of their widespread utility within the context of this project. Success relative to the development and validation of effective property models is predicted on a firm understanding of the basic physics governing flow through fractured media, specifically in the areas of unsaturated flow and transport in a single fracture and fracture-matrix interaction

Nitrogen fluxes through unsaturated zones in five agricultural settings across the United States

Science.gov (United States)

Green, C.T.; Fisher, L.H.; Bekins, B.A.

2008-01-01

The main physical and chemical controls on nitrogen (N) fluxes between the root zone and the water table were determined for agricultural sites in California, Indiana, Maryland, Nebraska, and Washington from 2004 to 2005. Sites included irrigated and nonirrigated fields; soil textures ranging from clay to sand; crops including corn, soybeans, almonds, and pasture; and unsaturated zone thicknesses ranging from 1 to 22 m. Chemical analyses of water from lysimeters and shallow wells indicate that advective transport of nitrate is the dominant process affecting the flux of N below the root zone. Vertical profiles of (i) nitrogen species, (ii) stable isotopes of nitrogen and oxygen, and (iii) oxygen, N, and argon in unsaturated zone air and correlations between N and other agricultural chemicals indicate that reactions do not greatly affect N concentrations between the root zone and the capillary fringe. As a result, physical factors, such as N application rate, water inputs, and evapotranspiration, control the differences in concentrations among the sites. Concentrations of N in shallow lysimeters exhibit seasonal variation, whereas concentrations in lysimeters deeper than a few meters are relatively stable. Based on concentration and recharge estimates, fluxes of N through the deep unsaturated zone range from 7 to 99 kg ha-1 yr-1. Vertical fluxes of N in ground water are lower due to spatial and historical changes in N inputs. High N fluxes are associated with coarse sediments and high N application rates. Copyright ?? 2008 by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America. All rights reserved.

Nitrate transport and transformation processes in unsaturated porous media

Science.gov (United States)

Tindall, James A.; Petrusak, Robin L.; McMahon, Peter B.

1995-01-01

A series of experiments was conducted on two contrasting agricultural soils to observe the influence of soil texture, preferential flow, and plants on nitrate transport and denitrification under unsaturated conditions. Calcium nitrate fertilizer was applied to the surface of four large undisturbed soil cores (30 cm diameter by 40 cm height). Two of the cores were a structured clay obtained from central Missouri and two were an unstructured fine sand obtained from central Florida. The cores were irrigated daily and maintained at a matric potential of -20 kPa, representative of soil tension in the rooting zone of irrigated agricultural fields. Volumetric water content (θ), concentration of nitrate-N in the soil solution, and nitrous oxide flux at the surface, 10, 20, and 30 cm were monitored daily. Leaching loss of surface-applied N03− -N was significant in both the sand and the clay. In unplanted sand cores, almost all of the applied nitrate was leached below 30 cm within 10 days. Gaseous N loss owing to denitrification was no greater than 2% of the nitrate-N applied to the unplanted sand cores and, in general, was less than 1 %. Although leaching was somewhat retarded in the clay cores, about 60% of the applied nitrate-N was leached from the unplanted clay soil in 5–6 weeks. Under unsaturated conditions, the clay had little to no tendency to denitrify despite the greater moisture content of the clay and retarded leaching of nitrate in the clay. The planted sand cores had surprisingly large gaseous N loss owing to denitrification, as much as 17% of the nitrate-N. Results from both the clay and sand experiments show that the dynamics of nitrate transport and transformation in unsaturated soils are affected by small, localized variations in the soil moisture content profile, the gaseous diffusion coefficient of the soil, the rate at which the nitrate pulse passes through the soil, the solubility of N2O and N2 and the diffusion of the gasses through the soil

Field determination of vertical permeability to air in the unsaturated zone

Science.gov (United States)

Weeks, Edwin P.

1978-01-01

The vertical permeability to air of layered materials in the unsaturated zone may be determined from air pressure data obtained at depth during a period when air pressure is changing at land surface. Such data may be obtained by monitoring barometric pressure with a microbarograph or surveying altimeter and simultaneously measuring down-hole pneumatic head differences in specially constructed piezometers. These data, coupled with air-filled porosity data from other sources, may be compared with the results of electric-analog or numerical solution of the one-dimensional diffusion equation to make a trial-and-error determination of the air permeability for each layer. The permeabilities to air may in turn be converted to equivalent hydraulic conductivity values if the materials are well drained, are permeable enough that the Klinkenberg effect is small, and are structurally unaffected by wetting. The method offers potential advantages over present methods to evaluate sites for artificial recharge by spreading; to evaluate ground-water pollution hazards from feedlots, sanitary landfills , and land irrigated with sewage effluent; and to evaluate sites for temporary storage of gas in the unsaturated zone. (Woodard-USGS)

Monte Carlo simulation of radioactive contaminant transport in unsaturated porous media

International Nuclear Information System (INIS)

Giacobbo, F.; Patelli, E.; Zio, E.

2005-01-01

In the current proposed solutions of radioactive waste repositories, the protective function against the radionuclide water-driven transport back to the biosphere is to be provided by an integrated system of artificial and natural geologic barriers. The complexity of the transport process in the barriers' heterogeneous media forces approximations to the classical analytical-numerical models, thus reducing their adherence to reality. In an attempt to overcome these difficulties, in the present paper we adopt a Monte Carlo simulation approach, previously developed on the basis of the Kolmogorov and Dmitriev theory of branching stochastic processes. The approach is here extended for describing transport through unsaturated porous media under unsteady flow conditions. This generalization entails the determination of the functional dependence of the parameters of the proposed transport model from the water content, which changes in space and time during the water infiltration process. The approach is verified with respect to a case of non-reactive transport under transient unsaturated field conditions by a comparison with a standard code based on the classical advection-dispersion equations. An application regarding linear reactive transport is then presented. (authors)

Colloid suspension stability and transport through unsaturated porous media

International Nuclear Information System (INIS)

McGraw, M.A.; Kaplan, D.I.

1997-04-01

Contaminant transport is traditionally modeled in a two-phase system: a mobile aqueous phase and an immobile solid phase. Over the last 15 years, there has been an increasing awareness of a third, mobile solid phase. This mobile solid phase, or mobile colloids, are organic or inorganic submicron-sized particles that move with groundwater flow. When colloids are present, the net effect on radionuclide transport is that radionuclides can move faster through the system. It is not known whether mobile colloids exist in the subsurface environment of the Hanford Site. Furthermore, it is not known if mobile colloids would likely exist in a plume emanating from a Low Level Waste (LLW) disposal site. No attempt was made in this study to ascertain whether colloids would form. Instead, experiments and calculations were conducted to evaluate the likelihood that colloids, if formed, would remain in suspension and move through saturated and unsaturated sediments. The objectives of this study were to evaluate three aspects of colloid-facilitated transport of radionuclides as they specifically relate to the LLW Performance Assessment. These objectives were: (1) determine if the chemical conditions likely to exist in the near and far field of the proposed disposal site are prone to induce flocculation (settling of colloids from suspension) or dispersion of naturally occurring Hanford colloids, (2) identify the important mechanisms likely involved in the removal of colloids from a Hanford sediment, and (3) determine if colloids can move through unsaturated porous media

Reactions of carbonyl compounds with α,β-unsaturated nitriles as a convenient pathway to carbo- and heterocycles

International Nuclear Information System (INIS)

Sharanin, Yu A; Goncharenko, M P; Litvinov, Victor P

1998-01-01

Published data on the methods for synthesis of carbo- and heterocyclic compounds based on reactions of α,β-unsaturated nitriles with carbonyl compounds and activated phenols are surveyed. It is demonstrated that all these reactions occur via nucleophilic addition of the carbanion generated from a carbonyl compound to the double bond of an unsaturated nitrile (the Michael reaction). The main routes of transformation of the adducts into carbo- and heterocyclic compounds are considered. The methods for regioselective preparation of fused 4H-pyrans or 1,4-dihydropyridines by varying conditions of cyclisation of Michael adducts are discussed. The bibliography includes 249 references.

Estimating unsaturated hydraulic conductivity from soil moisture-tim function

International Nuclear Information System (INIS)

El Gendy, R.W.

2002-01-01

The unsaturated hydraulic conductivity for soil can be estimated from o(t) function, and the dimensionless soil water content parameter (Se)Se (β - βr)/ (φ - θ)), where θ, is the soil water content at any time (from soil moisture depletion curve l; θ is the residual water content and θ, is the total soil porosity (equals saturation point). Se can be represented as a time function (Se = a t b ), where t, is the measurement time and (a and b) are the regression constants. The recommended equation in this method is given by

Products and mechanism of the reaction of Cl atoms with unsaturated alcohols

Science.gov (United States)

Rodríguez, Ana; Rodríguez, Diana; Soto, Amparo; Bravo, Iván; Diaz-de-Mera, Yolanda; Notario, Alberto; Aranda, Alfonso

2012-04-01

The products of the chlorine atom initiated oxidation of different unsaturated alcohols were determined at atmospheric pressure and ambient temperature, in a 400 L teflon reaction chamber using GC-FID and GC-MS for the analysis. The major products detected (with molar yields in brackets) are: chloroacetaldehyde (50 ± 8%) and acrolein (27 ± 2%) from allyl alcohol; acetaldehyde (77 ± 11%), chloroacetaldehyde (75 ± 18%), and methyl vinyl ketone (17 ± 2%) from 3-buten-2-ol; acetone (55 ± 4%) and chloroacetaldehyde (59 ± 8%) from 2-methyl-3-buten-2-ol; chloroacetone (18 ± 1%) and methacrolein (8 ± 1%) from 2-methyl-2-propen-1-ol; acetaldehyde (20 ± 1%), crotonaldehyde (6 ± 3%), 3-choloro-4-hydroxy-2-butanone (2 ± 2%) and 2-chloro-propanal (4 ± 5%) from crotyl alcohol; and acetone (24 ± 3%) from 3-methyl-2-buten-1-ol. The experimental data suggests that addition of Cl to the double bond of the unsaturated alcohol is the dominant reaction pathway compared to the H-abstraction channel.

The role of unsaturations in the Gamma irradiation of crosslinkable polymers

International Nuclear Information System (INIS)

Satti, Angel J.; Ciolino, Andrés E.; Andreucetti, Noemí A.; Vallés, Enrique M.

2015-01-01

Nowadays, the understanding of the interaction of ionizing radiations with polymeric materials is becoming increasingly important. It is well known that many parameters regarding the synthesis of the polymers noticeably affect the irradiation process. In this work, an analysis of the effect of the type and the position of unsaturations in the molecular structure of crosslinkable polymers is performed. For such purpose, two solid semycristalline metallocenic ethylene 1-olefin copolymers (mEOC) which contain a low concentration of unsaturations from the synthesis, and their hydrogenated samples, were irradiated along with liquid poly(dimethylsiloxane) (PDMS) homo and copolymers containing different location and concentration of vinyl groups, which were structurally tailored through anionic synthesis. The source of irradiation was 60 Co, under vacuum at room temperature, in all the cases. The results indicated that terminal vinyls drastically accelerate the crosslinking to lower doses, even at much lower concentrations than other type and location of unsaturations for both, mEOC and PDMS, type of polymers. - Graphical abstract: Irradiated PEX # (ethylene copolymers with an # amount of 1-hexene -H- or 1-octadecene -OD) and their non-vinyl containing hidrogenated samples (PEX #h), along with irradiated vinyl functionalized siloxane polymers. Numbers within parentheses correspond to the number of vinyl groups per polymer chain for each irradiated polymer. Note that PDVi have been crosslinked with the lower dose of irradiation, although it has only one vinyl group. However, that is a terminal vinyl, while for the other polydimethylsiloxane derivatives, vinyls are within the main chain. - Highlights: • Terminal vinyls from metallocenic synthesis accelerate radioinduced crosslinking. • Trans vinyl structures are generated during irradiation, but vinyldenes are reluctant to react. • The position of the vinyl groups noticeably affects the irradiation process. �

Solution of AntiSeepage for Mengxi River Based on Numerical Simulation of Unsaturated Seepage

Directory of Open Access Journals (Sweden)

Youjun Ji

2014-01-01

Full Text Available Lessening the leakage of surface water can reduce the waste of water resources and ground water pollution. To solve the problem that Mengxi River could not store water enduringly, geology investigation, theoretical analysis, experiment research, and numerical simulation analysis were carried out. Firstly, the seepage mathematical model was established based on unsaturated seepage theory; secondly, the experimental equipment for testing hydraulic conductivity of unsaturated soil was developed to obtain the curve of two-phase flow. The numerical simulation of leakage in natural conditions proves the previous inference and leakage mechanism of river. At last, the seepage control capacities of different impervious materials were compared by numerical simulations. According to the engineering actuality, the impervious material was selected. The impervious measure in this paper has been proved to be effectible by hydrogeological research today.

Asymptotically optimal unsaturated lattice cubature formulae with bounded boundary layer

Energy Technology Data Exchange (ETDEWEB)

Ramazanov, M D [Institute of Mathematics with Computing Centre, Ufa Science Centre, Russian Academy of Sciences, Ufa (Russian Federation)

2013-07-31

This paper describes a new algorithm for constructing lattice cubature formulae with bounded boundary layer. These formulae are unsaturated (in the sense of Babenko) both with respect to the order and in regard to the property of asymptotic optimality on W{sub 2}{sup m}-spaces, m element of (n/2,∞). Most of the results obtained apply also to W{sub 2}{sup μ}(R{sup n})-spaces with a hypoelliptic multiplier of smoothness μ. Bibliography: 6 titles.

Unsaturated medium hydrocarbons pollution evaluation

International Nuclear Information System (INIS)

Di Luise, G.

1991-01-01

When the so called porous unsaturated medium, that's the vertical subsoil section between both the ground and water-table level, is interested by a hydrocarbons spill, the problem to evaluate the pollution becomes difficult: considering, essentially, the natural coexistence in it of two fluids, air and water, and the interactions between them. This paper reports that the problems tend to increase when a third fluid, the pollutant, immiscible with water, is introduced into the medium: a three-phases flow, which presents several analogies with the flow conditions present in an oil-reservoir, will be established. In such a situation, it would be very useful to handle the matter by the commonly used parameters in the oil reservoirs studies such as: residual saturation, relative permeability, phases mobility, to derive a first semiquantitative estimation of the pollution. The subsoil pollution form hydrocarbons agents is one of the worldwide more diffused causes of contamination: such events are generally referable to two main effects: accidental (oil pipeline breakdowns, e.g.), and continuous (underground tanks breaks, industrial plants leakages, e.g.)

Soil water movement in the unsaturated zone of an inland arid region: Mulched drip irrigation experiment

Science.gov (United States)

Han, Dongmei; Zhou, Tiantian

2018-04-01

Agricultural irrigation with trans-basin water diversion can effectively relieve the water paucity in arid and semi-arid regions, however, this may be accompanied by eco-environmental problems (e.g., saline soils, rising groundwater levels, water quality problems). The mechanism of soil water movement under irrigation in the unsaturated zone of arid regions is a key scientific problem that should be solved in order to evaluate agricultural water management and further improve current irrigation practices. This study investigated the impact of drip irrigation on soil water movement in the unsaturated zone of a cotton field in an inland arid region (the Karamay Agricultural Development Area), northwest China. Combining in situ observational physical data with temporal variation in stable isotopic compositions of soil water, we described the soil water flow system and mechanism in severe (Plot 1) and mild (Plot 2) saline-alkali cotton fields. The infiltration depths are 0-150 cm for both plots. Drip irrigation scheduling makes no significant contribution to local groundwater recharge, however, groundwater can move into the unsaturated zone through capillary rise during cotton flowering and boll periods. Plot 2 is less prone to having secondary soil salinization than Plot 1 due to the existence of a middle layer (approximately 100 cm thick), which elongated the distance between the root zone and aquifer. Rise in the water table (approximately 60 cm for Plot 1 and 50 cm for Plot 2) could be caused by lateral groundwater flow instead of vertical infiltration. We estimated the soil water storage changes in the unsaturated zone and proposed a conceptual model for deciphering the movement process of soil water. This study provides a scientific basis for determining the rise of groundwater levels and potential development of saline soils and improving agricultural water management in arid regions.

Annual report on monitoring of the unsaturated zone and recharge areas at INEL to the state of Idaho INEL Oversight Committee

International Nuclear Information System (INIS)

King, B.; Bloomsburg, G.; Horn, D.; Liou, J.; Finnie, J.

1992-01-01

During the early years of the INEL, the USGS conducted extensive studies (sitewide drilling program) of the geology and hydrology of the area collecting varied data over the years. The unsaturated zone has not received much attention until recently. The studies that have been done are a result of problems or concerns arising from liquid radioactive waste disposal. The TRA facility has the most information published about its waste disposal activities. The ICPP has less data about the unsaturated zone due to the fact that most waste water disposal has been to a well. Little is known about the effect of waste water disposal at the NRF on the unsaturated zone. Essentially no information was found about waste disposal activities at other facilities, primarily because there does not appear to be any reported problems associated with waste water disposal at these locations. The RWMC has received much attention in the last few years as the result of being priority No. 1 in the superfund clean up of the INEL. A considerable amount of data are available describing the unsaturated zone at the RWMC. These data have been collected to field calibrate a radionuclide migration model for the RWMC

Catalytic Intermolecular Cross-Couplings of Azides and LUMO-Activated Unsaturated Acyl Azoliums

KAUST Repository

Li, Wenjun

2017-02-15

An example for the catalytic synthesis of densely functionalized 1,2,3-triazoles through a LUMO activation mode has been developed. The protocol is enabled by intermolecular cross coupling reactions of azides with in situ-generated alpha,beta-unsaturated acyl azoliums. High yields and broad scope as well as the investigation of reaction mechanism are reported.

Isotope studies of a thick unsaturated zone in a semi-arid area of Southern Africa

International Nuclear Information System (INIS)

Butler, M.J.; Verhagen, B.Th.

2001-01-01

Unsaturated zone profiles ranging in depth from 8 m to 22 m were obtained by hand augering an aeolian sand cover in the southern reaches of the semi-arid Kalahari thirstland. Moisture contents were rather low (<3 wt.%); in situ moisture chloride concentrations, measured by selective ion electrode following elutriation, are generally <500 ppm. Deuterium in the moisture was measured mass spectrometrically by direct quantitative conversion to hydrogen on zinc metal of moist soil samples. A novel technique of direct equilibration was developed for oxygen-18 analysis. Neither a thermonuclear tritium peak nor a stable isotope evaporation inversion near the surface could be observed in any of the profiles. Remarkable differences both laterally and vertically are observed in most parameters measured between profiles taken a few tens of metres apart. At greater depths, these differences become less pronounced. Recharge estimates based on chloride differ markedly from those obtained from tritium. Although the stable isotope values of the underlying saturated zone are similar to moisture in the deeper sections of the unsaturated zone profiles, the markedly lower chloride concentrations point towards preferential or bypass flow as an important mechanism of ground water recharge in the area. This can be regarded as a benchmark site on account of the wealth of unsaturated zone data as well as the detailed and ongoing rainfall record. (author)

Effect of saturated and unsaturated fatty acid supplementation on bio-plastic production under submerged fermentation.

Science.gov (United States)

Srivastava, S K; Tripathi, Abhishek Dutt

2013-10-01

Polyhydroxyalkanoates (PHAs) are intracellular reserve material stored by gram-negative bacteria under nutrient-limited condition. PHAs are utilized in biodegradable plastics (bio-plastics) synthesis due to their similarity with conventional synthetic plastic. In the present study, the effect of addition of saturated and unsaturated fatty acids (palmitic acid, stearic acid, oleic acid and linoleic acid) on the production of PHAs by the soil bacterium Alcaligenes sp. NCIM 5085 was studied. Fatty acid supplementation in basal media produced saturated and unsaturated PHAs of medium and short chain length. Gas chromatography analysis of palmitic acid-supplemented media showed the presence of short chain length (scl) PHAs which could potentially serve as precursors for bio-plastic production. The scl PHA was subsequently characterized as PHB by NMR and FTIR. On the other hand, oleic acid and linoleic acid addition showed both saturated and unsaturated PHAs of different chain lengths. Palmitic acid showed maximum PHB content of 70.8 % at concentration of 15 g l -1 under shake flask cultivation. When shake flask cultivation was scaled up in a 7.5-l bioreactor (working volume 3 l), 7.6 g l -1 PHA was produced with a PHB yield (Y P/X ) and productivity of 75.89 % and 0.14 g l -1  h, respectively.

Alkaline Ceramidase 3 (ACER3) Hydrolyzes Unsaturated Long-chain Ceramides, and Its Down-regulation Inhibits Both Cell Proliferation and Apoptosis*

OpenAIRE

Hu, Wei; Xu, Ruijuan; Sun, Wei; Szulc, Zdzislaw M.; Bielawski, Jacek; Obeid, Lina M.; Mao, Cungui

2010-01-01

Ceramides with different fatty acyl chains may vary in their physiological or pathological roles; however, it remains unclear how cellular levels of individual ceramide species are regulated. Here, we demonstrate that our previously cloned human alkaline ceramidase 3 (ACER3) specifically controls the hydrolysis of ceramides carrying unsaturated long acyl chains, unsaturated long-chain (ULC) ceramides. In vitro, ACER3 only hydrolyzed C18:1-, C20:1-, C20:4-ceramides, dihydroceramides, and phyto...

A New Mechanism of Canopy Effect in Unsaturated Freezing Soils

Directory of Open Access Journals (Sweden)

Teng Jidong

2016-01-01

Full Text Available Canopy effect refers to the phenomenon where moisture accumulates underneath an impervious cover. Field observation reveals that canopy effect can take place in relatively dry soils where the groundwater table is deep and can lead to full saturation of the soil immediately underneath the impervious cover. On the other hand, numerical analysis based on existing theories of heat and mass transfer in unsaturated soils can only reproduce a minor amount of moisture accumulation due to an impervious cover, particularly when the groundwater table is relatively deep. In attempt to explain the observed canopy effect in field, this paper proposes a new mechanism of moisture accumulation in unsaturated freezing soils: vapour transfer in such a soil is accelerated by the process of vapour-ice desublimation. A new approach for modelling moisture and heat movements is proposed, in which the phase change of evaporation, condensation and de-sublimation of vapor flow are taken into account. The computed results show that the proposed model can indeed reproduce the unusual moisture accumulation observed in relatively dry soils. The results also demonstrate that soil freezing fed by vapour transfer can result in a water content close to full saturation. Since vapour transfer is seldom considered in geotechnical design, the canopy effect deserves more attention during construction and earth works in cold and arid regions.

Hydrocarbons biodegradation in unsaturated porous medium; Biodegradation des hydrocarbures en milieu poreux insature

Energy Technology Data Exchange (ETDEWEB)

Gautier, C

2007-12-15

Biological processes are expected to play an important role in the degradation of petroleum hydrocarbons in contaminated soils. However, factors influencing the kinetics of biodegradation are still not well known, especially in the unsaturated zone. To address these biodegradation questions in the unsaturated zone an innovative experimental set up based on a physical column model was developed. This experimental set up appeared to be an excellent tool for elaboration of a structured porous medium, with well defined porous network and adjusted water/oil saturations. Homogeneous repartition of both liquid phases (i.e., aqueous and non aqueous) in the soil pores, which also contain air, was achieved using ceramic membranes placed at the bottom of the soil column. Reproducible interfaces (and connectivity) are developed between gas, and both non mobile water and NAPL phases, depending on the above-defined characteristics of the porous media and on the partial saturations of these three phases (NAPL, water and gas). A respirometric apparatus was coupled to the column. Such experimental set up have been validated with hexadecane in dilution in an HMN phase. This approach allowed detailed information concerning n-hexadecane biodegradation, in aerobic condition, through the profile of the oxygen consumption rate. We have taken benefit of this technique, varying experimental conditions, to determine the main parameters influencing the biodegradation kinetics and compositional evolution of hydrocarbons, under steady state unsaturated conditions and with respect to aerobic metabolism. Impacts of the nitrogen quantity and of three different grain sizes have been examined. Biodegradation of petroleum cut, as diesel cut and middle distillate without aromatic fraction, were, also studied. (author)

Poisson Coordinates.

Science.gov (United States)

Li, Xian-Ying; Hu, Shi-Min

2013-02-01

Harmonic functions are the critical points of a Dirichlet energy functional, the linear projections of conformal maps. They play an important role in computer graphics, particularly for gradient-domain image processing and shape-preserving geometric computation. We propose Poisson coordinates, a novel transfinite interpolation scheme based on the Poisson integral formula, as a rapid way to estimate a harmonic function on a certain domain with desired boundary values. Poisson coordinates are an extension of the Mean Value coordinates (MVCs) which inherit their linear precision, smoothness, and kernel positivity. We give explicit formulas for Poisson coordinates in both continuous and 2D discrete forms. Superior to MVCs, Poisson coordinates are proved to be pseudoharmonic (i.e., they reproduce harmonic functions on n-dimensional balls). Our experimental results show that Poisson coordinates have lower Dirichlet energies than MVCs on a number of typical 2D domains (particularly convex domains). As well as presenting a formula, our approach provides useful insights for further studies on coordinates-based interpolation and fast estimation of harmonic functions.

Polymerization of unsaturated monomers with radiation in the presence of salts

International Nuclear Information System (INIS)

Phalangas, C.J.; Restaino, A.J.; Yun, H.B.

1977-01-01

Improved process is claimed for the preparation of water-soluble, substantially linear, high molecular weight polymers, comprising irradiating an aqueous solution of an ethylenically unsaturated monomer and a water-soluble salt under controlled conditions of concentration, radiation intensity, conversion, and total radiation dose. The polymers may be obtained in aqueous gel form or recovered in the form of powder. The polymers are useful as flocculating, thickening, and mobility control agents

Lipase catalyzed epoxidation of fatty acid methyl esters derived from unsaturated vegetable oils in absence of carboxylic acid.

Science.gov (United States)

Sustaita-Rodríguez, Alejandro; Ramos-Sánchez, Víctor H; Camacho-Dávila, Alejandro A; Zaragoza-Galán, Gerardo; Espinoza-Hicks, José C; Chávez-Flores, David

2018-04-11

Nowadays the industrial chemistry reactions rely on green technologies. Enzymes as lipases are increasing its use in diverse chemical processes. Epoxidized fatty acid methyl esters obtained from transesterification of vegetable oils have recently found applications as polymer plasticizer, agrochemical, cosmetics, pharmaceuticals and food additives. In this research article, grapeseed, avocado and olive oils naturally containing high percents of mono and poly unsaturations were used as starting materials for the production of unsaturated fatty acid methyl esters. The effect of lauric acid as an active oxygen carrier was studied on epoxidation reactions where unsaturated fatty acid methyl esters were converted to epoxy fatty acid methyl esters using immobilized Candida antarctica Lipase type B as catalyst and hydrogen peroxide as oxygen donor at mild temperature and pressure conditions. After this study it was confirmed by 1 H NMR, 13 C NMR and GC-MS that the addition of lauric acid to the enzymatic reaction is unnecessary to transform the alkenes in to epoxides. It was found that quantitative conversions were possible in despite of a carboxylic acid absence.

Preparation of Acetylated Guar Gum – Unsaturated Polyester Composites & Effect of Water on Their Properties

Directory of Open Access Journals (Sweden)

David D’Melo

2012-07-01

Full Text Available Guar gum has seen extensive use in blends, however, its application as a filler in thermoset composites has as yet not been investigated. The effect of the addition of guar gum and its acetyl derivatives on the kinetics of water diffusion in unsaturated polyester composites was studied. The effect of water on the mechanical properties of the composites was studied with respect to the nature of filler, filler concentration and time of immersion. All the mechanical properties were observed to decrease on exposure to water. Further, it was observed that acetylated guar gum, with a degree of substitution of 0.21, showed the best mechanical properties, surpassing the other filled composites and that of the pure unsaturated polyester. Thus, acetylated guar gum showed promise as eco-friendly filler in composite formulation.

The resistance of titanium to pitting, microbially induced corrosion and corrosion in unsaturated conditions

International Nuclear Information System (INIS)

Shoesmith, D.W.; Ikeda, B.M.

1997-04-01

Titanium and its alloys (Grades-2, -12, -16) are candidate materials for Canadian nuclear waste containers on the basis of their apparent immunity to many localized corrosion processes. This simplifies markedly the effort needed to justify the use of these materials and to develop models to predict the lifetimes of containers. Here we review the pitting, microbially influenced corrosion (MIC), and corrosion under unsaturated conditions, of titanium. For all these processes, the properties of the passive oxide film are paramount in determining the metal's resistance to corrosion. A review of these oxide properties is included and the conditions to which the metal must be exposed if localized corrosion is to occur are defined. Since these conditions cannot be achieved under Canadian waste vault conditions, it can be concluded that pitting and MIC will not occur and that corrosion under unsaturated conditions is extremely unlikely. (author)

Determination of Transport Properties From Flowing Fluid Temperature Logging In Unsaturated Fractured Rocks: Theory And Semi-Analytical Solution

International Nuclear Information System (INIS)

Mukhopadhyay, Sumit; Tsang, Yvonne W.

2008-01-01

Flowing fluid temperature logging (FFTL) has been recently proposed as a method to locate flowing fractures. We argue that FFTL, backed up by data from high-precision distributed temperature sensors, can be a useful tool in locating flowing fractures and in estimating the transport properties of unsaturated fractured rocks. We have developed the theoretical background needed to analyze data from FFTL. In this paper, we present a simplified conceptualization of FFTL in unsaturated fractured rock, and develop a semianalytical solution for spatial and temporal variations of pressure and temperature inside a borehole in response to an applied perturbation (pumping of air from the borehole). We compare the semi-analytical solution with predictions from the TOUGH2 numerical simulator. Based on the semi-analytical solution, we propose a method to estimate the permeability of the fracture continuum surrounding the borehole. Using this proposed method, we estimated the effective fracture continuum permeability of the unsaturated rock hosting the Drift Scale Test (DST) at Yucca Mountain, Nevada. Our estimate compares well with previous independent estimates for fracture permeability of the DST host rock. The conceptual model of FFTL presented in this paper is based on the assumptions of single-phase flow, convection-only heat transfer, and negligible change in system state of the rock formation. In a sequel paper (Mukhopadhyay et al., 2008), we extend the conceptual model to evaluate some of these assumptions. We also perform inverse modeling of FFTL data to estimate, in addition to permeability, other transport parameters (such as porosity and thermal conductivity) of unsaturated fractured rocks

Fourier Transform Infrared Imaging Shows Reduced Unsaturated Lipid Content in the Hippocampus of a Mouse Model of Alzheimer’s Disease

OpenAIRE

Leskovjan, Andreana C.; Kretlow, Ariane; Miller, Lisa M.

2010-01-01

Polyunsaturated fatty acids are essential to brain functions such as membrane fluidity, signal transduction, and cell survival. It is also thought that low levels of unsaturated lipid in the brain may contribute to Alzheimer’s disease (AD) risk or severity. However, it is not known how accumulation of unsaturated lipids is affected in different regions of the hippocampus, which is a central target of AD plaque pathology, during aging. In this study, we used Fourier Transform Infrared Imaging ...

Experimental Determination of Hydraulic Properties of Unsaturated Calcarenites

Science.gov (United States)

Turturro, Antonietta Celeste; Andriani, Gioacchino Francesco; Clementina Caputo, Maria; Maggi, Sabino

2013-04-01

Understanding hydraulic properties is essential in the modeling of flow and solute transport through the vadose zone, to which problems of soil and groundwater pollution are related. The vadose zone, in fact, is of great importance in controlling groundwater recharge and transport of contaminants into and through the subsoil. The aim of this work is to determine experimentally in laboratory the hydraulic properties of unsaturated calcarenites using an approach including petrophysical determinations and methods for measuring water retention. For this purpose, samples of calcarenites belonging to the Calcarenite di Gravina Fm.(Pliocene-early Pleistocene), came from two different quarry districts located in Southern Italy (Canosa di Puglia and Massafra), were utilized. The water retention function, θ(h), which binds the water content, θ, to water potential, h, was determined in the laboratory by means two different experimental methods: the WP4-T psychrometer and the suction table. At last, a simple mathematical equation represented by van Genuchten's model is fitted to the experimental data and the unknown empirical parameters of this model are determined. Textural analysis on thin sections using optical petrographic microscopy and evaluation of total and effective porosity by means of standard geotechnical laboratory tests, mercury intrusion porosimetry and image analysis were also performed. In particular, a comparison between mercury porosimetry data and results of photomicrograph computer analysis through the methods of quantitative stereology was employed for providing pore size distributions. The results of this study identify the relationship between the hydraulic behavior, described by the water retention function, and pore size distribution for the calcarenites that are not easy to hydraulically characterize. This relationship could represent a useful tool to infer the unsaturated hydraulic properties of calcarenites and in general this approach could be

Validation studies for assessing unsaturated flow and transport through fractured rock

International Nuclear Information System (INIS)

Bassett, R.L.; Neuman, S.P.; Rasmussen, T.C.; Guzman, A.; Davidson, G.R.; Lohrstorfer, C.F.

1994-08-01

*The objectives of this contract are to examine hypotheses and conceptual models concerning unsaturated flow and transport through heterogeneous fractured rock and to design and execute confirmatory field and laboratory experiments to test these hypotheses and conceptual models. Important new information is presented such as the application and evaluation of procedures for estimating hydraulic, pneumatic, and solute transport coefficients for a range of thermal regimes. A field heater experiment was designed that focused on identifying the suitability of existing monitoring equipment to obtain required data. A reliable method was developed for conducting and interpreting tests for air permeability using a straddle-packer arrangement. Detailed studies of fracture flow from Queen Creek into the Magina Copper Company ore haulage tunnel have been initiated. These studies will provide data on travel time for transport of water and solute in unsaturated tuff. The collection of rainfall runoff, and infiltration data at two small watersheds at the Apache Leap Tuff Site enabled us to evaluate the quantity and rate of water infiltrating into the subsurface via either fractures or matrix. Characterization methods for hydraulic parameters relevant to Weigh-level waste transport, including fracture apertures, transmissivity, matrix porosity, and fracture wetting front propagation velocities, were developed

Validation studies for assessing unsaturated flow and transport through fractured rock

Energy Technology Data Exchange (ETDEWEB)

Bassett, R.L.; Neuman, S.P.; Rasmussen, T.C.; Guzman, A.; Davidson, G.R.; Lohrstorfer, C.F. [Arizona Univ., Tucson, AZ (United States). Dept. of Hydrology and Water Resources

1994-08-01

*The objectives of this contract are to examine hypotheses and conceptual models concerning unsaturated flow and transport through heterogeneous fractured rock and to design and execute confirmatory field and laboratory experiments to test these hypotheses and conceptual models. Important new information is presented such as the application and evaluation of procedures for estimating hydraulic, pneumatic, and solute transport coefficients for a range of thermal regimes. A field heater experiment was designed that focused on identifying the suitability of existing monitoring equipment to obtain required data. A reliable method was developed for conducting and interpreting tests for air permeability using a straddle-packer arrangement. Detailed studies of fracture flow from Queen Creek into the Magina Copper Company ore haulage tunnel have been initiated. These studies will provide data on travel time for transport of water and solute in unsaturated tuff. The collection of rainfall runoff, and infiltration data at two small watersheds at the Apache Leap Tuff Site enabled us to evaluate the quantity and rate of water infiltrating into the subsurface via either fractures or matrix. Characterization methods for hydraulic parameters relevant to Weigh-level waste transport, including fracture apertures, transmissivity, matrix porosity, and fracture wetting front propagation velocities, were developed.

MECHANICAL AND THERMAL PROPERTIES OF COMPOSITES FROM UNSATURATED POLYESTER FILLED WITH OIL PALM ASH

Directory of Open Access Journals (Sweden)

M.S. Ibrahim

2012-06-01

Full Text Available Oil palm ash (OPA is available in abundance, is renewable, can be obtained at no cost and shows good performance at high thermal conditions. Combinations of the unsaturated polyester with natural fillers have been reported to improve the mechanical and thermal properties of composites. Utilisation of oil palm ash as a filler in the manufacture of polymer composites can significantly reduce the requirement for other binders or matrixes of composite materials. This research uses oil palm ash as a filler to form composites through the investigation of the effect of different contents of filler on the properties of OPA-filled unsaturated polyester (UP/OPA composites. The effect of different volume fractions, i.e., 0, 10, 20 and 30 vol.% of oil palm ash introduced into 100, 90, 80 and 70 vol.% of an unsaturated polyester matrix on the composite mechanical properties, i.e., tensile and flexural, has been studied, together with thermal gravimetric analysis (TGA and differential scanning calorimetric (DSC. Specimens were prepared using compression moulding techniques based on the ASTM D790 and D5083 standards for flexural and tensile tests, respectively. The tensile and flexural mechanical properties of UP/OPA composites were improved in modulus by increasing the filler content. Thermal stability of the composites increased as the OPA filler content was increased, which was a logical consequence because of the high thermal stability of the silica compound of the OPA filler compared with that of the UP matrix. The results from the surface electron microscope (SEM analysis were the extension of mechanical and thermal tests.

Hypolipidemic action of garlic unsaturated oils in irradiated mice

International Nuclear Information System (INIS)

Gupta, N.K.

1988-01-01

Adult male Swiss albino mice were injected with 74 KBq g -1 body weight of radiocalcium 45 Ca in the presence and absence of unsaturated oils of garlic, and changes in the total lipids and triglycerides contents of liver were observed at various intervals from 1 to 14 days. The results obtained indic ate that the garlic oils prevented rapid increase in hepatic total lipids and triglycerides induced by radiocalcium and the values reached normal values earlier in garlic-treated than in irradiated animals. Possible mechanism(s) underlying hypolipidemic action of garlic oil have been discussed. (author). 22 refs

Thermal conductivity of unsaturated clay-rocks

Directory of Open Access Journals (Sweden)

D. Jougnot

2010-01-01

Full Text Available The parameters used to describe the electrical conductivity of a porous material can be used to describe also its thermal conductivity. A new relationship is developed to connect the thermal conductivity of an unsaturated porous material to the thermal conductivity of the different phases of the composite, and two electrical parameters called the first and second Archie's exponents. A good agreement is obtained between the new model and thermal conductivity measurements performed using packs of glass beads and core samples of the Callovo-Oxfordian clay-rocks at different saturations of the water phase. We showed that the three model parameters optimised to fit the new model against experimental data (namely the thermal conductivity of the solid phase and the two Archie's exponents are consistent with independent estimates. We also observed that the anisotropy of the effective thermal conductivity of the Callovo-Oxfordian clay-rock was mainly due to the anisotropy of the thermal conductivity of the solid phase.

Effects of volume change on the unsaturated hydraulic conductivity of Sphagnum moss

Science.gov (United States)

Golubev, V.; Whittington, P.

2018-04-01

Due to the non-vascular nature of Sphagnum mosses, the capitula (growing surface) of the moss must rely solely on capillary action to receive water from beneath. Moss subsides and swells in accordance with water table levels, an effect called "mire-breathing", which has been thought to be a self-preservation mechanism, although no systematic studies have been done to demonstrate exactly how volume change affects hydrophysical properties of moss. In this study, the unsaturated hydraulic conductivity (Kunsat) and water content of two different species of Sphagnum moss were measured at different compression rates, up to the maximum of 77%. The findings show that the Kunsat increases by up to an order of magnitude (10×) with compression up to a certain bulk density of the moss, after which higher levels of compression result in lowered unsaturated hydraulic conductivity. This was coupled with an increase in soil water retention with increased compression. The increase of the Kunsat with compression suggests that the mire-breathing effect should be considered a self-preservation mechanism to provide sufficient amount of water to growing moss in times of low water availability.

Physiologically based in silico modelling to examine DNA adduct formation by different food-borne a,ß-unsaturated aldehydes at realistic low dietary exposure levels

NARCIS (Netherlands)

Kiwamoto, R.

2015-01-01

Abstract (R.Kiwamoto ISBN 978-94-6257-284-3)

Various α,β-unsaturated aldehydes are present in fruits, vegetables, spices, or processed products containing these items as natural constituents or as added food flavouring agents. Because of the α,β-unsaturated aldehyde moiety the β carbon in

A set of constitutive relationships accounting for residual NAPL in the unsaturated zone.

Science.gov (United States)

Wipfler, E L; van der Zee, S E

2001-07-01

Although laboratory experiments show that non-aqueous phase liquid (NAPL) is retained in the unsaturated zone, no existing multiphase flow model has been developed to account for residual NAPL after NAPL drainage in the unsaturated zone. We developed a static constitutive set of saturation-capillary pressure relationships for water, NAPL and air that accounts for both this residual NAPL and entrapped NAPL. The set of constitutive relationships is formulated similarly to the set of scaled relationships that is frequently applied in continuum models. The new set consists of three fluid-phase systems: a three-phase system and a two-phase system, that both comply with the original constitutive model, and a newly introduced residual NAPL system. The new system can be added relatively easily to the original two- and three-phase systems. Entrapment is included in the model. The constitutive relationships of the non-drainable residual NAPL system are based on qualitative fluid behavior derived from a pore scale model. The pore scale model reveals that the amount of residual NAPL depends on the spreading coefficient and the water saturation. Furthermore, residual NAPL is history-dependent. At the continuum scale, a critical NAPL pressure head defines the transition from free, mobile NAPL to residual NAPL. Although the Pc-S relationships for water and total liquid are not independent in case of residual NAPL, two two-phase Pc-S relations can represent a three-phase residual system of Pc-S relations. A newly introduced parameter, referred to as the residual oil pressure head, reflects the mutual dependency of water and oil. Example calculations show consistent behavior of the constitutive model. Entrapment and retention in the unsaturated zone cooperate to retain NAPL. Moreover, the results of our constitutive model are in agreement with experimental observations.

Multicomponent synthesis of unsymmetrical unsaturated N-heterocyclic carbene precursors and their related transition-metal complexes

KAUST Repository

Queval, Pierre

2013-12-04

A low-cost, modular, and easily scalable multicomponent procedure affording access in good yields and excellent selectivity (up to 93 %) to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl-imidazolium salts is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron donor ability, high steric discrimination, and modular steric demand. A low-cost, modular, and easily scalable multicomponent procedure, affording access to a wide range of (a)chiral unsymmetrical 1-aryl-3-cycloalkyl- imidazolium salts in good yields and excellent selectivities, is disclosed. Electronic and steric properties of the corresponding unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands were evaluated and evidenced strong electron-donor ability, high steric discrimination, and modular steric demand. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental evidence of lateral flow in unsaturated homogeneous isotropic sloping soil due to rainfall

NARCIS (Netherlands)

Sinai, G.; Dirksen, C.

2006-01-01

This paper describes laboratory experimental evidence for lateral flow in the top layer of unsaturated sloping soil due to rainfall. Water was applied uniformly on horizontal and V-shaped surfaces of fine sand, at rates about 100 times smaller than the saturated hydraulic conductivity. Flow regimes

CO- and HCl-free synthesis of acid chlorides from unsaturated hydrocarbons via shuttle catalysis

Science.gov (United States)

Fang, Xianjie; Cacherat, Bastien; Morandi, Bill

2017-11-01

The synthesis of carboxylic acid derivatives from unsaturated hydrocarbons is an important process for the preparation of polymers, pharmaceuticals, cosmetics and agrochemicals. Despite its industrial relevance, the traditional Reppe-type carbonylation reaction using pressurized CO is of limited applicability to laboratory-scale synthesis because of: (1) the safety hazards associated with the use of CO, (2) the need for special equipment to handle pressurized gas, (3) the low reactivity of several relevant nucleophiles and (4) the necessity to employ different, often tailor-made, catalytic systems for each nucleophile. Herein we demonstrate that a shuttle-catalysis approach enables a CO- and HCl-free transfer process between an inexpensive reagent, butyryl chloride, and a wide range of unsaturated substrates to access the corresponding acid chlorides in good yields. This new transformation provides access to a broad range of carbonyl-containing products through the in situ transformation of the reactive acid chloride intermediate. In a broader context, this work demonstrates that isodesmic shuttle-catalysis reactions can unlock elusive catalytic reactions.

The resistance of titanium to pitting, microbially induced corrosion and corrosion in unsaturated conditions

Energy Technology Data Exchange (ETDEWEB)

Shoesmith, D W; Ikeda, B M

1997-04-01

Titanium and its alloys (Grades-2, -12, -16) are candidate materials for Canadian nuclear waste containers on the basis of their apparent immunity to many localized corrosion processes. This simplifies markedly the effort needed to justify the use of these materials and to develop models to predict the lifetimes of containers. Here we review the pitting, microbially influenced corrosion (MIC), and corrosion under unsaturated conditions, of titanium. For all these processes, the properties of the passive oxide film are paramount in determining the metal`s resistance to corrosion. A review of these oxide properties is included and the conditions to which the metal must be exposed if localized corrosion is to occur are defined. Since these conditions cannot be achieved under Canadian waste vault conditions, it can be concluded that pitting and MIC will not occur and that corrosion under unsaturated conditions is extremely unlikely. (author) 114 refs., 1 tab., 18 figs.

Radiation-induced polymerization of unsaturated phospholipid mixtures for the synthesis of artificial red cells

Science.gov (United States)

Hosoi, F.; Omichi, H.; Akama, K.; Awai, K.; Endo, S.; Nakano, Y.

1997-08-01

Radiation induced polymerization of phospholipid containing unsaturated acyl chains was applied to the synthesis of artificial red cells. Vesicles of 1,2-bis-(2,4-octadecadienoyl)-phosphatidylcholine (DODPC) and 1-stearoyl-2-(2,4-octadecadienoyl)-phosphatidylcholine (AODPC) were irradiated by 60Co γ-rays to obtain polymerized bilayer structure of these monomers. It was found that the polymerization of unsaturated groups located at 2-acyl chain of DODPC polymerized faster than those of AODPC. The difference was explained by the packed state of these monomers in the bilayer vesicles. The artificial red cell was obtained by irradiating the mixture of DODPC or AODPC with hemoglobin, cholesterol and palmitic acid sodium salt. The integrity of the irradiated hemoglobin in the vesicle was maintained by keeping the suspended solution at low temperature. On the other hand, oxidation of heme part became remarkable when the vesicle was kept at 37°C. The presence of extra hemoglobin outside the vesicle was found useful to prevent this oxidation.

A semi-analytical solution for slug tests in an unconfined aquifer considering unsaturated flow

Science.gov (United States)

Sun, Hongbing

2016-01-01

A semi-analytical solution considering the vertical unsaturated flow is developed for groundwater flow in response to a slug test in an unconfined aquifer in Laplace space. The new solution incorporates the effects of partial penetrating, anisotropy, vertical unsaturated flow, and a moving water table boundary. Compared to the Kansas Geological Survey (KGS) model, the new solution can significantly improve the fittings of the modeled to the measured hydraulic heads at the late stage of slug tests in an unconfined aquifer, particularly when the slug well has a partially submerged screen and moisture drainage above the water table is significant. The radial hydraulic conductivities estimated with the new solution are comparable to those from the KGS, Bouwer and Rice, and Hvorslev methods. In addition, the new solution also can be used to examine the vertical conductivity, specific storage, specific yield, and the moisture retention parameters in an unconfined aquifer based on slug test data.

Parametric analysis of a TOUGH2 model for the unsaturated zone at Yucca Mountain

Energy Technology Data Exchange (ETDEWEB)

Xiang, Y.; Mishra, S.; Dunlap, B. [CRWMS M& O/INTERA, Inc., Las Vegas, NV (United States)

1995-03-01

Yucca Mountain in Nevada is currently being investigated for suitability as a potential site for the disposal of high-level radioactive waste and spent nuclear fuel. As the most important natural barrier against radionuclide migration to the accessible environment, the unsaturated zone at Yucca mountain is a key constituent in assessing the ambient geohydrology. A three-dimensional site-scale TOUGH2 model of the unsaturated zone is currently under development by Lawrence Berkeley Laboratory (LBL) and the United States Geological Survey (USGS) consists of six hydrogeologic units - TCw (Tiva Canyon welded), PTn (Paintbrush nonwelded), TSw (Topopah Spring welded), TSv (Topopah Spring welded-vitrophyre), CHnz (Calico Hills nonwelded-vitric), and CHnz (Calico Hills nonwelded-zeolitic), which are further subdivided into seventeen layers to represent additional lithologic detail. Based on the work of Klavetter and Peters, the fractured units TCw and TSw are treated as equivalent continua with specified threshold saturation for triggering fracture flow.

Impact of urbanization on hydrochemical evolution of groundwater and on unsaturated-zone gas composition in the coastal city of Tel Aviv, Israel

Science.gov (United States)

Zilberbrand, M.; Rosenthal, E.; Shachnai, E.

2001-08-01

The coastal city of Tel Aviv was founded at the beginning of the 20th century. The number of its inhabitants and its water consumption increased rapidly. This study analyses a 15-year record (1934-1948) of pre-industrial development of groundwater chemistry in the urban area. Archive data on concentrations of major ions, dissolved gases (CO 2 and O 2), organic matter, and pH were available for each half-year during the period of 1934-1948. The major factors causing changes in the chemistry of groundwater flowing in three sandy sub-aquifers have been seawater encroachment due to overpumping, and infiltration of effluents from pit-latrine collectors. Influence of these factors decreases with depth. Landward-penetrating seawater passed through clayey coastal sediments, interbedded among sands and calcareous sandstones, and spread into the Kurkar Group aquifer. This has led to exchange of sodium (dominant in seawater) with calcium adsorbed on clay particles, enriching groundwater with calcium. Intensity of cation exchange decreases inland and with depth. Infiltration of pit-latrine effluents has introduced large amounts of ammonium into the unsaturated zone. Its rapid oxidation in unsaturated sediments has caused massive nitrate production, accompanied by pore-water acidification. This process induces dissolution of vadose carbonate, resulting in enrichment of groundwater recharge in calcium. Anthropogenically induced dissolution of calcite in the unsaturated zone has been the major factor for the increase of Ca 2+ concentration in groundwater, accounting for about 80% of this increase. In the interface zone, an additional 20% of calcium has been supplied by cation exchange. Owing to pH increase caused by denitrification in the aquifer, Ca 2+-rich waters supersaturated with calcite could be formed, especially in the capillary fringe of the uppermost sub-aquifer, which could induce calcite precipitation and ultimately lead to the cementation of sandy aquifers. Urban

Regional Quasi-Three-Dimensional Unsaturated-Saturated Water Flow Model Based on a Vertical-Horizontal Splitting Concept

Directory of Open Access Journals (Sweden)

Yan Zhu

2016-05-01

Full Text Available Due to the high nonlinearity of the three-dimensional (3-D unsaturated-saturated water flow equation, using a fully 3-D numerical model is computationally expensive for large scale applications. A new unsaturated-saturated water flow model is developed in this paper based on the vertical/horizontal splitting (VHS concept to split the 3-D unsaturated-saturated Richards’ equation into a two-dimensional (2-D horizontal equation and a one-dimensional (1-D vertical equation. The horizontal plane of average head gradient in the triangular prism element is derived to split the 3-D equation into the 2-D equation. The lateral flow in the horizontal plane of average head gradient represented by the 2-D equation is then calculated by the water balance method. The 1-D vertical equation is discretized by the finite difference method. The two equations are solved simultaneously by coupling them into a unified nonlinear system with a single matrix. Three synthetic cases are used to evaluate the developed model code by comparing the modeling results with those of Hydrus1D, SWMS2D and FEFLOW. We further apply the model to regional-scale modeling to simulate groundwater table fluctuations for assessing the model applicability in complex conditions. The proposed modeling method is found to be accurate with respect to measurements.

Inhibition of steroid 5 alpha-reductase by specific aliphatic unsaturated fatty acids.

Science.gov (United States)

Liang, T; Liao, S

1992-01-01

Human or rat microsomal 5 alpha-reductase activity, as measured by enzymic conversion of testosterone into 5 alpha-dihydrotestosterone or by binding of a competitive inhibitor, [3H]17 beta-NN-diethulcarbamoyl-4-methyl-4-aza-5 alpha-androstan-3-one ([3H]4-MA) to the reductase, is inhibited by low concentrations (less than 10 microM) of certain polyunsaturated fatty acids. The relative inhibitory potencies of unsaturated fatty acids are, in decreasing order: gamma-linolenic acid greater than cis-4,7,10,13,16,19-docosahexaenoic acid = cis-6,9,12,15-octatetraenoic acid = arachidonic acid = alpha-linolenic acid greater than linoleic acid greater than palmitoleic acid greater than oleic acid greater than myristoleic acid. Other unsaturated fatty acids such as undecylenic acid, erucic acid and nervonic acid, are inactive. The methyl esters and alcohol analogues of these compounds, glycerols, phospholipids, saturated fatty acids, retinoids and carotenes were inactive even at 0.2 mM. The results of the binding assay and the enzymic assay correlated well except for elaidic acid and linolelaidic acid, the trans isomers of oleic acid and linoleic acid respectively, which were much less active than their cis isomers in the binding assay but were as potent in the enzymic assay. gamma-Linolenic acid had no effect on the activities of two other rat liver microsomal enzymes: NADH:menadione reductase and glucuronosyl transferase. gamma-Linolenic acid, the most potent inhibitor tested, decreased the Vmax. and increased Km values of substrates, NADPH and testosterone, and promoted dissociation of [3H]4-MA from the microsomal reductase. gamma-Linolenic acid, but not the corresponding saturated fatty acid (stearic acid), inhibited the 5 alpha-reductase activity, but not the 17 beta-dehydrogenase activity, of human prostate cancer cells in culture. These results suggest that unsaturated fatty acids may play an important role in regulating androgen action in target cells. PMID:1637346

Unsaturated flow dynamics during irrigation with wastewater: field and modelling study

Science.gov (United States)

Martinez-Hernandez, V.; de Miguel, A.; Meffe, R.; Leal, M.; González-Naranjo, V.; de Bustamante, I.

2012-04-01

To deal with water scarcity combined with a growing water demand, the reuse of wastewater effluents of wastewater treatment plants (WWTP) for industrial and agricultural purposes is considered as a technically and economically feasible solution. In agriculture, irrigation with wastewater emerges as a sustainable practice that should be considered in such scenarios. Water infiltration, soil moisture storage and evapotranspiration occurring in the unsaturated zone are fundamental processes that play an important role in soil water balance. An accurate estimation of unsaturated flow dynamics (during and after irrigation) is essential to improve wastewater management (i.e. estimating groundwater recharge or maximizing irrigation efficiency) and to avoid possible soil and groundwater affections (i.e. predicting contaminant transport). The study site is located in the Experimental Plant of Carrión de los Céspedes (Seville, Spain). Here, treated wastewater is irrigated over the soil to enhance plants growth. To obtain physical characteristics of the soil (granulometry, bulk density and water retention curve), soil samples were collected at different depths. A drain gauge passive capillary lysimeter was installed to determine the volume of water draining from the vadose zone. Volumetric water content of the soil was monitored by measuring the dielectric constant using capacitance/frequency domain technology. Three soil moisture probes were located at different depths (20, 50 and 70 cm below the ground surface) to control the variation of the volumetric water content during infiltration. The main aim of this study is to understand water flow dynamics through the unsaturated zone during irrigation by using the finite element model Hydrus-1D. The experimental conditions were simulated by a 90 cm long, one dimensional solution domain. Specific climatic conditions, wastewater irrigation rates and physical properties of the soil were introduced in the model as input parameters

Plutonium-239 sorption and transport on/in unsaturated sediments. Comparison of batch and column experiments for determining sorption coefficients

International Nuclear Information System (INIS)

Jinchuan Xie; Jiachun Lu; Xiaohua Zhou; Xuhui Wang; Mei Li; Lili Du; Yueheng Liu; Guoqing Zhou

2013-01-01

Sorption (distribution) coefficients of plutonium were most often derived by static batch experiments. However, it is not clear how unsaturated flow conditions including moisture content and pore water velocity change the sorption coefficients. Transport experiments of plutonium through the unsaturated sediments packed into the columns were then performed in order to determine the sorption coefficients (column-K ds ). Static batch experiments were also conducted to obtain batch-K ds and then compare the differences between batch-K ds and column-K ds . The results show that unsaturated flow conditions had no significant effect on column-K ds , and the average column-K d value was 1.74 ± 0.02 m 3 /kg. By comparison, batch-K d values spanned several orders of magnitude, regardless of the specified liquid-solid conditions. Moreover, the batch-K d (22.7 m 3 /kg) at the standard L/S (4 mL/g) recommended by ASTM D 4319 was over an order of magnitude larger than the average column-K d . (author)

Exploration of a mechanism for the production of highly unsaturated fatty acids in Scenedesmus sp. at low temperature grown on oil crop residue based medium.

Science.gov (United States)

Lu, Qian; Li, Jun; Wang, Jinghan; Li, Kun; Li, Jingjing; Han, Pei; Chen, Paul; Zhou, Wenguang

2017-11-01

The ability of algae to produce lipids comprising of unsaturated fatty acids varies with strains and culture conditions. This study investigates the effect of temperature on the production of unsaturated fatty acids in Scenedesmus sp. grown on oil crop residue based medium. At low temperature (10°C), synthesis of lipids compromising of high contents of unsaturated fatty acids took place primarily in the early stage while protein accumulation mainly occurred in the late stage. This stepwise lipid-protein synthesis process was found to be associated with the contents of acetyl-CoA and α-KG in the algal cells. A mechanism was proposed and tested through simulation experiments which quantified the carbon flux allocation in algal cells at different cultivation stages. It is concluded that low culture temperature such as 10°C is suitable for the production of lipids comprising of unsaturated fatty acids. Copyright © 2017 Elsevier Ltd. All rights reserved.

A framework for sourcing of evaporation between saturated and unsaturated zone in bare soil condition

NARCIS (Netherlands)

Balugani, E.; Lubczynski, M.; Metselaar, K.A.

2016-01-01

Sourcing subsurface evaporation (Ess) into groundwater (Eg) and unsaturated zone (Eu) components has received little scientific attention so far, despite its importance in water management and agriculture. We propose a novel sourcing framework, with its implementation in dedicated post-processing

An analytical model for flow induced by a constant-head pumping in a leaky unconfined aquifer system with considering unsaturated flow

Science.gov (United States)

Lin, Ye-Chen; Li, Ming-Hsu; Yeh, Hund-Der

2017-09-01

A new mathematical model is developed to describe the flow in response to a constant-head pumping (or constant-head test, CHT) in a leaky unconfined aquifer system of infinite lateral extent with considering unsaturated flow. The model consists of an unsaturated zone on the top, an unconfined aquifer in the middle, and a second aquifer (aquitard) at the bottom. The unsaturated flow is described by Richard's equation, and the flows in unconfined aquifer and second layer are governed by the groundwater flow equation. The well partially penetrates the unconfined aquifer with a constant head in the well due to CHT. The governing equations of the model are linearized by the perturbation method and Gardner's exponential model is adopted to describe the soil retention curves. The solution of the model for drawdown distribution is obtained by applying the methods of Laplace transform and Weber transform. Then the solution for the wellbore flowrate is derived from the drawdown solution with Darcy's law. The issue of the equivalence of normalized drawdown predicted by the present solution for constant-head pumping and Tartakovsky and Neuman's (2007) solution for constant-rate pumping is discussed. On the basis of the wellbore flowrate solution, the results of the sensitivity analysis indicate that the wellbore flowrate is very sensitive to the changes in the radial hydraulic conductivity and the thickness of the saturated zone. Moreover, the results predicted from the present wellbore flowrate solution indicate that this new solution can reduce to Chang's et al. (2010a) solution for homogenous aquifers when the dimensionless unsaturated exponent approaches 100. The unsaturated zone can be considered as infinite extent in the vertical direction if the thickness ratio of the unsaturated zone to the unconfined aquifer is equal to or greater than one. As for the leakage effect, it can be ignored when the vertical hydraulic conductivity ratio (i.e., the vertical hydraulic

The role of Soil Water Retention Curve in slope stability analysis in unsaturated and heterogeneous soils.

Science.gov (United States)

Antinoro, Chiara; Arnone, Elisa; Noto, Leonardo V.

2015-04-01

The mechanisms of rainwater infiltration causing slope instability had been analyzed and reviewed in many scientific works. Rainwater infiltration into unsaturated soil increases the degree of saturation, hence affecting the shear strength properties and thus the probability of slope failure. It has been widely proved that the shear strength properties change with the soil water suction in unsaturated soils; therefore, the accuracy to predict the relationship between soil water content and soil water suction, parameterized by the soil-water characteristic curve, has significant effects on the slope stability analysis. The aim of this study is to investigate how the characterization of SWRC of differently structured unsaturated soils affects the slope stability on a simple infinite slope. In particular, the unimodal and bimodal distributions of the soil pore size were compared. Samples of 40 soils, highly different in terms of structure and texture, were collected and used to calibrate two bimodal SWRCs, i.e. Ross and Smettem (1993) and Dexter et al., (2008). The traditional unimodal van Genuchten (1980) model was also applied for comparison. Slope stability analysis was conducted in terms of Factor of Safety (FS) by applying the infinite slope model for unsaturated soils. In the used formulation, the contribution of the suction effect is tuned by a parameter 'chi' in a rate proportional to the saturation conditions. Different parameterizations of this term were also compared and analyzed. Results indicated that all three SWRC models showed good overall performance in fitting the sperimental SWRCs. Both the RS and DE models described adequately the water retention data for soils with a bimodal behavior confirmed from the analysis of pore size distribution, but the best performance was obtained by DE model confirmed. In terms of FS, the tree models showed very similar results as soil moisture approached to the saturated condition; however, within the residual zone

Suitability of parametric models to describe the hydraulic properties of an unsaturated coarse sand and gravel

Science.gov (United States)

Mace, Andy; Rudolph, David L.; Kachanoski , R. Gary

1998-01-01

The performance of parametric models used to describe soil water retention (SWR) properties and predict unsaturated hydraulic conductivity (K) as a function of volumetric water content (θ) is examined using SWR and K(θ) data for coarse sand and gravel sediments. Six 70 cm long, 10 cm diameter cores of glacial outwash were instrumented at eight depths with porous cup ten-siometers and time domain reflectometry probes to measure soil water pressure head (h) and θ, respectively, for seven unsaturated and one saturated steady-state flow conditions. Forty-two θ(h) and K(θ) relationships were measured from the infiltration tests on the cores. Of the four SWR models compared in the analysis, the van Genuchten (1980) equation with parameters m and n restricted according to the Mualem (m = 1 - 1/n) criterion is best suited to describe the θ(h) relationships. The accuracy of two models that predict K(θ) using parameter values derived from the SWR models was also evaluated. The model developed by van Genuchten (1980) based on the theoretical expression of Mualem (1976) predicted K(θ) more accurately than the van Genuchten (1980) model based on the theory of Burdine (1953). A sensitivity analysis shows that more accurate predictions of K(θ) are achieved using SWR model parameters derived with residual water content (θr) specified according to independent measurements of θ at values of h where θ/h ∼ 0 rather than model-fit θr values. The accuracy of the model K(θ) function improves markedly when at least one value of unsaturated K is used to scale the K(θ) function predicted using the saturated K. The results of this investigation indicate that the hydraulic properties of coarse-grained sediments can be accurately described using the parametric models. In addition, data collection efforts should focus on measuring at least one value of unsaturated hydraulic conductivity and as complete a set of SWR data as possible, particularly in the dry range.

Mono- and polynuclear Co(II) silanethiolates with aliphatic diamines

Science.gov (United States)

Pladzyk, Agnieszka; Baranowska, Katarzyna

2014-01-01

Four Co(II) complexes, [Co{SSi(OtBu)3}2(dmpda)] 1, [Co{SSi(OtBu)3}2(bda)2]n2 [Co{SSi(OtBu)3}2(pda)2]n3 and [Co{SSi(OtBu)3}2(hda)2]n4 [dmpda = 3-(dimethylamino)-1-propylamine; bda = 1.4-butanediamine; pda = 1.5-pentanediamine; had = 1.6-hexanediamine] have been synthesized and characterized using X-ray diffraction. Complex 1 is mononuclear and contains Co(II) coordinated by dmpda molecule in chelating mode, whereas compounds 3 and 4 are one-dimensional polymers with pda and hda diamines as bridges between the metallic centers respectively. In all complexes tri-tert-butoxysilanethiolate residue acts as terminal S-donor ligand. Full characterization of obtained compounds 1-4 was additionally carried out with the use of IR and UV-vis spectroscopy, elemental and thermal analysis.

Lipid droplets induced by secreted phospholipase A2 and unsaturated fatty acids protect breast cancer cells from nutrient and lipotoxic stress.

Science.gov (United States)

Jarc, Eva; Kump, Ana; Malavašič, Petra; Eichmann, Thomas O; Zimmermann, Robert; Petan, Toni

2018-03-01

Cancer cells driven by the Ras oncogene scavenge unsaturated fatty acids (FAs) from their environment to counter nutrient stress. The human group X secreted phospholipase A 2 (hGX sPLA 2 ) releases FAs from membrane phospholipids, stimulates lipid droplet (LD) biogenesis in Ras-driven triple-negative breast cancer (TNBC) cells and enables their survival during starvation. Here we examined the role of LDs, induced by hGX sPLA 2 and unsaturated FAs, in protection of TNBC cells against nutrient stress. We found that hGX sPLA 2 releases a mixture of unsaturated FAs, including ω-3 and ω-6 polyunsaturated FAs (PUFAs), from TNBC cells. Starvation-induced breakdown of LDs induced by low micromolar concentrations of unsaturated FAs, including PUFAs, was associated with protection from cell death. Interestingly, adipose triglyceride lipase (ATGL) contributed to LD breakdown during starvation, but it was not required for the pro-survival effects of hGX sPLA 2 and unsaturated FAs. High micromolar concentrations of PUFAs, but not OA, induced oxidative stress-dependent cell death in TNBC cells. Inhibition of triacylglycerol (TAG) synthesis suppressed LD biogenesis and potentiated PUFA-induced cell damage. On the contrary, stimulation of LD biogenesis by hGX sPLA 2 and suppression of LD breakdown by ATGL depletion reduced PUFA-induced oxidative stress and cell death. Finally, lipidomic analyses revealed that sequestration of PUFAs in LDs by sPLA 2 -induced TAG remodelling and retention of PUFAs in LDs by inhibition of ATGL-mediated TAG lipolysis protect from PUFA lipotoxicity. LDs are thus antioxidant and pro-survival organelles that guard TNBC cells against nutrient and lipotoxic stress and emerge as attractive targets for novel therapeutic interventions. Copyright © 2017 Elsevier B.V. All rights reserved.

Unsaturated free fatty acids increase benzodiazepine receptor agonist binding depending on the subunit composition of the GABAA receptor complex.

Science.gov (United States)

Witt, M R; Westh-Hansen, S E; Rasmussen, P B; Hastrup, S; Nielsen, M

1996-11-01

It has been shown previously that unsaturated free fatty acids (FFAs) strongly enhance the binding of agonist benzodiazepine receptor ligands and GABAA receptor ligands in the CNS in vitro. To investigate the selectivity of this effect, recombinant human GABAA/benzodiazepine receptor complexes formed by different subunit compositions (alpha x beta y gamma 2, x = 1, 2, 3, and 5; y = 1, 2, and 3) were expressed using the baculovirus-transfected Sf9 insect cell system. At 10(-4) M, unsaturated FFAs, particularly arachidonic (20:4) and docosahexaenoic (22:6) acids, strongly stimulated (> 200% of control values) the binding of [3H]flunitrazepam ([3H]FNM) to the alpha 3 beta 2 gamma 2 receptor combination in whole cell preparations. No effect or small increases in levels of unsaturated FFAs on [3H]FNM binding to alpha 1 beta x gamma 2 and alpha 2 beta x gamma 2 receptor combinations were observed, and weak effects (130% of control values) were detected using the alpha 5 beta 2 gamma 2 receptor combination. The saturated FFAs, stearic and palmitic acids, were without effect on [3H]FNM binding to any combination of receptor complexes. The hydroxylated unsaturated FFAs, ricinoleic and ricinelaidic acids, were shown to decrease the binding of [3H]FNM only if an alpha 1 beta 2 gamma 2 receptor combination was used. Given the heterogeneity of the GABAA/ benzodiazepine receptor subunit distribution in the CNS, the effects of FFAs on the benzodiazepine receptor can be assumed to vary at both cellular and regional levels.

A two-stage procedure for determining unsaturated hydraulic characteristics using a syringe pump and outflow observations

DEFF Research Database (Denmark)

Wildenschild, Dorthe; Jensen, Karsten Høgh; Hollenbeck, Karl-Josef

1997-01-01

A fast two-stage methodology for determining unsaturated flow characteristics is presented. The procedure builds on direct measurement of the retention characteristic using a syringe pump technique, combined with inverse estimation of the hydraulic conductivity characteristic based on one......-step outflow experiments. The direct measurements are obtained with a commercial syringe pump, which continuously withdraws fluid from a soil sample at a very low and accurate how rate, thus providing the water content in the soil sample. The retention curve is then established by simultaneously monitoring......-step outflow data and the independently measured retention data are included in the objective function of a traditional least-squares minimization routine, providing unique estimates of the unsaturated hydraulic characteristics by means of numerical inversion of Richards equation. As opposed to what is often...

Bayesian estimation of the hydraulic and solute transport properties of a small-scale unsaturated soil column

Directory of Open Access Journals (Sweden)

Moreira Paulo H. S.

2016-03-01

Full Text Available In this study the hydraulic and solute transport properties of an unsaturated soil were estimated simultaneously from a relatively simple small-scale laboratory column infiltration/outflow experiment. As governing equations we used the Richards equation for variably saturated flow and a physical non-equilibrium dual-porosity type formulation for solute transport. A Bayesian parameter estimation approach was used in which the unknown parameters were estimated with the Markov Chain Monte Carlo (MCMC method through implementation of the Metropolis-Hastings algorithm. Sensitivity coefficients were examined in order to determine the most meaningful measurements for identifying the unknown hydraulic and transport parameters. Results obtained using the measured pressure head and solute concentration data collected during the unsaturated soil column experiment revealed the robustness of the proposed approach.

Influence of transient flow on the mobility of strontium in unsaturated sand column

International Nuclear Information System (INIS)

Mazet, P.

2008-10-01

The reactive transport of 85 Sr was studied on laboratory columns, focusing on the influence of transient unsaturated flow (cycles of infiltration and redistribution) associated with controlled geochemistry (constant concentrations of major elements and stable strontium in water). An original experimental tool (gamma attenuation system) allows us to follow at the same time the variations of humidity of the soil and the migration of radionuclide, in a non-destroying and definite way. First stage of this study concerned the implementation of the experimental tool to measure transient hydraulic events within the columns of sand. Several experiments of transport of 85 Sr were then performed with different water condition (saturated, unsaturated, permanent and transient flow). Experimental results were simulated using the computer codes HYDRUS-1D (phenomenological approach with partition coefficient K d ) and HYTEC (mechanistic geochemical/transport approach). Confrontation between experience and modelling shows that, for our operating conditions, transfer of 85 Sr can be predicted with an 'operational' approach using: 1) simplified geochemical model with partition coefficient K d concerning interactive reaction with the soil (K d value determined independently on saturated column, with the same water geochemistry), 2) permanent saturated (or unsaturated) flow, taking into account the cumulated infiltrated water during unsaturated transient hydraulic events concerning hydrodynamic. Generalization of these results (area of validity) suggests that the 'cumulated infiltrated water + K d ' approach can be use, for controlled water geochemistry, when the numerical value of K d is fairly strong (K d ≥≥1), and that it is insensitive to the value of the water content. Moreover, the presence of immobile water (∼10%) recorded with tritium transport, is undetectable with strontium. Explanation of this result is allocated to the different characteristic time residence

Unsaturated macrocyclic dihydroxamic acid siderophores produced by Shewanella putrefaciens using precursor-directed biosynthesis.

Science.gov (United States)

Soe, Cho Z; Codd, Rachel

2014-04-18

To acquire iron essential for growth, the bacterium Shewanella putrefaciens produces the macrocyclic dihydroxamic acid putrebactin (pbH2; [M + H(+)](+), m/zcalc 373.2) as its native siderophore. The assembly of pbH2 requires endogenous 1,4-diaminobutane (DB), which is produced from the ornithine decarboxylase (ODC)-catalyzed decarboxylation of l-ornithine. In this work, levels of endogenous DB were attenuated in S. putrefaciens cultures by augmenting the medium with the ODC inhibitor 1,4-diamino-2-butanone (DBO). The presence in the medium of DBO together with alternative exogenous non-native diamine substrates, (15)N2-1,4-diaminobutane ((15)N2-DB) or 1,4-diamino-2(E)-butene (E-DBE), resulted in the respective biosynthesis of (15)N-labeled pbH2 ((15)N4-pbH2; [M + H(+)](+), m/zcalc 377.2, m/zobs 377.2) or the unsaturated pbH2 variant, named here: E,E-putrebactene (E,E-pbeH2; [M + H(+)](+), m/zcalc 369.2, m/zobs 369.2). In the latter system, remaining endogenous DB resulted in the parallel biosynthesis of the monounsaturated DB-E-DBE hybrid, E-putrebactene (E-pbxH2; [M + H(+)](+), m/zcalc 371.2, m/zobs 371.2). These are the first identified unsaturated macrocyclic dihydroxamic acid siderophores. LC-MS measurements showed 1:1 complexes formed between Fe(III) and pbH2 ([Fe(pb)](+); [M](+), m/zcalc 426.1, m/zobs 426.2), (15)N4-pbH2 ([Fe((15)N4-pb)](+); [M](+), m/zcalc 430.1, m/zobs 430.1), E,E-pbeH2 ([Fe(E,E-pbe)](+); [M](+), m/zcalc 422.1, m/zobs 422.0), or E-pbxH2 ([Fe(E-pbx)](+); [M](+), m/zcalc 424.1, m/zobs 424.2). The order of the gain in siderophore-mediated Fe(III) solubility, as defined by the difference in retention time between the free ligand and the Fe(III)-loaded complex, was pbH2 (ΔtR = 8.77 min) > E-pbxH2 (ΔtR = 6.95 min) > E,E-pbeH2 (ΔtR = 6.16 min), which suggests one possible reason why nature has selected for saturated rather than unsaturated siderophores as Fe(III) solubilization agents. The potential to conduct multiple types of ex situ chemical

Production of metal particles and clusters

Science.gov (United States)

Mcmanus, S. P.

1982-01-01

The feasibility of producing novel metals or metal clusters in a low gravity environment was studied. The production of coordinately unsaturated metal carbonyls by thermolysis or photolysis of stable metal carbonyls has the potential to generate novel catalysts by this technique. Laser irradiation of available metal carbonyls was investigated. It is found that laser induced decomposition of metal carbonyls is feasible for producing a variety of coordinately unsaturated species. Formation of clustered species does occur but is hampered by weak metal-metal bonds.

NNWSI waste form test method for unsaturated disposal conditions

International Nuclear Information System (INIS)

Bates, J.K.; Gerding, T.J.

1985-03-01

A test method has been developed to measure the release of radionuclides from the waste package under simulated NNWSI repository conditions, and to provide information concerning materials interactions that may occur in the repository. Data are presented from Unsaturated testing of simulated Savannah River Laboratory 165 glass completed through 26 weeks. The relationship between these results and those from parametric and analog testing are described. The data indicate that the waste form test is capable of producing consistent, reproducible results that will be useful in evaluating the role of the waste package in the long-term performance of the repository. 6 refs., 7 figs., 5 tabs

Study of transport in unsaturated sands using radioactive tracers

International Nuclear Information System (INIS)

Merritt, W.F.; Pickens, J.F.; Allison, G.B.

1979-01-01

A laboratory experiment was conducted to investigate the mixing that occurs as a series of labelled pulses of water are transported by gravity drainage down through a sand filled column having a water table imposed at the bottom. It also demonstrated the utility of gamma-ray emitting radioactive tracers in studying transport in unsaturated or saturated porous media. The motivation for pursuing this topic was developed from observing that the content of oxygen-18, deuterium and tritium in rainwater shows marked temporal variations whereas their concentrations below the water table in shallow ground water flow systems are generally found to show much less variation. (auth)

Unsaturated hydraulic conductivity of sandy soil columns packed to different bulk densities and water uptake by plantroots

NARCIS (Netherlands)

Rossi-Pisa, P.

1978-01-01

This paper describes a laboratory metbod used to determine both the soil moisture retention curve and the unsaturated hydraulic conductivity in soil columns under transient flow conditions during evaporation.

Unsaturated hydraulic properties of xerophilous mosses: towards implementation of moss covered soils in hydrological models

NARCIS (Netherlands)

Voortman, B.R.; Bartholomeus, R.P.; Bodegom, van P.M.; Gooren, H.P.A.; Zee, van der S.E.A.T.M.; Witte, J.P.M.

2014-01-01

Evaporation from mosses and lichens can form a major component of the water balance, especially in ecosystems where mosses and lichens often grow abundantly, such as tundra, deserts and bogs. To facilitate moss representation in hydrological models, we parameterized the unsaturated hydraulic

Sediment properties and water movement through shallow unsaturated alluvium at an arid site for disposal of low-level radioactive waste near Beatty, Nye County, Nevada

Science.gov (United States)

Fischer, Jeffrey M.

1992-01-01

A commercial disposal facility for low-level radioactive waste has been in operation near Beatty, Nevada, since 1962. The facility is in the arid Amargosa Desert where wastes are buried in trenches excavated into unsaturated alluvial sediments. Thick unsaturated zones in arid environments offer many potential advantages for disposal of radioactive wastes, but little is known about the natural movement of water near such facilities. Thus, a study was begun in 1982 to better define the direction and rates of water movement through the unsaturated zone in undisturbed sediments near the disposal facility. This report discusses the analyses of data collected between 1983 and 1988.

Modeling erosion of unsaturated compacted bentonite by groundwater flow; pinhole erosion test case

International Nuclear Information System (INIS)

Laurila, T.; Sane, P.; Olin, M.; Koskinen, K.

2012-01-01

swelling rate to erosion rate. Expressing eroded mass as a function of time as M(t) ∝ tβ. we note that for non-swelling material the wall shear -based erosion model gives β = 0,5. We find this limit in our model by suppressing swelling, and we observe that β increases when ratio of swelling to erosion increases, approaching values β ≅ 1 for strong swelling. It follows that the long term erosion of backfill and buffer materials are expected to differ, with erosion rates in the more compact buffer dropping slower. The result also suggests that the lower the initial erosion, the longer one can expect that rate to be maintained. We solve the model in cylindrically symmetric coordinates using COMSOL Multiphysics software, and fit parameters to match pinhole experiments on MX-80 bentonite with different salinities of the water inflow. Significant scatter within the experimental data makes it difficult to definitively validate models. Figure 1 shows erosion behavior in the model at the limit of vanishing swelling, and contrasts it to the highly-swelling case. Observations from the pinhole experiments, as well as from down-scaled piping erosion tests, show that erosion rates in buffer material don't drop significantly in time, suggesting a consistent with high swelling. In the larger piping erosion tests a seemingly steady state in the erosion rate is reached for an extended amount of time. The effects of scatter are reduced using statistical analysis of this state. An important experimental finding of unsaturated erosion is that larger salinities lead to larger erosion rates, in contrast to saturated erosion where the opposite has been observed. We expect this effect to be due to the processes of saturation, suction and permeability. Future work aims to model the dominant processes in this effect, as pertains to Posiva reference conditions for the Olkiluoto site, without going to the full complexity of (T)HM modeling, such as the Barcelona expansible model

Effects of sand compaction and mixing on pore structure and the unsaturated soil hydraulic properties

NARCIS (Netherlands)

Mahmoodlu, Mojtaba Ghareh; Raoof, A.; Sweijen, T.; van Genuchten, M. Th

2016-01-01

The hydraulic properties of unsaturated porous media very much depend on their pore structure as defined by the size, arrangement, and connectivity of pores. Several empirical and quasi-empirical approaches have been used over the years to derive pore structure information from the particle size

A framework for sourcing of evaporation between saturated and unsaturated zone in bare soil condition

NARCIS (Netherlands)

Balugani, E.; Lubczynski, M.W.; Metselaar, Klaas

2016-01-01

Sourcing subsurface evaporation (E_ss) into groundwater (E_g) and unsaturated zone (E_u) components has received little scientific attention so far, despite its importance in water management and agriculture. We propose a novel sourcing framework, with its

Study on the response of unsaturated soil slope based on the effects of rainfall intensity and slope angle

Science.gov (United States)

Ismail, Mohd Ashraf Mohamad; Hamzah, Nur Hasliza

2017-07-01

Rainfall has been considered as the major cause of the slope failure. The mechanism leading to slope failures included the infiltration process, surface runoff, volumetric water content and pore-water pressure of the soil. This paper describes a study in which simulated rainfall events were used with 2-dimensional soil column to study the response of unsaturated soil behavior based on different slope angle. The 2-dimensional soil column is used in order to demonstrate the mechanism of the slope failure. These unsaturated soil were tested with four different slope (15°, 25°, 35° and 45°) and subjected to three different rainfall intensities (maximum, mean and minimum). The following key results were obtained: (1) the stability of unsaturated soil decrease as the rainwater infiltrates into the soil. Soil that initially in unsaturated state will start to reach saturated state when rainwater seeps into the soil. Infiltration of rainwater will reduce the matric suction in the soil. Matric suction acts in controlling soil shear strength. Reduction in matric suction affects the decrease in effective normal stress, which in turn diminishes the available shear strength to a point where equilibrium can no longer be sustained in the slope. (2) The infiltration rate of rainwater decreases while surface runoff increase when the soil nearly achieve saturated state. These situations cause the soil erosion and lead to slope failure. (3) The steepness of the soil is not a major factor but also contribute to slope failures. For steep slopes, rainwater that fall on the soil surface will become surface runoff within a short time compare to the water that infiltrate into the soil. While for gentle slopes, water that becomes surface runoff will move slowly and these increase the water that infiltrate into the soil.

Development of models for fast fluid pathways through unsaturated heterogeneous porous media

International Nuclear Information System (INIS)

Robey, T.H.

1994-11-01

The pre-waste-emplacement ground water travel time requirement is a regulatory criterion that specifies ground water travel time to the accessible environment shall be greater than 1,000 years. Satisfying the ground water travel time criterion for the potential repository at Yucca Mountain requires the study of fast travel path formation in the unsaturated zone and development of models that simulate the formation of fast paths. Conceptual models for unsaturated flow that have been used for total-systems performance assessment generally fall into the categories of composite-porosity or fracture models. The actual hydrologic conditions at Yucca Mountain are thought to lie somewhere between the extremes of these two types of models. The current study considers the effects of heterogeneities on composite-porosity models and seeks to develop numerical methods (and models) that can produce locally saturated zones where fracture flow can occur. The credibility of the model and numerical methods is investigated by using test data from the INTRAVAL project (Swedish Nuclear Inspectorate, 1992) to attempt to predict in-situ volumetric water content at specific locations in Yucca Mountain. Work based on the numerical methods presented in this study is eventually intended to allow the calculation of ground water travel times in heterogeneous media. 60 refs

Regional coupling of unsaturated and saturated flow and transport modeling - implementation at an alpine foothill aquifer in Austria

Science.gov (United States)

Klammler, G.; Rock, G.; Kupfersberger, H.; Fank, J.

2012-04-01

For many European countries nitrate leaching from the soil zone into the aquifer due to surplus application of mineral fertilizer and animal manure by farmers constitutes the most important threat to groundwater quality. Since this is a diffuse pollution situation measures to change agricultural production have to be investigated at the aquifer scale. In principal, the problem could be solved by the 3 dimensional equation describing variable saturated groundwater flow and solute transport. However, this is computationally prohibitive due to the temporal and spatial scope of the task, particularly in the framework of running numerous simulations to compromise between conflicting interests (i.e. good groundwater status and high agricultural yield). For the aquifer 'Westliches Leibnitzer Feld' we break down this task into 1d vertical movement of water and nitrate mass in the unsaturated zone and 2d horizontal flow of water and solutes in the saturated compartment. The aquifer is located within the Mur Valley about 20 km south of Graz and consists of early Holocene gravel with varying amounts of sand and some silt. The unsaturated flow and nitrate leaching package SIMWASER/STOTRASIM (Stenitzer, 1988; Feichtinger, 1998) is calibrated to the lysimeter data sets and further on applied to so called hydrotopes which are unique combinations of soil type and agricultural management. To account for the unknown regional distribution of crops grown and amount, timing and kind of fertilizers used a stochastic tool (Klammler et al, 2011) is developed that generates sequences of crop rotations derived from municipal statistical data. To match the observed nitrate concentrations in groundwater with a saturated nitrate transport model it is of utmost importance to apply a realistic input distribution of nitrate mass in terms of spatial and temporal characteristics. A table is generated by running SIMWASER/STOTRASIM that consists of unsaturated water and nitrate fluxes for each 10 cm

Modeling of flow and mass transport processes in unsaturated soils in combination with technical facilities; Modellierung von Stroemungs- und Stofftransportprozessen bei Kombination der ungesaettigten Bodenzone mit technischen Anlagen

Energy Technology Data Exchange (ETDEWEB)

Hasan, Issa

2014-07-01

The modelling of complex systems such as the underground is a means to describe the processes occurring in the reality. The conducting of experiments on a model to obtain qualitative evidence about a real system is referred to as a simulation. Thereby, various models (e.g. physical and mathematical models) can be used. The unsaturated zone (vadose zone) is the region between the land surface and the water table, in which the water content is less than full saturation, and the pressure is lower than the atmospheric pressure. The unsaturated zone is very significant for agriculture, geobiology, aerobic degradation processes and groundwater recharge. The processes of water flow and solute transport in the unsaturated zone can be described by means of numerical simulation programs. The aim of the present work is a comprehensive validation of the simulation program PCSiWaPro {sup registered} (developed at the TU-Dresden, Institute of Waste Management and Contaminated Site Treatment) for different applications. Another aim of this work is to investigate the applicability of the current version of PCSiWaPro {sup registered} for different cases of a combination between the unsaturated zone and technical facilities. Four application cases with different objectives were investigated within the present work, which are: the simulation of decentralized wastewater infiltration with corresponding column and field experiments, the computation of groundwater recharge by means of lysimeters, the water balance of earth dams and the modelling of landfill covering systems. The application cases differ from each other by the objective of the simulation, the geometry, the size, the specified initial and boundary conditions, the simulation time, the applied materials, the coordinate system, the input and output data. The simulation results clearly showed that PCSiWaPro {sup registered} is applicable for all investigated cases under consideration of different flow and solute transport

Simulation of unsaturated flow and nonreactive solute transport in a heterogeneous soil at the field scale

International Nuclear Information System (INIS)

Rockhold, M.L.

1993-02-01

A field-scale, unsaturated flow and solute transport experiment at the Las Cruces trench site in New Mexico was simulated as part of a ''blind'' modeling exercise to demonstrate the ability or inability of uncalibrated models to predict unsaturated flow and solute transport in spatially variable porous media. Simulations were conducted using a recently developed multiphase flow and transport simulator. Uniform and heterogeneous soil models were tested, and data from a previous experiment at the site were used with an inverse procedure to estimate water retention parameters. A spatial moment analysis was used to provide a quantitative basis for comparing the mean observed and simulated flow and transport behavior. The results of this study suggest that defensible predictions of waste migration and fate at low-level waste sites will ultimately require site-specific data for model calibration

Synthesis of Phosphatidylcholine Containing Highly Unsaturated Fatty Acid by Phospholipase A2 and Effect on Retinoic Acid Induced Differentiation of HL-60 Cells

OpenAIRE

細川, 雅史; 大島, 宏哲; 甲野, 裕之; 高橋, 是太郎; 羽田野, 六男; 小田島, 粛夫

1993-01-01

Phosphatidylcholine containing highly unsaturated fatty acid (HUFA-PC) was prepared by porcine pancreatic phospholipase A2, which catalyzed esterification between lysophosphatidylcholine (LPC) and highly unsaturated fatty acid (HUFA), under a scaled-up reaction system. Fatty acid mixture prepared from sardine oil, purified eicosapentaenoic acid (EPA), and purified docosahexaenoic acid (DHA) were used as the substrates of HUFA. The yield of HUFA-PC was 17.0-19.9%. Synthesized phosphatidylcholi...

Mechanical properties of composites based on unsaturated polyester resins obtained by chemical recycling of poly(ethylene terephthalate

Directory of Open Access Journals (Sweden)

Marinković Aleksandar D.

2013-01-01

Full Text Available Composites based on unsaturated polyester (UPe resins and fumed silica AEROSIL® RY 50, NY 50, RX 50 and NAX 50, as well as graphite, TiO2 or organically modified clay CLOISITE 30B were prepared in order to investigate the influence of reinforcing agents on the mechanical properties of composites. Unsaturated polyester resins were synthesized from maleic anhydride and products of glycolysis, obtained by depolymerization of poly(ethylene terephthalate with dipropylene glycol (UPe1 resin and triethylene glycol (UPe2 resin in the presence of tetrabutyl titanate catalyst. The obtained unsaturated polyesters were characterized by FTIR spectroscopy, acid and hydroxyl values, and their mechanical properties were also examined. Significant increase of the tensile modulus, tensile strength and decrease of the elongation at break was observed for composites prepared after addition of 10 wt.% of graphite or 10 wt.% of TiO2 to the UPe resins, indicating strong interaction between matrix and filler particles. On the other hand, nanocomposites prepared using UPe2 and hydrophobically modified silica nanoparticles showed lower tensile strength and tensile modulus than polymer matrix. The presence of CLOISITE 30B had no significant influence on the mechanical properties of UPe1, while tensile strength and tensile modulus of UPe2 increased after adding 10 wt.% of clay. [Projekat Ministarstva nauke Republike Srbije, br. 172013

In situ crystallization and transformation kinetics of polymorphic forms of saturated-unsaturated-unsaturated triacylglycerols: 1-palmitoyl-2,3-dioleoyl glycerol, 1-stearoyl-2,3-dioleoyl glycerol, and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol.

Science.gov (United States)

Bayés-García, L; Calvet, T; Cuevas-Diarte, M A; Ueno, S

2016-07-01

We examined the influence of dynamic thermal treatment (variation of cooling/heating rates) on the polymorphic crystallization and transformation pathways of 1-palmitoyl-2,3-dioleoyl glycerol (POO), 1-stearoyl-2,3-dioleoyl glycerol (SOO), and 1-palmitoyl-2-oleoyl-3-linoleoyl glycerol (POL), which are major saturated-unsaturated-unsaturated (SUU) triacylglycerols (TAGs) of vegetable oils and animal fats (e.g., palm oil, olive oil, and Iberian ham fat). Using mainly a combination of differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD), we analyzed the polymorphic behavior of TAGs when high (15°Cmin -1 ), intermediate (2°Cmin -1 ), and low (0.5°Cmin -1 ) cooling and heating rates were applied. Multiple polymorphic forms were detected in POO, SOO, and POL (sub-α, α, β' 2 , and β' 1 ). Transient disordered phases, defined as kinetic liquid crystal (KLC) phases, were determined in POO and SOO for the first time. The results demonstrated that more stable forms were directly obtained from the melt by decreasing the cooling rates, whereas less stable forms predominated at high cooling rates, as confirmed in our previous work. Regarding heating rate variation, we confirmed that the nature of the polymorphic transformations observed (solid-state, transformation through KLC phase, or melt-mediation) depended largely on the heating rate. These results were discussed considering the activation energies involved in each process and compared with previous studies on TAGs with different saturated-unsaturated structures (1,3-dioleoyl-2-palmitoylglycerol, 1,3-dipalmitoyl-2-oleoyl-glycerol, trioleoyl glycerol, and 1,2-dioleoyl-3-linoleoyl glycerol). Copyright © 2016 Elsevier Ltd. All rights reserved.

An experimental program for testing the validity of flow and transport models in unsaturated tuff: The Yucca Mountain Project

International Nuclear Information System (INIS)

Shephard, L.E.; Glass, R.J.; Siegel, M.D.; Tidwell, V.C.

1990-01-01

Groundwater flow and contaminant transport through the unsaturated zone are receiving increased attention as options for waste disposal in saturated media continue to be considered as a potential means for resolving the nation's waste management concerns. An experimental program is being developed to test the validity of conceptual flow and transport models that are being formulated to predict the long-term performance at Yucca Mountain. This program is in the developmental stage and will continue to evolve as information is acquired and knowledge is improved with reference to flow and transport in unsaturated fractured media. The general approach for directing the validation effort entails identifying those processes which may cause the site to fail relative to imposed regulatory requirements, evaluating the key assumptions underlying the conceptual models used or developed to describe these processes, and developing new conceptual models as needed. Emphasis is currently being placed in four general areas: flow and transport in unsaturated fractures; fracture-matrix interactions; infiltration flow instability; and evaluation of scale effects in heterogeneous fractured media. Preliminary results and plans or each of these areas for both the laboratory and field investigation components will be presented in the manuscript. 1 ref

Disposal of high-level radioactive wastes in the unsaturated zone: technical considerations and response to comments. Final report

International Nuclear Information System (INIS)

Hackbarth, C.J.; Nicholson, T.J.; Evans, D.D.

1985-10-01

On July 22, 1985, the US Nuclear Regulatory Commission (NRC) promulgated amendments to 10 CFR Part 60 concerning disposal of high-level radioactive waste (HLW) in geologic repositories in the unsaturated zone (50 FR 29641). This report contains a discussion of the principal technical issues considered by the NRC staff during the development of these amendments. It expands or revises certain technical discussions originally presented in draft NUREG-1046 (February 1984) based on public comment letters and an increasing understanding of the physical, geochemical, and hydrogeologic processes operative in unsaturated geologic media. The following issues related to disposal of HLW within the unsaturated zone are discussed: hydrogeologic properties and conditions, heat dissipation and temperature, geochemisty, retrievability, potential for exhumation of the radioactive waste by natural causes and by human intrusion, the effects of future climatic changes on the level of the regional water table, and transport of radionuclides in the gaseous state. The changes to 10 CFR Part 60 in definitions, siting criteria, and design criteria for the geologic repository operations area are discussed. Other criteria examined by the NRC staff but which were not changed in rule are the minimum 300-meter depth for waste emplacement, limitations on exploratory boreholes, backfill requirements, waste package design criteria, and provisions for ventilation

Proceedings of workshop 5: Flow and transport through unsaturated fractured rock -- related to high-level radioactive waste disposal

International Nuclear Information System (INIS)

Evans, D.D.; Nicholson, T.J.

1993-06-01

The ''Workshop on Flow and Transport Through Unsaturated Fractured Rock Related to High-Level Radioactive Waste Disposal'' was cosponsored by the NRC, the Center for Nuclear Waste Regulatory Analyses, and the University of Arizona (UAZ) and was held in Tucson, Arizona, on January 7--10, 1991. The focus of this workshop, similar to the earlier four (the first being in 1982), related to hydrogeologic technical issues associated with possible disposal of commercial high-level nuclear waste (HLW) in a geologic repository within an unsaturated fractured rock system which coincides with the UAZ field studies on HLW disposal. The presentations and discussions centered on flow and transport processes and conditions, relevant parameters, as well as state-of-the-art measurement techniques, and modeling capabilities. The workshop consisted of: four half-day technical meetings, a one day field visit to the Apache Leap test site to review ongoing field studies that are examining site characterization techniques and developing data sets for model validation studies, and a final half-day session devoted to examining research needs related to modeling groundwater flow and radionuclide transport in unsaturated, fractured rock. These proceedings provide extended abstracts of the technical presentations and short summaries of the research group reports

Unsaturated flow and transport research questions and priorities

International Nuclear Information System (INIS)

Chery, D.L.

1993-01-01

A little over two years ago, a similar meeting (Workshop IV - Flow and Transport through Unsaturated Fractured Rock; Related to High-Level Radioactive Waste Disposal) was held her in Tucson, Arizona, to discuss the same issues discussed here the past 4 days. This presentation revisits what was said 2 years ago, reviews research needs that have been articulated by the licensing staff of the Division of High-Level Waste Management, Nuclear Regulatory Commission, and presents some of the thoughts on research needs resulting from the deliberations of a special committee of the National Research Council. After considering these aspects the questions of what has been accomplished in the past 2 years and where attention and energies should be focused in the coming few years, can be asked. 3 refs

Single-Step Access to Long-Chain α,ω-Dicarboxylic Acids by Isomerizing Hydroxycarbonylation of Unsaturated Fatty Acids

KAUST Repository

Goldbach, Verena

2016-11-09

Dicarboxylic acids are compounds of high value, but to date long-chain alpha,omega-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionalization. Within this paper, we established a direct access to alpha,omega-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)(2)] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH(2))(OTf)(2) to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the Pd-II precursor, which proceeds via a reductive elimination step forming a Pd species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic

Maximum likelihood Bayesian averaging of airflow models in unsaturated fractured tuff using Occam and variance windows

NARCIS (Netherlands)

Morales-Casique, E.; Neuman, S.P.; Vesselinov, V.V.

2010-01-01

We use log permeability and porosity data obtained from single-hole pneumatic packer tests in six boreholes drilled into unsaturated fractured tuff near Superior, Arizona, to postulate, calibrate and compare five alternative variogram models (exponential, exponential with linear drift, power,

Recent advances in the chemical modification of unsaturated polymers

Science.gov (United States)

Schulz, D. N.; Turner, S. R.; Golub, M. A.

1982-01-01

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

Ruthenium-catalyzed direct C3 alkylation of indoles with α,β-unsaturated ketones.

Science.gov (United States)

Li, Shuai-Shuai; Lin, Hui; Zhang, Xiao-Mei; Dong, Lin

2015-01-28

In this paper, a simple and highly efficient ruthenium-catalyzed direct C3 alkylation of indoles with various α,β-unsaturated ketones without chelation assistance has been developed. This novel C-H activation methodology exhibits a broad substrate scope such as different substituted indoles, pyrroles, and other azoles. Further synthetic applications of the alkylation products can lead to more attractive 3,4-fused tricyclic indoles.

Environmental isotope profiles of the soil water in loess unsaturated zone in semi-arid areas of china

International Nuclear Information System (INIS)

Lin Ruifen; Wei Keqin

2001-01-01

According to the IAEA Research Contract No. 9402, soil cores CHN/97 and CHN/98 were taken from loess deposits of China in Inner-Mongolia and Shanxi Province, respectively. Isotope and chemical constituents of the interstitial water from these cores, compared with data obtained from the same places before, were used for estimating the infiltration rate. Tritium profiles from the loess unsaturated zone show clearly defined peaks of 1963 fallout. It implies that piston-flow model is the dominant process for soil water movement in the highly homogeneous loess deposits. It has been shown from this study that vertical infiltration through the unsaturated zone accounts for 12%-13% of the annual precipitation and perhaps is not the main mechanism of groundwater recharge in semi-arid loess areas. (author)

A facile one-pot synthesis of (Z-α-chloro-α,β-unsaturated esters from alcohols

Directory of Open Access Journals (Sweden)

U. Karama

2017-05-01

Full Text Available Treatment of N-Chlorosuccinimide with (ethoxycarbonylmethylene-triphenylphosphorane followed by oxidation of alcohol using DMSO/SO3.Pyridine complex as a mild oxidant and trapping of the aldehydes constitutes a stereoselective single flask procedure for the preparation of Z-configured α-chloro-α,β-unsaturated esters.

Sampling silica and ferrihydrite colloids with fiberglass wicks under unsaturated conditions.

Science.gov (United States)

Shira, Jason M; Williams, Barbara C; Flury, Markus; Czigány, Szabolcs; Tuller, Markus

2006-01-01

The suitability of passive capillary samplers (PCAPS) for collection of representative colloid samples under partially saturated conditions was evaluated by investigating the transport of negatively and positively charged colloids in fiberglass wicks. A synthetic pore water solution was used to suspend silica microspheres (330 nm in diameter) and ferrihydrite (172 nm in diameter) for transport experiments on fiberglass wicks. Breakthrough curves were collected for three unsaturated flow rates with silica microspheres and one unsaturated flow rate with ferrihydrite colloids. A moisture characteristic curve, relating tensiometer measurements of matric potential to moisture content, was developed for the fiberglass wick. Results indicate that retention of the silica and the ferrihydrite on the wick occurred; that is, the wicks did not facilitate quantitative sampling of the colloids. For silica microspheres, 90% of the colloids were transmitted through the wicks. For ferrihydrite, 80 to 90% of the colloids were transmitted. The mechanisms responsible for the retention of the colloids on the fiberglass wicks appeared to be physicochemical attachment and not thin-film, triple-phase entrapment, or mechanical straining. Visualization of pathways by iron staining indicates that flow is preferential at the center of twisted bundles of filaments. Although axial preferential flow in PCAPS may enhance their hydraulic suitability for sampling mobile colloids, we conclude that without specific preparation to reduce attachment or retention, fiberglass wicks should only be used for qualitative sampling of pore water colloids.

Modelling free surface aquifers to analyze the interaction between groundwater and sinuous streams

DEFF Research Database (Denmark)

Balbarini, Nicola; Boon, W. M.; Bjerg, Poul Løgstrup

and errors. In addition, when streams are sinuous, groundwater flow is truly 3-dimensional, with strong vertical flows and sharp changes in horizontal direction. Here 3 different approaches to simulating free surface aquifers are compared for simulating groundwater-stream interaction. The aim of the models......: a saturated-unsaturated flow model, moving mesh, and a new coordinate transformation. The saturated/unsaturated model couples the saturated groundwater flow equation with a solution of Richards equation. The moving mesh solves the saturated groundwater equation with a free surface and deformable numerical...... finite element mesh. Finally, the new coordinate transform method employs a coordinate transform so that the saturated groundwater flow equation is solved on a fixed finite element mesh with a stationary free surface. This paper describes in detail the new coordinate transform method. It employs...

Bayesian estimation of the hydraulic and solute transport properties of a small-scale unsaturated soil column

NARCIS (Netherlands)

Moreira, Paulo H S; Van Genuchten, Martinus Th; Orlande, Helcio R B; Cotta, Renato M.

2016-01-01

In this study the hydraulic and solute transport properties of an unsaturated soil were estimated simultaneously from a relatively simple small-scale laboratory column infiltration/outflow experiment. As governing equations we used the Richards equation for variably saturated flow and a physical

Triaxial- and uniaxial-compression testing methods developed for extraction of pore water from unsaturated tuff, Yucca Mountain, Nevada

Energy Technology Data Exchange (ETDEWEB)

Mower, T.E.; Higgins, J.D. [Colorado School of Mines, Golden, CO (USA). Dept. of Geology and Geological Engineering; Yang, I.C. [Geological Survey, Denver, CO (USA). Water Resources Div.

1989-12-31

To support the study of hydrologic system in the unsaturated zone at Yucca Mountain, Nevada, two extraction methods were examined to obtain representative, uncontaminated pore-water samples from unsaturated tuff. Results indicate that triaxial compression, which uses a standard cell, can remove pore water from nonwelded tuff that has an initial moisture content greater than 11% by weight; uniaxial compression, which uses a specifically fabricated cell, can extract pore water from nonwelded tuff that has an initial moisture content greater than 8% and from welded tuff that has an initial moisture content greater than 6.5%. For the ambient moisture conditions of Yucca Mountain tuffs, uniaxial compression is the most efficient method of pore-water extraction. 12 refs., 7 figs., 2 tabs.

A statistical approach to evaluate hydrocarbon remediation in the unsaturated zone

International Nuclear Information System (INIS)

Hajali, P.; Marshall, T.; Overman, S.

1991-01-01

This paper presents an evaluation of performance and cleanup effectiveness of a vapor extraction system (VES) in extracting chlorinated hydrocarbons and petroleum-based hydrocarbons (mineral spirits) from the unsaturated zone. The statistical analysis of soil concentration data to evaluate the VES remediation success is described. The site is a former electronics refurbishing facility in southern California; soil contamination from organic solvents was found mainly in five areas (Area A through E) beneath two buildings. The evaluation begins with a brief description of the site background, discusses the statistical approach, and presents conclusions

Advective and diffusive contributions to reactive gas transport during pyrite oxidation in the unsaturated zone

NARCIS (Netherlands)

Binning, P. J.; POSTMA, D; Russell, T. F.; Wesselingh, J. A.; Boulin, P. F.

2007-01-01

[1] Pyrite oxidation in unsaturated mine waste rock dumps and soils is limited by the supply of oxygen from the atmosphere. In models, oxygen transport through the subsurface is often assumed to be driven by diffusion. However, oxygen comprises 23.2% by mass of dry air, and when oxygen is consumed

Coordinate measuring machines

DEFF Research Database (Denmark)

De Chiffre, Leonardo

This document is used in connection with three exercises of 2 hours duration as a part of the course GEOMETRICAL METROLOGY AND MACHINE TESTING. The exercises concern three aspects of coordinate measuring: 1) Measuring and verification of tolerances on coordinate measuring machines, 2) Traceabilit...... and uncertainty during coordinate measurements, 3) Digitalisation and Reverse Engineering. This document contains a short description of each step in the exercise and schemes with room for taking notes of the results.......This document is used in connection with three exercises of 2 hours duration as a part of the course GEOMETRICAL METROLOGY AND MACHINE TESTING. The exercises concern three aspects of coordinate measuring: 1) Measuring and verification of tolerances on coordinate measuring machines, 2) Traceability...

Elucidating the mechanical effects of pore water pressure increase on the stability of unsaturated soil slopes

Science.gov (United States)

Buscarnera, G.

2012-12-01

The increase of the pore water pressure due to rain infiltration can be a dominant component in the activation of slope failures. This paper shows an application of the theory of material stability to the triggering analysis of this important class of natural hazards. The goal is to identify the mechanisms through which the process of suction removal promotes the initiation of mechanical instabilities. The interplay between increase in pore water pressure, and failure mechanisms is investigated at material point level. In order to account for multiple failure mechanisms, the second-order work criterion is used and different stability indices are devised. The paper shows that the theory of material stability can assess the risk of shear failure and static liquefaction in both saturated and unsaturated contexts. It is shown that the combined use of an enhanced definition of second-order work for unsaturated porous media and a hydro-mechanical constitutive framework enables to retrieve bifurcation conditions for water-infiltration processes in unsaturated deposits. This finding discloses the importance of the coupling terms that incorporate the interaction between the solid skeleton and the pore fluids. As a consequence, these theoretical results suggest that some material properties that are not directly associated with the shearing resistance (e.g., the potential for wetting compaction) can play an important role in the initiation of slope failures. According to the proposed interpretation, the process of pore pressure increase can be understood as a trigger of uncontrolled strains, which at material point level are reflected by the onset of bifurcation conditions.

Interpretation of chemical and isotopic data from boreholes in the unsaturated zone at Yucca Mountain, Nevada

International Nuclear Information System (INIS)

Yang, I.C.; Rattray, G.W.; Yu, P.

1996-01-01

Analyses of pore water from boreholes at Yucca Mountain indicate that unsaturated-zone pore water has significantly larger concentrations of chloride and dissolved solids than the saturated-zone water or perched-water bodies. Chemical compositions are of the calcium sulfate or calcium chloride types in the Paintbrush Group (Tiva Canyon, Yucca Mountain, Pah Canyon, and bedded tuffs), and sodium carbonate or bicarbonate type water in the Calico Hills Formation. Tritium profiles from boreholes at Yucca Mountain indicate tritium-concentration inversions (larger tritium concentrations are located below the smaller tritium concentration in a vertical profile) occur in many places. These inversions indicate preferential flow through fractures. Rock-gas compositions are similar to that of atmospheric air except that carbon dioxide concentrations are generally larger than those in the air. The delta carbon-13 values of gas are fairly constant from surface to 365.8 meters, indicating little interaction between the gas CO 2 and caliche in the soil. Model calculations indicate that the gas transport in the unsaturated zone at Yucca Mountain agrees well with the gas-diffusion process. Tritium-modeling results indicate that the high tritium value of about 100 tritium units in the Calico Hills Formation of UZ-16 is within limits of a piston-flow model with a water residence time of 32 to 35 years. The large variations in tritium concentrations with narrow peaks imply piston flow or preferential fracture flow rather than matrix flow. In reality, the aqueous-phase flow in the unsaturated zone is between piston and well-mixed flows but is closer to a piston flow

Assimilation of ambient seismic noise in hydrological models allows estimation of hydraulic conductivity in unsaturated media

Science.gov (United States)

Fores, B.; Champollion, C.; Mainsant, G.; Fort, A.; Albaric, J.

2016-12-01

Karstic hydrosystems represent one of the main water resources in the Mediterranean area but are challenging for geophysical methods. The GEK (Geodesy in Karstic Environment) observatory has been setup in 2011 to study the unsaturated zone of a karstic system in the south of France. The unsaturated zone (the epikarst) is thick and up to 100m on the site. Since 2011, gravity, rainfall and evapotranspiration are monitored. Together, they allow precise estimation of the global water storage changes but lack depth resolution. Surface waves velocity variations, obtained from ambient seismic noise monitoring are used here to overcome this lack. Indeed, velocities depend on saturation and the depths where changes occur can be defined as surface waves are dispersive. From October 2014 to November 2015, two seismometers have been recording noise. Velocity changes at a narrow frequency band (6-8 Hz) have shown a clear annual cycle. Minimum velocity is several months late on precipitations, which is coherent with a slow infiltration and a maximum sensitivity at -40m for these frequencies and this site. Models have been made with the Hydrus-1D software which allows modeling 1D-flow in variably saturated media. With a stochastic sampling, we have researched the underground parameters that reproduce the most the different observations (gravity, evapotranspiration and rainfall, and velocity changes). We show that velocity changes clearly constrain the hydraulic conductivity of the medium. Ambient seismic noise is therefore a promising method to study unsaturated zone which are too deep or too heterogeneous for classic methods.

Molecular Fluoride-Bridged 3d-4f Complexes and Their Magnetic Properties

DEFF Research Database (Denmark)

Pedersen, K. S.; Bendix, J.

2016-01-01

trifluorides with very high lattice enthalpies, building block approaches are not limited to robust systems and use of labile transition metal fluoride complexes has met with unexpected success. The physical properties of fluoride-bridged 3d-4f systems are crucially dependent on coordination geometries, which...... be utilized efficiently in tailored synthesis of polynuclear complexes and extended structures. In particular, the strong affinity of the lanthanides for fluoride makes it a good choice for directed synthesis of mixed lanthanide-transition metal complexes. Despite the competition from formation of lanthanide...

Effective stress in unsaturated soils: A thermodynamic approach based on the interfacial energy and hydromechanical coupling

NARCIS (Netherlands)

Nikooee, E.; Habibagahi, G.; Hassanizadeh, S.M.; Ghahramani, A.

2012-01-01

In recent years, the effective stress approach has received much attention in the constitutive modeling of unsaturated soils. In this approach, the effective stress parameter is very important. This parameter needs a correct definition and has to be determined properly. In this paper, a

Comparison of Three Model Concepts for Streaming Potential in Unsaturated Porous Media

Science.gov (United States)

Huisman, J. A.; Satenahalli, P.; Zimmermann, E.; Vereecken, H.

2017-12-01

Streaming potential is the electric potential generated by fluid flow in a charged porous medium. Although streaming potential in saturated conditions is well understood, there still is considerable debate about the adequate modelling of streaming potential signals in unsaturated soil because different concepts are available to estimate the effective excess charge in unsaturated conditions. In particular, some studies have relied on the volumetric excess charge, whereas others proposed to use the flux-averaged excess charge derived from the water retention or relative permeability function. The aim of this study is to compare measured and modelled streaming potential signals for two different flow experiments with sand. The first experiment is a primary gravity drainage of a long column equipped with non-polarizing electrodes and tensiometers, as presented in several previous studies. Expected differences between the three concepts for the effective excess charge are only moderate for this set-up. The second experiment is a primary drainage of a short soil column equipped with non-polarizing electrodes and tensiometers using applied pressure, where differences between the three concepts are expected to be larger. A comparison of the experimental results with a coupled model of streaming potential for 1D flow problems will provide insights in the ability of the three model concepts for effective excess charge to describe observed streaming potentials.

Arylation of beta, gamma-unsaturated lactones by a Heck-Matsuda reaction: an unexpected route to aryldiazene butenolides and pyridazinones

Energy Technology Data Exchange (ETDEWEB)

Taylor, Jason G.; Correia, Carlos Roque D., E-mail: roque@iqm.unicamp.b [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2010-07-01

The palladium catalysed coupling of aryldiazonium salts with {beta}-{gamma}-unsaturated lactones under basic conditions has been investigated. Both (3H)-furanone and {alpha}-angelicalactone were evaluated as substrates in the Heck Matsuda reaction but both failed to afford the desired arylated butenolides. Under basic conditions, {beta}-{gamma}-unsaturated lactones generate highly nucleophilic enolates that preferentially undergo azo coupling reactions with arenediazonium salts to afford aryldiazene butenolides. The electronic and steric effect of the substituents on the aryldiazonium salt in the azo coupling reaction is described. Aryldiazene-lactone derivatives were obtained in good yields from a highly facile and straightforward procedure. An aminoisomaleimide was formed from (3H)-furanone and cyclized to the corresponding pyridazinones in modest yield. (author)

Decomposition of groundwater level fluctuations using transfer modelling in an area with shallow to deep unsaturated zones

Science.gov (United States)

Gehrels, J. C.; van Geer, F. C.; de Vries, J. J.

1994-05-01

Time series analysis of the fluctuations in shallow groundwater levels in the Netherlands lowlands have revealed a large-scale decline in head during recent decades as a result of an increase in land drainage and groundwater withdrawal. The situation is more ambiguous in large groundwater bodies located in the eastern part of the country, where the unsaturated zone increases from near zero along the edges to about 40 m in the centre of the area. As depth of the unsaturated zone increases, groundwater level reacts with an increasing delay to fluctuations in climate and influences of human activities. The aim of the present paper is to model groundwater level fluctuations in these areas using a linear stochastic transfer function model, relating groundwater levels to estimated precipitation excess, and to separate artificial components from the natural groundwater regime. In this way, the impact of groundwater withdrawal and the reclamation of a 1000 km 2 polder area on the groundwater levels in the adjoining higher ground could be assessed. It became evident that the linearity assumption of the transfer functions becomes a serious drawback in areas with the deepest groundwater levels, because of non-linear processes in the deep unsaturated zone and the non-synchronous arrival of recharge in the saturated zone. Comparison of the results from modelling the influence of reclamation with an analytical solution showed that the lowering of groundwater level is partly compensated by reduced discharge and therefore is less than expected.

EFSA ; Scientific Opinion on Flavouring Group Evaluation 98 (FGE.98): Consideration of three ring-unsaturated delta-lactones)

DEFF Research Database (Denmark)

Larsen, John Christian; Nørby, Karin Kristiane; Beltoft, Vibe Meister

evaluation is necessary, as laid down in Commission Regulation (EC) No 1565/2000. The present consideration concerns a group of three unsaturated delta-lactones [FL-no: 10.031, 10.037 and 10.044] previously evaluated by the JECFA at their 49th meeting in 1997. The JECFA considered that further information...... on the metabolism of these three substances was required and that they should be evaluated together with other substances containing alpha,beta-unsaturation and that, therefore, their evaluation should be deferred. However, the EFSA Panel has considered that these three JECFA evaluated aliphatic lactones can...... be hydrolysed and metabolised to innocuous products in line with the aliphatic lactones evaluated by EFSA in FGE.10Rev2. The substances were evaluated through a stepwise approach that integrates information on structure-activity relationships, intake from current uses, toxicological threshold of concern...

Balancing practicality and hydrologic realism: a parsimonious approach for simulating rapid groundwater recharge via unsaturated-zone preferential flow

Science.gov (United States)

Mirus, Benjamin B.; Nimmo, J.R.

2013-01-01

The impact of preferential flow on recharge and contaminant transport poses a considerable challenge to water-resources management. Typical hydrologic models require extensive site characterization, but can underestimate fluxes when preferential flow is significant. A recently developed source-responsive model incorporates film-flow theory with conservation of mass to estimate unsaturated-zone preferential fluxes with readily available data. The term source-responsive describes the sensitivity of preferential flow in response to water availability at the source of input. We present the first rigorous tests of a parsimonious formulation for simulating water table fluctuations using two case studies, both in arid regions with thick unsaturated zones of fractured volcanic rock. Diffuse flow theory cannot adequately capture the observed water table responses at both sites; the source-responsive model is a viable alternative. We treat the active area fraction of preferential flow paths as a scaled function of water inputs at the land surface then calibrate the macropore density to fit observed water table rises. Unlike previous applications, we allow the characteristic film-flow velocity to vary, reflecting the lag time between source and deep water table responses. Analysis of model performance and parameter sensitivity for the two case studies underscores the importance of identifying thresholds for initiation of film flow in unsaturated rocks, and suggests that this parsimonious approach is potentially of great practical value.

Studies on the role of unsaturation in the fatty acid surfactant molecule on the thermal conductivity of magnetite nanofluids.

Science.gov (United States)

Lenin, Ramanujam; Joy, Pattayil Alias

2017-11-15

To study the role of unsaturation in the surfactant molecule on the thermal conductivity of magnetite nanofluids, four different fatty acid (stearic, oleic, linoleic, and linolenic acids with different degree of unsaturation) coated magnetite nanoparticles of comparable size are prepared and dispersed in toluene. It is found that the nanofluid with the saturated fatty acid coated nanoparticles show larger viscosity than the fluid with the unsaturated fatty acid coated particles at all concentrations. Thermal conductivity studies show enhancement only above a critical concentration for all fluids. The critical concentration for thermal conductivity enhancement varies with the surfactant, possibly due to the difference in the degree of aggregation of the nanoparticles in the fluid, because of the difference in the conformation of the surfactant molecules on the nanoparticle's surface. The experimental thermal conductivity follows the Maxwell model at higher concentrations. From the overall studies, it is observed that the thermal conductivity of the fluids with aggregated or assembled nanoparticles shows slightly larger enhancement than that of the fluids with isolated particles. However, in the presence of a magnetic field, the fluids with isolated nanoparticles showed relatively larger enhancement, possibly due to the easy response of the isolated magnetite nanoparticles to the applied field. Copyright © 2017 Elsevier Inc. All rights reserved.

Boundary integral methods for unsaturated flow

International Nuclear Information System (INIS)

Martinez, M.J.; McTigue, D.F.

1990-01-01

Many large simulations may be required to assess the performance of Yucca Mountain as a possible site for the nations first high level nuclear waste repository. A boundary integral equation method (BIEM) is described for numerical analysis of quasilinear steady unsaturated flow in homogeneous material. The applicability of the exponential model for the dependence of hydraulic conductivity on pressure head is discussed briefly. This constitutive assumption is at the heart of the quasilinear transformation. Materials which display a wide distribution in pore-size are described reasonably well by the exponential. For materials with a narrow range in pore-size, the exponential is suitable over more limited ranges in pressure head. The numerical implementation of the BIEM is used to investigate the infiltration from a strip source to a water table. The net infiltration of moisture into a finite-depth layer is well-described by results for a semi-infinite layer if αD > 4, where α is the sorptive number and D is the depth to the water table. the distribution of moisture exhibits a similar dependence on αD. 11 refs., 4 figs.,

Reactions of CH-acids with α,β-unsaturated aldehydes in ionic liquids

DEFF Research Database (Denmark)

Kryshtal, G. V.; Zhdankina, G. M.; Astakhova, Irina Kira

2004-01-01

Metal carbonate-catalyzed reactions of CH-acids (diethyl malonate, ethyl acetoacetate, ethyl cyanoacetate, and ethyl 2-acetyl- and 2-ethoxycarbonyl-5,9- dimethyldeca-4,8-dienoates) with α,β-unsaturated aldehydes (acrolein, crotonaldehyde, citral) were studied in an ionic liquid, 1-butyl-3......- methylimidazolium hexafluorophosphate [bmim][PF 6], and in a 1-butyl-3-methylimidazolium bromide ([bmim][Br]) - benzene system. The reactions with acrolein and crotonaldehyde afforded Michael addition products, those with citral resulted in Knoevenagel addition products. Sonication increased the yields...

Modeling studies of unsaturated flow with long-term permeability change at Yucca Mountain

International Nuclear Information System (INIS)

Zhang Chengyuan; Liu Xiaoyan; Liu Quansheng

2008-01-01

The amount of water seeping into the waste emplacement drifts is crucial for the performance of underground nuclear waste repository, since it controls the corrosion rates of waste packages and the mobilization rate of radionuclides. It is limited by water flow through drift vicinity. In the present work we study the potential rates of water flow around drifts as a function of predicted long-term change of permeability at Yucca Mountain, based on a dual-continuum model of the unsaturated flow in fractured rock mass. For stage of DECOVALEX Ⅳ, we used a simplified practical model on unsaturated flow in Yucca Mountain case simulation. These models contain main physical processes that should be considered, including thermal expansion, thermal radiation, water-rock coupling and stress-induced change of permeability. Comparative study with other DECOVALEX team's results shows that they are both good enough and flexible enough to include more physical processes. We can draw the conclusion that it is necessary to model stress-induced changes in permeability and relative processes in future studies, because there are obvious differences (in water saturation and water flux) between simulation cases with and without variable permeability, especially in areas very close to the drift. (authors)

Salt content impact on the unsaturated property of bentonite-sand buffer backfilling materials

Energy Technology Data Exchange (ETDEWEB)

Zhang Ming [Key Laboratory of Mechanics on Disaster and Environment in Western China, Lanzhou University, Lanzhou 730000 (China); Zhang Huyuan, E-mail: p1314lvp@yahoo.com.cn [Key Laboratory of Mechanics on Disaster and Environment in Western China, Lanzhou University, Lanzhou 730000 (China); Jia Lingyan; Cui Suli [Key Laboratory of Mechanics on Disaster and Environment in Western China, Lanzhou University, Lanzhou 730000 (China)

2012-09-15

Highlights: Black-Right-Pointing-Pointer SWCC and infiltration process of bentonite-sand mixtures is researched. Black-Right-Pointing-Pointer The k{sub u} of bentonite-sand mixtures was evaluated as the buffer backfilling materials. Black-Right-Pointing-Pointer Salt content impacting on the unsaturated property of bentonite-sand materials is small. - Abstract: Bentonite mixed with sand is often considered as possible engineered barrier in deep high-level radioactive waste disposal in China. In the present work, the vapor transfer technique and water infiltration apparatus were used to measure the soil water characteristic curve (SWCC) and unsaturated hydraulic conductivity (k{sub u}) of bentonite-sand mixtures (B/S) effected by salt content. Results show, the water-holding capacity and k{sub u} increase slightly with the concentration of Na{sup +} in pore liquid increasing from 0 g/L to 12 g/L, similar with the solution concentration of Beishan groundwater in China. Salt content in the laboratory produced only one order of magnitude increase in k{sub u}, which is the 'safe' value. The different pore liquid concentrations used in this study led to small differences in thickness of diffuse double layer of bentonite in mixtures, this might explain why some differences have been found in final values of k{sub u}.

Two-phase unsaturated flow at Yucca Mountain, Nevada - A Report on Current Understanding

International Nuclear Information System (INIS)

Pruess, K.

1998-01-01

The U.S. civilian nuclear waste program is unique in its focus on disposal of high-level wastes in the unsaturated zone (UZ), above the water table. The potential repository site currently under investigation is located in a semi-arid region of the southwestern U.S. at Yucca Mountain, Nevada. The geology of the site consists of layered sequences of faulted, fractured, and bedded tuffs. The groundwater table is approximately 600 m beneath the land surface, while the proposed repository horizon is at a nominal depth of approximately 375 m. In this kind of environment, two-phase flow is not just a localized perturbation to natural conditions, as in the saturated zone, but is the predominant mode of water and gas flow. The purpose of this report is to review the current understanding of gas and water flow, and mass transport, in the unique hydrogeologic environment of Yucca Mountain. Characteristics of the Yucca Mountain site are examined, and concepts and mathematical modeling approaches are described for variably saturated flow in thick unsaturated zones of fractured rock. The paper includes a brief summary of the disposal concept and repository design, as developed by a team of engineering contractors to the U.S. Department of Energy (DOE), with strong participation from the DOE National Laboratories

Estimation of Unsaturated Zone Traveltimes for Rainier Mesa and Shoshone Mountain, Nevada Test Site, Nevada, Using a Source-Responsive Preferential-Flow Model

Science.gov (United States)

Ebel, Brian A.; Nimmo, John R.

2009-01-01

Traveltimes for contaminant transport by water from a point in the unsaturated zone to the saturated zone are a concern at Rainier Mesa and Shoshone Mountain in the Nevada Test Site, Nevada. Where nuclear tests were conducted in the unsaturated zone, contaminants must traverse hundreds of meters of variably saturated rock before they enter the saturated zone in the carbonate rock, where the regional groundwater system has the potential to carry them substantial distances to a location of concern. The unsaturated-zone portion of the contaminant transport path may cause a significant delay, in addition to the time required to travel within the saturated zone, and thus may be important in the overall evaluation of the potential hazard from contamination. Downward contaminant transport through the unsaturated zone occurs through various processes and pathways; this can lead to a broad distribution of contaminant traveltimes, including exceedingly slow and unexpectedly fast extremes. Though the bulk of mobile contaminant arrives between the time-scale end members, the fastest contaminant transport speed, in other words the speed determined by the combination of possible processes and pathways that would bring a measureable quantity of contaminant to the aquifer in the shortest time, carries particular regulatory significance because of its relevance in formulating the most conservative hazard-prevention scenarios. Unsaturated-zone flow is usually modeled as a diffusive process responding to gravity and pressure gradients as mediated by the unsaturated hydraulic properties of the materials traversed. The mathematical formulation of the diffuse-flow concept is known as Richards' equation, which when coupled to a solute transport equation, such as the advection-dispersion equation, provides a framework to simulate contaminant migration in the unsaturated zone. In recent decades awareness has increased that much fluid flow and contaminant transport within the unsaturated

Estimation of unsaturated zone traveltimes for Rainier Mesa and Shoshone Mountain, Nevada Test Site, Nevada, using a source-responsive preferential-flow model

Energy Technology Data Exchange (ETDEWEB)

Brian A. Ebel; John R. Nimmo

2009-09-11

Traveltimes for contaminant transport by water from a point in the unsaturated zone to the saturated zone are a concern at Rainier Mesa and Shoshone Mountain in the Nevada Test Site, Nevada. Where nuclear tests were conducted in the unsaturated zone, contaminants must traverse hundreds of meters of variably saturated rock before they enter the saturated zone in the carbonate rock, where the regional groundwater system has the potential to carry them substantial distances to a location of concern. The unsaturated-zone portion of the contaminant transport path may cause a significant delay, in addition to the time required to travel within the saturated zone, and thus may be important in the overall evaluation of the potential hazard from contamination. Downward contaminant transport through the unsaturated zone occurs through various processes and pathways; this can lead to a broad distribution of contaminant traveltimes, including exceedingly slow and unexpectedly fast extremes. Though the bulk of mobile contaminant arrives between the time-scale end members, the fastest contaminant transport speed, in other words the speed determined by the combination of possible processes and pathways that would bring a measureable quantity of contaminant to the aquifer in the shortest time, carries particular regulatory significance because of its relevance in formulating the most conservative hazard-prevention scenarios. Unsaturated-zone flow is usually modeled as a diffusive process responding to gravity and pressure gradients as mediated by the unsaturated hydraulic properties of the materials traversed. The mathematical formulation of the diffuse-flow concept is known as Richards' equation, which when coupled to a solute transport equation, such as the advection-dispersion equation, provides a framework to simulate contaminant migration in the unsaturated zone. In recent decades awareness has increased that much fluid flow and contaminant transport within the

Bridging effective stress and soil water retention equations in deforming unsaturated porous media : A Thermodynamic Approach

NARCIS (Netherlands)

Huyghe, J. M.; Nikooee, E.; Hassanizadeh, S. M.

The finite deformation of an unsaturated porous medium is analysed from first principles of mixture theory. An expression for Bishop’s effective stress is derived from (1) the deformation-dependent Brooks and Corey’s water retention curve and (2) the restrictions on the constitutive relationships of

Coordinated School Health and the Contribution of a District Wellness Coordinator

Science.gov (United States)

Westrich, Lisa; Sanchez, Monika; Strobel, Karen

2015-01-01

Background: A San Francisco Bay Area school health initiative was established in fall 2010 to improve wellness programs in 4 local school districts using the Coordinated School Health (CSH) model. This study examines the role of district-wide wellness coordinators and the ways in which they contribute to intentional coordination of health and…

Modeling Raw Sewage Leakage and Transport in the Unsaturated Zone of Carbonate Aquifer Using Carbamazepine as an Indicator

Science.gov (United States)

Yakirevich, A.; Kuznetsov, M.; Livshitz, Y.; Gasser, G.; Pankratov, I.; Lev, O.; Adar, E.; Dvory, N. Z.

2016-12-01

Fast contamination of groundwater in karstic aquifers can be caused due to leaky sewers, for example, or overflow from sewer networks. When flowing through a karst system, wastewater has the potential to reach the aquifer in a relatively short time. The Western Mountain Aquifer (Yarkon-Taninim) of Israel is one of the country's major water resources. During late winter 2013, maintenance actions were performed on a central sewage pipe that caused raw sewage to leak into the creek located in the study area. The subsequent infiltration of sewage through the thick ( 100 m) fractured/karst unsaturated zone led to a sharp increase in contaminant concentrations in the groundwater, which was monitored in a well located 29 meters from the center of the creek. Carbamazepine (CBZ) was used as an indicator for the presence of untreated raw sewage and its quantification in groundwater. The ultimate research goal was to develop a mathematical model for quantifying flow and contaminant transport processes in the fractured-porous unsaturated zone and karstified groundwater system. A quasi-3D dual permeability numerical model, representing the 'vadose zone - aquifer' system, was developed by a series of 1D equations solved in variably-saturated zone and by 3D-saturated flow and transport equation in groundwater. The 1D and 3D equations were coupled at the moving phreatic surface. The model was calibrated and applied to a simulated water flow scenario and CBZ transport during and after the observed sewage leakage event. The results of simulation showed that after the leakage stopped, significant amounts of CBZ were retained in the porous matrix of the unsaturated zone below the creek. Water redistribution and slow recharge during the dry summer season contributed to elevated CBZ concentrations in the groundwater in the vicinity of the creek and tens of meters downstream. The resumption of autumn rains enhanced flushing of CBZ from the unsaturated zone and led to an increase in

Estimation of deep infiltration in unsaturated limestone environments using cave lidar and drip count data

Science.gov (United States)

Mahmud, K.; Mariethoz, G.; Baker, A.; Treble, P. C.; Markowska, M.; McGuire, E.

2016-01-01

Limestone aeolianites constitute karstic aquifers covering much of the western and southern Australian coastal fringe. They are a key groundwater resource for a range of industries such as winery and tourism, and provide important ecosystem services such as habitat for stygofauna. Moreover, recharge estimation is important for understanding the water cycle, for contaminant transport, for water management, and for stalagmite-based paleoclimate reconstructions. Caves offer a natural inception point to observe both the long-term groundwater recharge and the preferential movement of water through the unsaturated zone of such limestone. With the availability of automated drip rate logging systems and remote sensing techniques, it is now possible to deploy the combination of these methods for larger-scale studies of infiltration processes within a cave. In this study, we utilize a spatial survey of automated cave drip monitoring in two large chambers of Golgotha Cave, south-western Western Australia (SWWA), with the aim of better understanding infiltration water movement and the relationship between infiltration, stalactite morphology, and unsaturated zone recharge. By applying morphological analysis of ceiling features from Terrestrial LiDAR (T-LiDAR) data, coupled with drip time series and climate data from 2012 to 2014, we demonstrate the nature of the relationships between infiltration through fractures in the limestone and unsaturated zone recharge. Similarities between drip rate time series are interpreted in terms of flow patterns, cave chamber morphology, and lithology. Moreover, we develop a new technique to estimate recharge in large-scale caves, engaging flow classification to determine the cave ceiling area covered by each flow category and drip data for the entire observation period, to calculate the total volume of cave discharge. This new technique can be applied to other cave sites to identify highly focussed areas of recharge and can help to better

One-pot preparation of unsaturated polyester nanocomposites containing functionalized graphene sheets via a novel solvent-exchange method

Science.gov (United States)

This paper reports a convenient one-pot method integrating a novel solvent-exchange method into in situ melt polycondensation to fabricate unsaturated polyester nanocomposites containing functionalized graphene sheets (FGS). A novel solvent-exchange method was first developed to prepare graphene oxi...

EU REPRO: The Production of fish feed enriched with poly-unsaturated fatty acid

CSIR Research Space (South Africa)

Erasmus, C

2007-01-01

Full Text Available .2 The Production of Fish Feed enriched with poly-unsaturated fatty acids Corinda Erasmus Annali Jacobs Gerda Lombard Petrus van Zyl Judy Reddy Ntombikayise Nkomo Elizabeth Timme Partner 11 Slide 2 © CSIR 2006 www... www.csir.co.za FLOW DIAGRAM OF THE PRODUCTION OF EPA- ENRICHED FISH FEED BSG (SPENT GRAIN) Eicosapentaenoic Acid (EPA) Protein-rich BSG FISH FEED PELLETS MODIFICATION OF BSG (ENZYME/CHEMICAL/MECHANICAL) FERMENTATION (RECOVERY OF EPA...

Unsaturated Groundwater Flow Beneath Upper Mortandad Canyon, Los Alamos, New Mexico

Energy Technology Data Exchange (ETDEWEB)

Dander, David Carl [Univ. of Arizona, Tucson, AZ (United States)

1998-10-15

Mortandad Canyon is a discharge site for treated industrial effluents containing radionuclides and other chemicals at Los Alamos National Laboratory, New Mexico. This study was conducted to develop an understanding of the unsaturated hydrologic behavior below the canyon floor. The main goal of this study was to evaluate the hypothetical performance of the vadose zone above the water table. Numerical simulations of unsaturated groundwater flow at the site were conducted using the Finite Element Heat and Mass Transfer (FEHM) code. A two-dimensional cross-section along the canyon's axis was used to model flow between an alluvial groundwater system and the regional aquifer approximately 300 m below. Using recharge estimated from a water budget developed in 1967, the simulations showed waters from the perched water table reaching the regional aquifer in 13.8 years, much faster than previously thought. Additionally, simulations indicate that saturation is occurring in the Guaje pumice bed an d that the Tshirege Unit 1B is near saturation. Lithologic boundaries between the eight materials play an important role in flow and solute transport within the system. Horizontal flow is shown to occur in three thin zones above capillary barriers; however, vertical flow dominates the system. Other simulations were conducted to examine the effects of changing system parameters such as varying recharge inputs, varying the distribution of recharge, and bypassing fast-path fractured basalt of uncertain extent and properties. System sensitivity was also explored by changing model parameters with respect to size and types of grids and domains, and the presence of dipping stratigraphy.

Tung oil-based unsaturated co-ester macromonomer for thermosetting polymers: Synergetic synthesis and copolymerization with styrene

Science.gov (United States)

A novel unsaturated co-ester (co-UE) macromonomer containing both maleates and acrylates was synthesized from tung oil (TO) and its chemical structure was characterized by FT-IR, 1H-NMR, 13C-NMR, and gel permeation chromatography (GPC). The monomer was synthesized via a new synergetic modification o...

Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

KAUST Repository

Lamberti, Marina

2012-01-23

The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

Coordinatively unsaturated ruthenium complexes as efficient alkyneazide cycloaddition catalysts

KAUST Repository

Lamberti, Marina; Fortman, George C.; Poater, Albert; Broggi, Julie; Slawin, Alexandra M. Z.; Cavallo, Luigi; Nolan, Steven P.

2012-01-01

The performance of 16-electron ruthenium complexes with the general formula Cp*Ru(L)X (in which L = phosphine or N-heterocyclic carbene ligand; X = Cl or OCH2CF3) was explored in azidealkyne cycloaddition reactions that afford the 1,2,3- triazole products. The scope of the Cp*Ru(PiPr 3)Cl precatalyst was investigated for terminal alkynes leading to new 1,5-disubstituted 1,2,3-triazoles in high yields. Mechanistic studies were conducted and revealed a number of proposed intermediates. Cp*Ru- (PiPr3)(2-HCCPh)Cl was observed and characterized by 1H, 13C, and 31P NMR at temperatures between 273 and 213 K. A rare example of N,N-κ2-phosphazide complex, Cp*Ru(κ2- iPr3PN3Bn)Cl, was fully characterized, and a single-crystal X-ray diffraction structure was obtained. DFT calculations describe a complete map of the catalytic reactivity with phenylacetylene and/or benzylazide. © 2012 American Chemical Society.

Unsaturated zone leaching models for assessing risk to groundwater of contaminated sites

DEFF Research Database (Denmark)

Troldborg, Mads; Binning, Philip John; Nielsen, Signe

2009-01-01

and aqueous phase contaminant transport equation. The equation has the same general form as the standard advection-diffusion equation for which many analytical solutions have been derived. Four new analytical solutions are developed using this approach: a three-dimensional solution accounting for infiltration......, lateral gas diffusion, sorption and degradation; a simple one-dimensional screening model, and two one-dimensional radial gas diffusion models for use in simulating volatile organic contaminant diffusion in unsaturated soils with an impermeable cover. The models show that both degradation and diffusion...

Soil Gas Dynamics and Microbial Activity in the Unsaturated Zone of a Regulated River

Science.gov (United States)

Christensen, H.; Ferencz, S. B.; Cardenas, M. B.; Neilson, B. T.; Bennett, P. C.

2017-12-01

Over 60% of the world's rivers are dammed, and are therefore regulated. In some river systems, river regulation is the dominant factor governing fluid exchange and soil gas dynamics in the hyporheic region and overlying unsaturated zone of the river banks. Where this is the case, it is important to understand the effects that an artificially-induced change in river stage can have on the chemical, plant, and microbial components of the unsaturated zone. Daily releases from an upstream dam cause rapid stage fluctuations in the Lower Colorado River east of Austin, Texas. For this study, we utilized an array of water and gas wells along a transect perpendicular to the river to investigate the biogeochemical process occurring in this mixing zone. The gas wells were installed at several depths up to 1.5 meters, and facilitated the continuous monitoring of soil gases as the pulse percolated through the river bank. Water samples collected from the screened wells penetrated to depths below the water table and were analyzed for nutrients, carbon, and major ions. Additionally, two soil cores were taken at different distances from the river and analyzed for soil moisture and grain size. These cores were also analyzed for microbial activity using the total heterotroph count method and the acetylene inhibition technique, a sensitive method of measuring denitrifying activity. The results provide a detailed picture of soil gas flux and biogeochemical processes in the bank environment in a regulated river. Findings indicate that a river pulse that causes a meter-scale change in river stage causes small, centimeter-scale pulses in the water table. We propose that these conditions create an area of elevated microbial respiration at the base of the unsaturated zone that appears to be decoupled from normal diurnal fluctuations. Along the transect, CO2 concentrations increased with increasing depth down to the water table. CO2 concentrations were highest in the time following a pulse

An improved analysis of gravity drainage experiments for estimating the unsaturated soil hydraulic functions

Science.gov (United States)

Sisson, James B.; van Genuchten, Martinus Th.

1991-04-01

The unsaturated hydraulic properties are important parameters in any quantitative description of water and solute transport in partially saturated soils. Currently, most in situ methods for estimating the unsaturated hydraulic conductivity (K) are based on analyses that require estimates of the soil water flux and the pressure head gradient. These analyses typically involve differencing of field-measured pressure head (h) and volumetric water content (θ) data, a process that can significantly amplify instrumental and measurement errors. More reliable methods result when differencing of field data can be avoided. One such method is based on estimates of the gravity drainage curve K'(θ) = dK/dθ which may be computed from observations of θ and/or h during the drainage phase of infiltration drainage experiments assuming unit gradient hydraulic conditions. The purpose of this study was to compare estimates of the unsaturated soil hydraulic functions on the basis of different combinations of field data θ, h, K, and K'. Five different data sets were used for the analysis: (1) θ-h, (2) K-θ, (3) K'-θ (4) K-θ-h, and (5) K'-θ-h. The analysis was applied to previously published data for the Norfolk, Troup, and Bethany soils. The K-θ-h and K'-θ-h data sets consistently produced nearly identical estimates of the hydraulic functions. The K-θ and K'-θ data also resulted in similar curves, although results in this case were less consistent than those produced by the K-θ-h and K'-θ-h data sets. We conclude from this study that differencing of field data can be avoided and hence that there is no need to calculate soil water fluxes and pressure head gradients from inherently noisy field-measured θ and h data. The gravity drainage analysis also provides results over a much broader range of hydraulic conductivity values than is possible with the more standard instantaneous profile analysis, especially when augmented with independently measured soil water retention data.

User's Guide: Database of literature pertaining to the unsaturated zone and surface water-ground water interactions at the Idaho National Engineering Laboratory

International Nuclear Information System (INIS)

Hall, L.F.

1993-05-01

Since its beginnings in 1949, hydrogeologic investigations at the Idaho National Engineering Laboratory (INEL) have resulted in an extensive collection of technical publications providing information concerning ground water hydraulics and contaminant transport within the unsaturated zone. Funding has been provided by the Department of Energy through the Department of Energy Idaho Field Office in a grant to compile an INEL-wide summary of unsaturated zone studies based on a literature search. University of Idaho researchers are conducting a review of technical documents produced at or pertaining to the INEL, which present or discuss processes in the unsaturated zone and surface water-ground water interactions. Results of this review are being compiled as an electronic database. Fields are available in this database for document title and associated identification number, author, source, abstract, and summary of information (including types of data and parameters). AskSam reg-sign, a text-based database system, was chosen. WordPerfect 5.1 copyright is being used as a text-editor to input data records into askSam

Variationally optimal selection of slow coordinates and reaction coordinates in macromolecular systems

Science.gov (United States)

Noe, Frank

To efficiently simulate and generate understanding from simulations of complex macromolecular systems, the concept of slow collective coordinates or reaction coordinates is of fundamental importance. Here we will introduce variational approaches to approximate the slow coordinates and the reaction coordinates between selected end-states given MD simulations of the macromolecular system and a (possibly large) basis set of candidate coordinates. We will then discuss how to select physically intuitive order paremeters that are good surrogates of this variationally optimal result. These result can be used in order to construct Markov state models or other models of the stationary and kinetics properties, in order to parametrize low-dimensional / coarse-grained model of the dynamics. Deutsche Forschungsgemeinschaft, European Research Council.

Influence of the molecular structure on hydrolysability of unsaturated polyesters

International Nuclear Information System (INIS)

Pays, M.F.; Denis, V.

1993-09-01

EDF has decided to replace conventional materials by glass reinforced plastics for certain PWR water distribution systems (raw water system, essential service water system, firefighting water distribution system, etc...). Since steel corrodes rapidly in these pipings, introducing composite materials will be economically beneficial if the long-term resistance of these materials can be guaranteed. However, due to hydrolysis of the resin or of the fiber-matrix interface, composite materials deteriorations may occur during service life. This paper reports on the hydrolysis resistance of polyester and vinylester resins. - Model monomers were studied to relate the molecular structure to the hydrolysis resistance. Two ester categories were determined, the diacids and the diols. For the diacids, we obtained the following classification in increasing order of resistance: < maleates < ethoxysuccinates < succinates < fumerates < terephtalates < orthophtalates < isophtalates and for the diols: trioxyethylene glycol << butane diol ∼ ethylene glycol < neopentyl glycol < bisphenol A. The positions obtained for neopentyl glycol and isophtalic acid on this scale justify their inclusion in the formulation of hydrolysis-resistant resins. Since aliphatic unsaturated esters are highly sensitive to hydrolysis, the cross linking procedures for these materials, notably the post-cure stages, must be the subject of particular care. - The hydrolytic degradation of cross linked materials was studied. It was shown that hydrolysis could be monitored by a simple gravimetric method. Used in association with accelerated aging tests, it predicts the time lapse to initiation of the phenomenon. The better hydrolysis resistance of vinylester resins as compared with unsaturated polyesters has been demonstrated. However, forecasting over a 30-year life span is difficult to guarantee in that this involves indicating in the resin specifications the in-service stress which it will be required to

Near-Horizon Geodesics for Astrophysical and Idealised Black Holes: Coordinate Velocity and Coordinate Acceleration

Directory of Open Access Journals (Sweden)

Petarpa Boonserm

2018-05-01

Full Text Available Geodesics (by definition have an intrinsic 4-acceleration zero. However, when expressed in terms of coordinates, the coordinate acceleration d 2 x i / d t 2 can very easily be non-zero, and the coordinate velocity d x i / d t can behave unexpectedly. The situation becomes extremely delicate in the near-horizon limit—for both astrophysical and idealised black holes—where an inappropriate choice of coordinates can quite easily lead to significant confusion. We shall carefully explore the relative merits of horizon-penetrating versus horizon-non-penetrating coordinates, arguing that in the near-horizon limit the coordinate acceleration d 2 x i / d t 2 is best interpreted in terms of horizon-penetrating coordinates.

Coupled Hydromechanical and Electromagnetic Responses in Unsaturated Porous Media: Theory, Observation, and Numerical Simulations

Science.gov (United States)

Mahardika, Harry

Hydromechanical energy can be partially converted into electromagnetic energy due to electrokinetic effect, where mechanical energy causes the relative displacement of the charged pore water with respect to the solid skeleton of the porous material and generated electrical current density. An application of this phenomenon is seismoelectric method, a geophysical method in which electromagnetic signals are recorded and associated with the propagation of seismic waves. Due to its coupling nature, seismoelectric method promises advantages in characterizing the subsurface properties and geometry compared to independent employments of seismic or electromagnetic acquisition alone. Since the recorded seismoelectric signal are sensitive to water content changes this method have been applied for groundwater studies to delineates vadoze zone-aquifer boundary since the last twenty years. The problem, however, the existing governing equations of coupled seismic and electromagnetic are not accounted for unsaturated conditions and its petrophysical sensitivity to water content. In this thesis we extend the applications of seismoelectric method for unsaturated porous medium for several geophysical problems. (1) We begin our study with numerical study to localize and characterize a seismic event induced by hydraulic fracturing operation sedimentary rocks. In this problem, we use the fully-saturated case of seismoelectric method and we propose a new joint inversion scheme (seismic and seismoelectric) to determine the position and moment tensor that event. (2) We expand the seismoelectric theory for unsaturated condition and show that the generation of electrical current density are depend on several important petrophysical properties that are sensitive to water content. This new expansion of governing equation provide us theory for developing a new approach for seismoelectric method to image the oil water encroachment front during water flooding of an oil reservoir or an aquifer

Metamodeling and mapping of nitrate flux in the unsaturated zone and groundwater, Wisconsin, USA

Science.gov (United States)

Nolan, Bernard T.; Green, Christopher T.; Juckem, Paul F.; Liao, Lixia; Reddy, James E.

2018-04-01

Nitrate contamination of groundwater in agricultural areas poses a major challenge to the sustainability of water resources. Aquifer vulnerability models are useful tools that can help resource managers identify areas of concern, but quantifying nitrogen (N) inputs in such models is challenging, especially at large spatial scales. We sought to improve regional nitrate (NO3-) input functions by characterizing unsaturated zone NO3- transport to groundwater through use of surrogate, machine-learning metamodels of a process-based N flux model. The metamodels used boosted regression trees (BRTs) to relate mappable landscape variables to parameters and outputs of a previous "vertical flux method" (VFM) applied at sampled wells in the Fox, Wolf, and Peshtigo (FWP) river basins in northeastern Wisconsin. In this context, the metamodels upscaled the VFM results throughout the region, and the VFM parameters and outputs are the metamodel response variables. The study area encompassed the domain of a detailed numerical model that provided additional predictor variables, including groundwater recharge, to the metamodels. We used a statistical learning framework to test a range of model complexities to identify suitable hyperparameters of the six BRT metamodels corresponding to each response variable of interest: NO3- source concentration factor (which determines the local NO3- input concentration); unsaturated zone travel time; NO3- concentration at the water table in 1980, 2000, and 2020 (three separate metamodels); and NO3- "extinction depth", the eventual steady state depth of the NO3- front. The final metamodels were trained to 129 wells within the active numerical flow model area, and considered 58 mappable predictor variables compiled in a geographic information system (GIS). These metamodels had training and cross-validation testing R2 values of 0.52 - 0.86 and 0.22 - 0.38, respectively, and predictions were compiled as maps of the above response variables. Testing

An Approach Using Gas Monitoring to Find the Residual TCE Location in the Unsaturated Zone of Woosan Industrial Complex (WIC), Korea

Science.gov (United States)

Koh, Y.; Lee, S.; Yang, J.; Lee, K.

2012-12-01

An area accommodating various industrial facilities has fairly high probability of groundwater contamination with multiple chlorinated solvents such as trichloroethene (TCE), carbon tetrachloride (CT), and chloroform (CF). Source tracing of chlorinated solvents in the unsaturated zone is an essential procedure for the management and remediation of contaminated area. From the previous study on seasonal variations in hydrological stresses and spatial variations in geologic conditions on a TCE plume, the existence of residual DNAPLs at or above the water table has proved. Since TCE is one of the frequently detected VOCs (Volatile Organic Compounds) in groundwater, residual TCE can be detected by gas monitoring. Therefore, monitoring of temporal and spatial variations in the gas phase TCE contaminant at an industrial complex in Wonju, Korea, were used to find the residual TCE locations. As pilot tests, TCE gas samples collected in the unsaturated zone at 4 different wells were analyzed using SPME (Solid Phase MicroExtraction) fiber and Gas Chromatography (GC). The results indicated that detecting TCE in gas phase was successful from these wells and TCE analysis on gas samples, collected from the unsaturated zone, will be useful for source area characterization. However, some values were too high to doubt the accuracy of the current method, which needs a preliminary lab test with known concentrations. The modified experiment setups using packer at different depths are in process to find residual TCE locations in the unsaturated zone. Meanwhile, several PVD (polyethylene-membrane Passive Vapor Diffusion) samplers were placed under water table to detect VOCs by equilibrium between air in the vial and VOCs in pore water.

Busted Butte Unsaturated Zone Transport Test: Fiscal Year 1998 Status Report Yucca Mountain Site Characterization Program Deliverable SPU85M4

International Nuclear Information System (INIS)

Bussod, G.Y.; Turin, H.J.; Lowry, W.E.

1999-01-01

This report describes the status of the Busted Butte Unsaturated Zone Transport Test (UZTT) and documents the progress of construction activities and site and laboratory characterization activities undertaken in fiscal year 1998. Also presented are predictive flow-and-transport simulations for Test Phases 1 and 2 of testing and the preliminary results and status of these test phases. Future anticipated results obtained from unsaturated-zone (UZ) transport testing in the Calico Hills Formation at Busted Butte are also discussed in view of their importance to performance assessment (PA) needs to build confidence in and reduce the uncertainty of site-scale flow-and-transport models and their abstractions for performance for license application. The principal objectives of the test are to address uncertainties associated with flow and transport in the UZ site-process models for Yucca Mountain, as identified by the PA working group in February 1997. These include but are not restricted to: (1) The effect of heterogeneities on flow and transport in unsaturated and partially saturated conditions in the Calico Hills Formation. In particular, the test aims to address issues relevant to fracture-matrix interactions and permeability contrast boundaries; (2) The migration behavior of colloids in fractured and unfractured Calico Hills rocks; (3) The validation through field testing of laboratory sorption experiments in unsaturated Calico Hills rocks; (4) The evaluation of the 3-D site-scale flow-and-transport process model (i.e., equivalent-continuum/dual-permeability/discrete-fracture-fault representations of flow and transport) used in the PA abstractions for license application; and (5) The effect of scaling from lab scale to field scale and site scale

Optimal Choice of Soil Hydraulic Parameters for Simulating the Unsaturated Flow: A Case Study on the Island of Miyakojima, Japan

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Ken Okamoto

2015-10-01

Full Text Available We examined the influence of input soil hydraulic parameters on HYDRUS-1D simulations of evapotranspiration and volumetric water contents (VWCs in the unsaturated zone of a sugarcane field on the island of Miyakojima, Japan. We first optimized the parameters for root water uptake and examined the influence of soil hydraulic parameters (water retention curve and hydraulic conductivity on simulations of evapotranspiration. We then compared VWCs simulated using measured soil hydraulic parameters with those using pedotransfer estimates obtained with the ROSETTA software package. Our results confirm that it is important to always use soil hydraulic parameters based on measured data, if available, when simulating evapotranspiration and unsaturated water flow processes, rather than pedotransfer functions.

Ethylenediaminetetraacetates of neodymium and alkaline earth metals

International Nuclear Information System (INIS)

Barinov, A.V.; Pechurova, L.I.; Martynenko, K.I.; Popov, K.I.; Spitsyn, V.I.

1977-01-01

The possibilities have been studied of the formation of polynuclear complexonates of alkaline-earth metals (Ca, Sr, and Ba) based on neodymium derivatives EDTA of the composition NdA - . By pH-metry, electron spectroscopy, and derivatography it has been shown that the structure of complexes M 2 (NdA) 2 (where M- Ca, Sr, or Ba; A- EDTA) in the solution is not polynuclear. Hydroxopolynuclear complexes do not form under conditions studied. The data obtained agree with an assumption about polynuclear structure of the solid complex Ca(NdA) 2 x17 H 2 O and gradual weakening of the polynuclear nature upon substitution of Ca 2+ with Sr 2+ and Ba 2+

Field research program for unsaturated flow and transport experimentation

International Nuclear Information System (INIS)

Tidwell, V.C.; Rautman, C.A.; Glass, R.J.

1992-01-01

As part of the Yucca Mountain Site Characterization Project, a field research program has been developed to refine and validate models for flow and transport through unsaturated fractured rock. Validation of these models within the range of their application for performance assessment requires a more sophisticated understanding of the processes that govern flow and transport within fractured porous media than currently exists. In particular, our research is prioritized according to understanding and modeling processes that, if not accurately incorporated into performance assessment models, would adversely impact the project's ability to evaluate repository performance. For this reason, we have oriented our field program toward enhancing our understanding of scaling processes as they relate to effective media property modeling, as well as to the conceptual modeling of complex flow and transport phenomena

Distribution of gases in the unsaturated zone at a low-level radioactive-waste disposal site near Sheffield, Illinois

Science.gov (United States)

Striegl, Robert G.

1988-01-01

The unsaturated zone is a medium that provides pneumatic communication for the movement of gases from wastes buried in landfills to the atmosphere, biota, and groundwater. Gases in unsaturated glacial and eolian deposits near a waste-disposal trench at the low-level radioactive-waste disposal site near Sheffield, Bureau County, Illinois, were identified, and the spatial and temporal distributions of the partial pressures of those gases were determined for the period January 1984 through January 1986. Methods for the collection and analyses of the gases are described, as are geologic and hydrologic characteristics of the unsaturated zone that affect gas transport. The identified gases, which are of natural and of waste origin, include nitrogen, oxygen, and argon, carbon dioxide, methane, propane, butane, tritiated water vapor, 14carbon dioxide, and 222 radon. Concentrations of methane and 14carbon dioxide originated at the waste, as shown by partial-pressure gradients of the gases; 14carbon dioxide partial pressures exceeded natural background partial pressures by factors greater than 1 million at some locations. Variations in partial pressures of oxygen and carbon dioxide were seasonal among piezometers because of increased root and soil-microbe respiration during summer. Variations in methane and 14carbon dioxide partial pressures were apparently related to discrete releases from waste sources at unpredictable intervals of time. No greater than background partial pressures for tritiated water vapor or 222 radon were measured. (USGS)

Coordination, non-coordination and semi-coordination of perchlorates in the lanthanide adducts Ln (CLO4)3. 6dmba

International Nuclear Information System (INIS)

Tfouni, E.; Giesbrecht, E.

1983-01-01

The coordination or not of the perchlorate anions in the previously reported Ln(CLO 4 ) 3 .6 dmba is discussed. The analysis of the infrared spectral data and molar conductance data indicate that they may be formulated as [Ln(dmba) 6 (CLO 4 )n] (CLO 4 ) sub(3-n), n=0,1,2. The individual compounds may be a mixture of species with different n values and/or pure compounds with semi-coordinated and non-coordinated perchlorates. (Author) [pt

Unsaturated Lipids Change in Olive Tree Drupe and Seed during Fruit Development and in Response to Cold-Stress and Acclimation

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Simone D’Angeli

2016-11-01

Full Text Available The olive tree is a plant of economic value for the oil of its drupe. It is a cultigen complex composed of genotypes with differences in cold-hardiness. About 90% of the oil is stored in oil bodies (OBs in the drupe during the oleogenic phase. Phenols and lipids contribute to oil quality, but the unsaturated fatty acid (FA fraction is emerging as the most important for quality, because of the very high content in oleic acid, the presence of ω6-linoleic acid and ω3-linolenic acid, and the very low saturated FA content. Another 10% of oil is produced by the seed. Differences in unsaturated FA-enriched lipids exist among seed coat, endosperm, and embryo. Olive oil quality is also affected by the environmental conditions during fruit growth and genotype peculiarities. Production of linoleic and α-linolenic acids, fruit growth, fruit and leaf responses to low temperatures, including cuticle formation, and cold-acclimation are related processes. The levels of unsaturated FAs are changed by FA-desaturase (FAD activities, involving the functioning of chloroplasts and endoplasmic reticulum. Cold induces lipid changes during drupe and seed development, affecting FADs, but its effect is related to the genotype capability to acclimate to the cold.

Magnetic Coordinate Systems

Science.gov (United States)

Laundal, K. M.; Richmond, A. D.

2017-03-01

Geospace phenomena such as the aurora, plasma motion, ionospheric currents and associated magnetic field disturbances are highly organized by Earth's main magnetic field. This is due to the fact that the charged particles that comprise space plasma can move almost freely along magnetic field lines, but not across them. For this reason it is sensible to present such phenomena relative to Earth's magnetic field. A large variety of magnetic coordinate systems exist, designed for different purposes and regions, ranging from the magnetopause to the ionosphere. In this paper we review the most common magnetic coordinate systems and describe how they are defined, where they are used, and how to convert between them. The definitions are presented based on the spherical harmonic expansion coefficients of the International Geomagnetic Reference Field (IGRF) and, in some of the coordinate systems, the position of the Sun which we show how to calculate from the time and date. The most detailed coordinate systems take the full IGRF into account and define magnetic latitude and longitude such that they are constant along field lines. These coordinate systems, which are useful at ionospheric altitudes, are non-orthogonal. We show how to handle vectors and vector calculus in such coordinates, and discuss how systematic errors may appear if this is not done correctly.

Unsaturated zone waters from the Nopal I natural analog, Chihuahua, Mexico -- Implications for radionuclide mobility at Yucca Mountain

Energy Technology Data Exchange (ETDEWEB)

Pickett, D.A.; Murphy, W.M.

1999-07-01

Chemical and U-Th isotopic data on unsaturated zone waters from the Nopal I natural analog reveal effects of water-rock interaction and help constrain models of radionuclide release and transport at the site and, by analogy, at the proposed nuclear waste repository at Yucca Mountain. Geochemical reaction-path modeling indicates that, under oxidizing conditions, dissolution of uraninite (spent fuel analog) by these waters will lead to eventual schoepite precipitation regardless of initial silica concentration provided that groundwater is not continuously replenished. Thus, less soluble uranyl silicates may not dominate the initial alteration assemblage and keep dissolved U concentrations low. Uranium-series activity ratios are consistent with models of U transport at the site and display varying degrees of leaching versus recoil mobilization. Thorium concentrations may reflect the importance of colloidal transport of low-solubility radionuclides in the unsaturated zone.

Unsaturated zone waters from the Nopal I natural analog, Chihuahua, Mexico -- Implications for radionuclide mobility at Yucca Mountain

International Nuclear Information System (INIS)

Pickett, D.A.; Murphy, W.M.

1999-01-01

Chemical and U-Th isotopic data on unsaturated zone waters from the Nopal I natural analog reveal effects of water-rock interaction and help constrain models of radionuclide release and transport at the site and, by analogy, at the proposed nuclear waste repository at Yucca Mountain. Geochemical reaction-path modeling indicates that, under oxidizing conditions, dissolution of uraninite (spent fuel analog) by these waters will lead to eventual schoepite precipitation regardless of initial silica concentration provided that groundwater is not continuously replenished. Thus, less soluble uranyl silicates may not dominate the initial alteration assemblage and keep dissolved U concentrations low. Uranium-series activity ratios are consistent with models of U transport at the site and display varying degrees of leaching versus recoil mobilization. Thorium concentrations may reflect the importance of colloidal transport of low-solubility radionuclides in the unsaturated zone

An Equal-Strain Analytical Solution for the Radial Consolidation of Unsaturated Soils by Vertical Drains considering Drain Resistance

Directory of Open Access Journals (Sweden)

Feng Zhou

2018-01-01

Full Text Available Developing an analytical solution for the consolidation of unsaturated soils remains a challenging task due to the complexity of coupled governing equations for air and water phases. This paper presents an equal-strain model for the radial consolidation of unsaturated soils by vertical drains, and the effect of drain resistance is also considered. Simplified governing equations are established, and an analytical solution to calculate the excess pore-air and pore-water pressures is derived by using the methods of matrix analysis and eigenfunction expansion. The average degrees of consolidation for air and water phases and the ground surface settlement are also given. The solutions of the equal-strain model are verified by comparing the proposed free-strain model with the equal-strain model, and reasonably good agreement is obtained. Moreover, parametric studies regarding the drain resistance effect are graphically presented.

Motor coordination uses external spatial coordinates independent of developmental vision.

Science.gov (United States)

Heed, Tobias; Röder, Brigitte

2014-07-01

The constraints that guide bimanual movement coordination are informative about the processing principles underlying movement planning in humans. For example, symmetry relative to the body midline benefits finger and hand movements independent of hand posture. This symmetry constraint has been interpreted to indicate that movement coordination is guided by a perceptual code. Although it has been assumed implicitly that the perceptual system at the heart of this constraint is vision, this relationship has not been tested. Here, congenitally blind and sighted participants made symmetrical and non-symmetrical (that is, parallel) bimanual tapping and finger oscillation movements. For both groups, symmetrical movements were executed more correctly than parallel movements, independent of anatomical constraints like finger homology and hand posture. For the blind, the reliance on external spatial factors in movement coordination stands in stark contrast to their use of an anatomical reference frame in perceptual processing. Thus, the externally coded symmetry constraint evident in bimanual coordination can develop in the absence of the visual system, suggesting that the visual system is not critical for the establishment of an external-spatial reference frame in movement coordination. Copyright © 2014 Elsevier B.V. All rights reserved.

Actinic radiation-curable formulations from the reaction product of organic isocyanate, poly(alkylene oxide) polyol and an unsaturated addition-polymerizable monomeric compound having a single isocyanate-reactive hydrogen group

International Nuclear Information System (INIS)

Howard, D.D.

1979-01-01

Energy-curable compositions which can be cured in the presence of air by exposure to actinic radiation contain at least one unsaturated urethane oligomer. The oligomer comprises the reaction product of at least one poly(alkylene oxide) polyol, at least one polyisocyanate, and at least one unsaturated active hydrogen-containing compound

General hydroisotopic study of direct infiltration and evaporation process through the unsaturated zone in Damascus oasis, Syrian Arab Republic

International Nuclear Information System (INIS)

Abou Zakhem, B.; Hafez, R.

2001-01-01

Damascus oasis plays an important economical and environmental role in the city life because it presents the surrounding green places and the groundwater is the main sources for irrigation. In this study we will focus on the unsaturated zone in Damascus oasis. Environmental isotopes as 18 O, 2 H and 3 H are considered one of the most important techniques that are used in unsaturated zone study in order to study the water movement mechanism, estimate the effective velocity, the rate and spatial variations of the direct infiltration through this zone.The Deuterium profile allow to estimate the direct evaporation rate, and it is observed that the evaporation in the eastern part of the studied area is 5-6.5 mm/y. The Tritium peak of profile that is belonging to the atmospheric nuclear tests at the beginning of the sixties indicates the effective infiltration velocity of 27.8 mm/y. The effective porosity was estimated about 6.5% and the permeability parameter is 0.6*10 -10 m/s. The direct infiltration rate was estimated by the chemical Chloride balance in the studied profiles in addition to their spatial distribution where it was distinguished between the eastern area where the direct infiltration is less than 2 mm/y characterized by very fine clay soils and western area where the direct infiltration rate is more than 2 mm/y with sandy soils. It is thought that the lower part of the unsaturated zone indicated the direct infiltration rate about 3.5 mm/y, under more wet climatic conditions where the rainfall was about 423 mm/y, this wet period was extended from about 432 y to more than 760y ago.The Nitrate concentration variation with depth indicated that unsaturated zone play important role as purification zone, and the groundwater which has more than 5 m depth is prevented from pollution, whereas the groundwater that has less than 5 m depth is more prone to pollution by high concentration of Nitrates. (author)

Investigating the Constrained Action Hypothesis: A Movement Coordination and Coordination Variability Approach.

Science.gov (United States)

Vidal, Anthony; Wu, Will; Nakajima, Mimi; Becker, James

2017-09-19

The purpose of this study was to examine the effects of focus of attention cues on movement coordination and coordination variability in the lower extremity. Twenty participants performed the standing long jump under both internal and external focus of attention conditions. A modified vector coding technique was used to evaluate the influence of attentional focus cues on lower extremity coordination patterns and coordination variability during the jumps. Participants jumped significantly further under an external focus of attention condition compared with an internal focus of attention condition (p = .035, effect size = .29). Focus of attention also influenced coordination between the ankle and knee, F(6, 19) = 2.87, p = .012, effect size = .388, with participants primarily using their knees under the internal focus of attention, and using both their ankles and knees under the external focus of attention. Attentional focus cues did not influence ankle-knee, F(1, 19) = 0.02, p = .98, effect size = .02, or hip-knee, F(1, 19) = 5.00, p = .49, effect size = .16, coordination variability. Results suggest that while attentional focus may not directly influence movement coordination condition, there is still a change in movement strategy resulting in greater jump distances following an external focus of attention.