Review of progress in understanding the fluid geochemistry of the Cerro Prieto Geothermal System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Truesdell, A.H.; Nehring, N.L.; Thompson, J.M.

1982-08-10

Fluid geochemistry has played a major role in the authors present understanding of the Cerro Prieto geothermal system. Fluid chemical and isotopic compositions have been used to indicate the origin of water, salts, and gases, original subsurface temperature and fluid flow, fluid-production mechanims, and production-induced aquifer boiling and cold-water entry. The extensive geochemical data and interpretation for Cerro Prieto published from 1964 to 1981 are reviewed and discussed. Fluid geochemistry must continue to play an important role in the further development of the Cerro Prieto field.

Sedimentary and pore water geochemistry linked to deglaciation and postglacial development of Lake Vättern, Sweden

NASA Astrophysics Data System (ADS)

Swärd, Henrik; O´Regan, Matt; Kylander, Malin; Greenwood, Sarah; Mörth, Magnus; Jakobsson, Martin

2017-04-01

Lake Vättern, in south central Sweden, underwent profound environmental changes during the Late Weichselian deglaciation of Fennoscandia. It evolved from (i) a sub/proglacial lake situated at the westernmost rim of the Baltic Ice Lake (BIL) into (ii) a brackish to marine phase where the Vättern basin was a part of the Yoldia Sea connecting the North and Baltic Seas, and finally to (iii) a freshwater basin as isostatic rebound following deglaciation led to its isolation. The sedimentary and pore water geochemical signatures associated with these dramatic environmental changes were investigated in a 74 m composite sediment core from southern Lake Vättern. This was accomplished using high-resolution X-ray fluorescence measurements of elemental data along with discrete measurements of total organic carbon (TOC), δ13C, mineralogical composition (XRD) and pore water chemistry. Proglacial sediments in Lake Vättern are devoid of organic matter, and show cyclic trends in elemental data, grain size and mineralogy. These are interpreted as varved sediments whose thickness decreases upcore from decimeters to millimeters. The coarse grained varves are enriched in Ca, Si, Zr and Sr and contain calcite while the fine grained varves are enriched in K, Rb, Ti and Fe and lack calcite. Overall, the presence of calcite is limited to the proglacial sediments and reflected in the elemental data by an abrupt decrease of Ca at the (i)/(ii) transition. This suggests a glacial/glaciofluvial origin for the calcite, likely eroded from local limestones that borders the lake basin in the northeast. The saline incursion at the beginning of phase (ii) is evident in pore water chemistry by a significant increase of the major sea water species (Cl, Na, Mg, K and Ca) but is not clearly seen in the sedimentary geochemistry. Increased biological production in and around the lake during stage (iii) is strongly reflected in sedimentary geochemistry showing decreasing detrital inputs, increasing TOC

Scale-dependent temporal variations in stream water geochemistry

USGS Publications Warehouse

Nagorski, S.A.; Moore, J.N.; McKinnon, Temple E.; Smith, D.B.

2003-01-01

A year-long study of four western Montana streams (two impacted by mining and two "pristine") evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentrations were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal-nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Scale-dependent temporal variations in stream water geochemistry.

PubMed

Nagorski, Sonia A; Moore, Iohnnie N; McKinnon, Temple E; Smith, David B

2003-03-01

A year-long study of four western Montana streams (two impacted by mining and two "pristine") evaluated surface water geochemical dynamics on various time scales (monthly, daily, and bi-hourly). Monthly changes were dominated by snowmelt and precipitation dynamics. On the daily scale, post-rain surges in some solute and particulate concentrations were similar to those of early spring runoff flushing characteristics on the monthly scale. On the bi-hourly scale, we observed diel (diurnal-nocturnal) cycling for pH, dissolved oxygen, water temperature, dissolved inorganic carbon, total suspended sediment, and some total recoverable metals at some or all sites. A comparison of the cumulative geochemical variability within each of the temporal groups reveals that for many water quality parameters there were large overlaps of concentration ranges among groups. We found that short-term (daily and bi-hourly) variations of some geochemical parameters covered large proportions of the variations found on a much longer term (monthly) time scale. These results show the importance of nesting short-term studies within long-term geochemical study designs to separate signals of environmental change from natural variability.

Applied Geochemistry Special Issue on Environmental geochemistry of modern mining

USGS Publications Warehouse

Seal, Robert R.; Nordstrom, D. Kirk

2015-01-01

Environmental geochemistry is an integral part of the mine-life cycle, particularly for modern mining. The critical importance of environmental geochemistry begins with pre-mining baseline characterization and the assessment of environmental risks related to mining, continues through active mining especially in water and waste management practices, and culminates in mine closure. The enhanced significance of environmental geochemistry to modern mining has arisen from an increased knowledge of the impacts that historical and active mining can have on the environment, and from new regulations meant to guard against these impacts. New regulations are commonly motivated by advances in the scientific understanding of the environmental impacts of past mining. The impacts can be physical, chemical, and biological in nature. The physical challenges typically fall within the purview of engineers, whereas the chemical and biological challenges typically require a multidisciplinary array of expertise including geologists, geochemists, hydrologists, microbiologists, and biologists. The modern mine-permitting process throughout most of the world now requires that potential risks be assessed prior to the start of mining. The strategies for this risk assessment include a thorough characterization of pre-mining baseline conditions and the identification of risks specifically related to the manner in which the ore will be mined and processed, how water and waste products will be managed, and what the final configuration of the post-mining landscape will be.In the Fall 2010, the Society of Economic Geologists held a short course in conjunction with the annual meeting of the Geological Society of America in Denver, Colorado (USA) to examine the environmental geochemistry of modern mining. The intent was to focus on issues that are pertinent to current and future mines, as opposed to abandoned mines, which have been the focus of numerous previous short courses. The geochemical

Merging metagenomics and geochemistry reveals environmental controls on biological diversity and evolution.

PubMed

Alsop, Eric B; Boyd, Eric S; Raymond, Jason

2014-05-28

The metabolic strategies employed by microbes inhabiting natural systems are, in large part, dictated by the physical and geochemical properties of the environment. This study sheds light onto the complex relationship between biology and environmental geochemistry using forty-three metagenomes collected from geochemically diverse and globally distributed natural systems. It is widely hypothesized that many uncommonly measured geochemical parameters affect community dynamics and this study leverages the development and application of multidimensional biogeochemical metrics to study correlations between geochemistry and microbial ecology. Analysis techniques such as a Markov cluster-based measure of the evolutionary distance between whole communities and a principal component analysis (PCA) of the geochemical gradients between environments allows for the determination of correlations between microbial community dynamics and environmental geochemistry and provides insight into which geochemical parameters most strongly influence microbial biodiversity. By progressively building from samples taken along well defined geochemical gradients to samples widely dispersed in geochemical space this study reveals strong links between the extent of taxonomic and functional diversification of resident communities and environmental geochemistry and reveals temperature and pH as the primary factors that have shaped the evolution of these communities. Moreover, the inclusion of extensive geochemical data into analyses reveals new links between geochemical parameters (e.g. oxygen and trace element availability) and the distribution and taxonomic diversification of communities at the functional level. Further, an overall geochemical gradient (from multivariate analyses) between natural systems provides one of the most complete predictions of microbial taxonomic and functional composition. Clustering based on the frequency in which orthologous proteins occur among metagenomes

History of the recognition of organic geochemistry in geoscience

USGS Publications Warehouse

Kvenvolden, K.A.

2002-01-01

The discipline of organic geochemistry is an outgrowth of the application of the principles and methods of organic chemistry to sedimentary geology. Its origin goes back to the last part of the nineteenth century and the first part of the twentieth century concurrent with the evolution of the applied discipline of petroleum geochemistry. In fact, organic geochemistry was strongly influenced by developments in petroleum geochemistry. Now, however, organic geochemistry is considered an umbrella geoscience discipline of which petroleum geochemistry is an important component.

Impact of Phosphogypsum waste on the Geochemistry of the coastal water of Ghannouche -Gabes (SE of Tunisia).

NASA Astrophysics Data System (ADS)

Ben Amor, R.; Fathallah, S.; Gueddari, M.

2009-04-01

Impact of Phosphogypsum waste on the Geochemistry of the coastal water of Ghannouche -Gabes (SE of Tunisia). R. Ben Amor, S. Fathallah, M. Gueddari (R.U. of Geochemistry and of Environmental Geology, Faculty of Sciences of Tunis, Department of Geology, 2092 Manar I) Corresponding author: R. Ben Amor; E-mail:magba_rim@yahoo.fr The littoral Ghannouche - Gabes (SE of Tunisia), has been known since the 1970's, an important industrialization especially after the installation of the chemical complex for the treatment of phosphates. These industries are at the origin of various waste materials, the most significant one is phosphogypsum (PG) which is released into the sea. The aim of this paper is to identify and to analyze the different entropic and natural factors, which govern the chemical composition in major elements, dissolved oxygen, pH and temperature of Ghannouche -Gabes coastal water, while studying, in particular, the impact of PG waste on the spatial distribution of these parameters. The result of the chemical analyses of the samples taken in June 2003, show that Na, K and Cl are conserved in solution and they evolve with constant Na/Cl and K/Cl ratio. The values of these ratios are similar to sea water average. The concentration of the other elements are controlled, first, by processes of precipitation or dissolution of the carbonated (Ca, Mg and HCO3) or sulphated (Ca and SO4) minerals, and second, by dilution or evaporation phenomena and by the phosphogypsum waste. The spatial distribution of these elements, of the pH, the dissolved oxygen and the temperature and the result of the saturation index with respect to calcite, gypsum and fluorite, by using of the PhreeqC program, show that the zone, located at north of the study area, between the commercial and the fishing port, is highly influenced by the PG waste. In this area, where the PG is released and which is relatively sheltered by the dams of the commercial and fishing port, waters are characterised by

Groundwater geochemistry in shallow aquifers above longwall mines in Illinois, USA

NASA Astrophysics Data System (ADS)

Booth, C. J.; Bertsch, L. P.

1999-12-01

Aquifers above high-extraction underground coal mines are not affected by mine drainage, but they may still exhibit changes in groundwater chemistry due to alterations in groundwater flow induced by mine subsidence. At two active longwall mine sites in Illinois, USA, glacial-drift aquifers were largely unaffected by mining, but the geochemistry of the bedrock aquifers changed during the post-mining water-level recovery. At the Jefferson site, brackish, high-sulfate water present in the upper bedrock shale briefly had lower values of total dissolved solids (TDS) after mining due to increased recharge from the overlying drift, whereas TDS and sulfate increased in the sodium-bicarbonate water present in the underlying sandstone due to downward leakage from the shale and lateral inflow of water through the sandstone. At the Saline site, sandstones contained water ranging from brackish sodium-chloride to fresh sodium-bicarbonate type. Post-mining recovery of the potentiometric levels was minimal, and the water had minor quality changes. Longwall mining affects geochemistry due to subsidence-related fracturing, which increases downward leakage from overlying units, and due to the temporary potentiometric depression and subsequent recovery, whereby water from surrounding areas of the aquifer recharges the affected zone above and adjacent to the mine.

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake, Bermuda

USGS Publications Warehouse

Hatcher, P.G.; Simoneit, B.R.T.; MacKenzie, F.T.; Neumann, A.C.; Thorstenson, D.C.; Gerchakov, S.M.

1982-01-01

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 104 yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n-C22 with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n-C31 with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry. ?? 1982.

Organic geochemistry - A retrospective of its first 70 years

USGS Publications Warehouse

Kvenvolden, K.A.

2006-01-01

Organic geochemistry had its origin in the early part of the 20th century when organic chemists and geologists realized that detailed information on the organic materials in sediments and rocks was scientifically interesting and of practical importance. The generally acknowledged "father" of organic geochemistry is Alfred E. Treibs (1899-1983), who discovered and described, in 1936, porphyrin pigments in shale, coal, and crude oil, and traced the source of these molecules to their biological precursors. Thus, the year 1936 marks the beginning of organic geochemistry. However, formal organization of organic geochemistry dates from 1959 when the Organic Geochemistry Division (OGD) of The Geochemical Society was founded in the United States, followed 22 years later (1981) by the establishment of the European Association of Organic Geochemists (EAOG). Organic geochemistry (1) has its own journal, Organic Geochemistry (beginning in 1979) which, since 1988, is the official journal of the EAOG, (2) convenes two major conferences [International Meeting on Organic Geochemistry (IMOG), since 1962, and Gordon Research Conferences on Organic Geochemistry (GRC), since 1968] in alternate years, and (3) is the subject matter of several textbooks. Organic geochemistry is now a widely recognized geoscience in which organic chemistry has contributed significantly not only to geology (i.e., petroleum geochemistry, molecular stratigraphy) and biology (i.e., biogeochemistry), but also to other disciplines, such as chemical oceanography, environmental science, hydrology, biochemical ecology, archaeology, and cosmochemistry.

Maps showing water geochemistry of the Buffalo Peaks Wilderness Study Area, Lake, Park, and Chaffee Counties, Colorado

USGS Publications Warehouse

Nowlan, G.A.; Ficklin, Walter H.; Dover, Robert A.

1985-01-01

This report presents results of geochemical studies carried out in June and July of 1982 in the Buffalo Peaks Wilderness Study Area, Colo. (see index map). Samples of water were collected from 84 streams and 18 springs draining the study area. Tabulations of the analyses and a sample locality map are in Ficklin and others (1984). The geochemistry of stream sediments and panned concentrates of the study area is in Nowlan and Gerstel (1985). The geology of the study area and vicinity is in Hedlund (1985). The mineral resource potential of the study area is described in Hedlund and others (1983). This report (1) assists in the assessment of the mineral resource potential of the Buffalo Peaks Wilderness Study Area; and (2) compares analyses of water samples with analyses of stream-sediment and panned-concentrate samples (Nowlan and Gerstel, 1985).

Temporal Geochemistry Data from Five Springs in the Cement Creek Watershed, San Juan County, Colorado

USGS Publications Warehouse

Johnson, Raymond H.; Wirt, Laurie; Leib, Kenneth J.

2008-01-01

Temporal data from five springs in the Cement Creek watershed, San Juan County, Colorado provide seasonal geochemical data for further research in the formation of ferricretes. In addition, these data can be used to help understand the ground-water flow system. The resulting data demonstrate the difficulty in gathering reliable seasonal data from springs, show the unique geochemistry of each spring due to local geology, and provide seasonal trends in geochemistry for Tiger Iron Spring.

Teaching Environmental Geochemistry as a Service-Learning Course (Invited)

NASA Astrophysics Data System (ADS)

Ku, T. C.

2010-12-01

Service-learning courses seek to broaden students’ understanding of class content through activities, which are, at the same time, of service to the community. At Wesleyan University, I have taught an Environmental Geochemistry and Laboratory course three times as a service-learning course. The course meets for two 80-minute lecture periods and one 3-hour lab period each week and class sizes have been 19-27 students. The lectures cover traditional geochemistry topics such as equilibrium thermodynamics, acid-base equilibria, oxidation-reduction reactions, and isotope geochemistry, while the lab periods focus on a semester-long environmental project in collaboration with a community organization. Problem sets and class exercises are chosen to demonstrate how theoretical concepts are applied to topics relevant to the service-learning project. The three service-learning projects and associated community partners were entitled 1) “An Initial Assessment of the North End Middletown Landfill as a Renewable Energy Sources” in collaboration with The Johan Center for Earth and Art, 2) “The Water and Sediment Geochemistry of Beseck Lake, CT: Implications for Cultural Eutrophication” in collaboration with the Beseck Lake Association, and 3) “Geochemistry and Hydrology of Jobs Pond, CT” with the Jobs Pond Water Quality Commission. Initial contact with the community partner was made through Wesleyan’s Center for Community Partnerships or through the Connecticut Department of Environmental Protection. At the start of each semester, the lead member(s) of the community organization present their environmental problem to the class. This initial meeting allows the students to hear about the problem from the community’s perspective. The faculty member collaborates with the community organization to design 5-8 mini-projects and the students are assigned group projects (2-5 students) through a ranking system. Throughout the semester each group works on their project

Dynamical Geochemistry

NASA Astrophysics Data System (ADS)

Davies, G. F.

2009-12-01

Dynamical and chemical interpretations of the mantle have hitherto remained incompatible, despite substantial progress over recent years. It is argued that both the refractory incompatible elements and the noble gases can be reconciled with the dynamical mantle when mantle heterogeneity is more fully accounted for. It is argued that the incompatible-element content of the MORB source is about double recent estimates (U~10 ng/g) because enriched components have been systematically overlooked, for three main reasons. (1) in a heterogeneous MORB source, melts from enriched pods are not expected to equilibrate fully with the peridotite matrix, but recent estimates of MORB-source composition have been tied to residual (relatively infertile) peridotite composition. (2) about 25% of the MORB source comes from plumes, but plume-like components have tended to be excluded. (3) a focus on the most common “normal” MORBs, allegedly representing a “depleted” MORB source, has overlooked the less-common but significant enriched components of MORBs, of various possible origins. Geophysical constraints (seismological and topographic) exclude mantle layering except for the thin D” layer and the “superpiles” under Africa and the Pacific. Numerical models then indicate the MORB source comprises the rest of the mantle. Refractory-element mass balances can then be accommodated by a MORB source depleted by only a factor of 2 from chondritic abundances, rather than a factor of 4-7. A source for the hitherto-enigmatic unradiogenic helium in OIBs also emerges from this picture. Melt from subducted oceanic crust melting under MORs will react with surrounding peridotite to form intemediate compositions here termed hybrid pyroxenite. Only about half of the hybrid pyroxenite will be remelted, extracted and degassed at MORs, and the rest will recirculate within the mantle. Over successive generations starting early in Earth history, volatiles will come to reside mainly in the hybrid

Stable isotope geochemistry of pore waters from the New Jersey shelf - No evidence for Pleistocene melt water

NASA Astrophysics Data System (ADS)

van Geldern, Robert; Hayashi, Takeshi; Böttcher, Michael E.; Mottl, Michael J.; Barth, Johannes A. C.; Stadler, Susanne

2013-04-01

Ocean Drilling Program, Volume 313, Tokyo, available at: http://publications.iodp.org/proceedings/313/313toc.htm. van Geldern, R., Hayashi, T., Böttcher, M. E., Mottl, M. J., Barth, J. A. C., and Stadler, S., 2013, Stable isotope geochemistry of pore waters and marine sediments from the New Jersey shelf: Methane formation and fluid origin: Geosphere, v. 9, no. 1, p. in press.

Principles and Applications of Geochemistry, 2nd Edition

NASA Astrophysics Data System (ADS)

Marcantonio, Franco

Many academic geology departments do not include geochemistry in their undergraduate core curriculums. The second edition of Principles and Applications of Geochemistry demonstrates why this should change. Gunter Faure's book clearly shows the important role played by quantitative geochemical analysis in our understanding of Earth processes, both natural and anthropogenic. Intended as an introductory inorganic geochemistry text for senior undergraduates or first-year graduate students, the book makes even the most difficult concepts readily understandable. Beyond its lucid technical explanations, it also includes engaging discussions of the history of geochemistry as a science.

Origins of organic geochemistry

USGS Publications Warehouse

Kvenvolden, K.A.

2008-01-01

When organic geochemistry actually began as a recognized geoscience is a matter of definition and perspective. Constraints on its beginning are placed by the historical development of its parent disciplines, geology and organic chemistry. These disciplines originated independently and developed in parallel, starting in the latter half of the 18th century and flourishing thereafter into the 21st century. Organic geochemistry began sometime between 1860 and 1983; I argue that 1930 is the best year to mark its origin.

Influence of rock composition on the geochemistry of stream and spring waters from mountainous watersheds in the Gunnison, Uncompahgre, and Grand Mesa National Forests, Colorado

USGS Publications Warehouse

Miller, William Roger

2002-01-01

The ranges of geochemical baselines for stream and spring waters were determined and maps were constructed showing acid-neutralizing capacity and potential release of total dissolved solids for streams and spring waters for watersheds underlain by each of ten different rock composition types in the Gunnison, Uncompahgre, and Grand Mesa National Forests, Colorado (GMUG). Water samples were collected in mountainous headwater watersheds that have comparatively high precipitation and low evapotranspiration rates and that generally lack extensive ground-water reservoirs. Mountainous headwaters react quickly to changes in input of water from rain and melting snow and they are vulnerable to anthropogenic impact. Processes responsible for the control and mobility of elements in the watersheds were investigated. The geochemistry of water from the sampled watersheds in the GMUG, which are underlain by rocks that are relatively unmineralized, is compared to the geochemistry of water from the mineralized Redcloud Peak area. The water with the highest potential for release of total dissolved solids is from watersheds that are underlain by Paleozoic sedimentary rocks; that high potential is caused primarily by gypsum in those rocks. Water that has the highest acid-neutralizing capacity is from watersheds that are underlain by Paleozoic sedimentary rocks. The water from watersheds underlain by the Mancos Shale has the next highest acid-neutralizing capacity. Water that has the lowest acid-neutralizing capacity is from watersheds that are underlain by Tertiary ash-flow tuff. Tertiary sedimentary rocks containing oil shale, the Mesavede Formation containing coal, and the Mancos Shale all contain pyrite with elevated metal contents. In these mountainous head-water areas, water from watersheds underlain by these rock types is only slightly impacted by oxidation of pyrite, and over-all it is of good chemical quality. These geochemical baselines demonstrate the importance of rock

Reservoir Characterization using geostatistical and numerical modeling in GIS with noble gas geochemistry

NASA Astrophysics Data System (ADS)

Vasquez, D. A.; Swift, J. N.; Tan, S.; Darrah, T. H.

2013-12-01

The integration of precise geochemical analyses with quantitative engineering modeling into an interactive GIS system allows for a sophisticated and efficient method of reservoir engineering and characterization. Geographic Information Systems (GIS) is utilized as an advanced technique for oil field reservoir analysis by combining field engineering and geological/geochemical spatial datasets with the available systematic modeling and mapping methods to integrate the information into a spatially correlated first-hand approach in defining surface and subsurface characteristics. Three key methods of analysis include: 1) Geostatistical modeling to create a static and volumetric 3-dimensional representation of the geological body, 2) Numerical modeling to develop a dynamic and interactive 2-dimensional model of fluid flow across the reservoir and 3) Noble gas geochemistry to further define the physical conditions, components and history of the geologic system. Results thus far include using engineering algorithms for interpolating electrical well log properties across the field (spontaneous potential, resistivity) yielding a highly accurate and high-resolution 3D model of rock properties. Results so far also include using numerical finite difference methods (crank-nicholson) to solve for equations describing the distribution of pressure across field yielding a 2D simulation model of fluid flow across reservoir. Ongoing noble gas geochemistry results will also include determination of the source, thermal maturity and the extent/style of fluid migration (connectivity, continuity and directionality). Future work will include developing an inverse engineering algorithm to model for permeability, porosity and water saturation.This combination of new and efficient technological and analytical capabilities is geared to provide a better understanding of the field geology and hydrocarbon dynamics system with applications to determine the presence of hydrocarbon pay zones (or

Geology and geochemistry of the Atacama Desert.

PubMed

Tapia, J; González, R; Townley, B; Oliveros, V; Álvarez, F; Aguilar, G; Menzies, A; Calderón, M

2018-02-14

The Atacama Desert, the driest of its kind on Earth, hosts a number of unique geological and geochemical features that make it unlike any other environment on the planet. Considering its location on the western border of South America, between 17 and 28 °S, its climate has been characterized as arid to hyperarid for at least the past 10 million years. Notably dry climatic conditions of the Atacama Desert have been related to uplift of the Andes and are believed to have played an important role in the development of the most distinctive features of this desert, including: (i) nitrates and iodine deposits in the Central Depression, (ii) secondary enrichment in porphyry copper deposits in the Precordillera, (iii) Li enrichment in salt flats of the Altiplano, and (iv) life in extreme habitats. The geology and physiography of the Atacama Desert have been largely shaped by the convergent margin present since the Mesozoic era. The geochemistry of surface materials is related to rock geochemistry (Co, Cr, Fe, Mn, V, and Zn), salt flats, and evaporite compositions in endorheic basins (As, B, and Li), in addition to anthropogenic activities (Cu, Mo, and Pb). The composition of surface water is highly variable, nonetheless in general it presents a circumneutral pH with higher conductivity and total dissolved solids in brines. Major water constituents, with the exception of HCO 3 - , are generally related to the increase of salinity, and despite the fact that trace elements are not well-documented, surface waters of the Atacama Desert are enriched in As, B, and Li when compared to the average respective concentrations in rivers worldwide.

Exploration Geochemistry.

ERIC Educational Resources Information Center

Closs, L. Graham

1983-01-01

Contributions in mineral-deposit model formulation, geochemical exploration in glaciated and arid environments, analytical and sampling problems, and bibliographic research were made in symposia held and proceedings volumes published during 1982. Highlights of these symposia and proceedings and comments on trends in exploration geochemistry are…

Fifty years of IMOG (International Meetings on Organic Geochemistry)

USGS Publications Warehouse

Kvenvolden, Keith A.

2012-01-01

IMOG2011 is the 25th of a series of international meetings on organic geochemistry that began in 1962. Thus, this 25th meeting marks the 50th anniversary year of IMOG, which has (a) had a rich history with meetings taking place in 11 different countries, (b) published Proceedings, titled “Advances in Organic Geochemistry,” from each meeting that now number 24 volumes totaling almost 18,000 pages, and (c) documented the content and development of the science of organic geochemistry. IMOG2011 adds a new milestone to the progress of organic geochemistry through time.

Applicability of Electrical and Electroanalytical Techniques to Detect Water and Characterize the Geochemistry of Undisturbed Planetary Soils

NASA Technical Reports Server (NTRS)

Seshadri, S.; Buehler, M. G.; Anderson, R. C.; Kuhlman, G. M.; Keymeulen, D.; Cheung, I. W.; Schaap, M. G.

2005-01-01

The search for life is a primary goal of NASA s planetary exploration program. The search is, of necessity, tiered in both the detection approach (looking for evidence of microbial fossils or the presence of water in the geological history of a planetary body and/or looking for evidence of water, energy sources, precursors to life, signatures of life and/or life itself in the present day planetary environment) and in the survey method (scale, range, specificity) employed. Terrestrial investigations suggests that life as we know it requires water. Thus, the search for extant microbial life and habitats requires identifying water-bearing soils. Determining Reduction-Oxidation (REDOX) couples present in water, once it is found, provides information on soil geochemistry and identifies potential chemical energy sources for life. Mars offers a near-term target for conducting this search. The identification of gully formation [1], layered deposits [2] and elemental ratios of bromine and chlorine [3] present indirect evidence that water was abundant locally in the Martian past. Additionally, Viking images of polar ice and frost formation on the surface of Mars demonstrate that water can exist in at least some near-surface regions of present-day Mars. Atmospheric pressure data further suggest that liquid water may be stable for short periods of time in the mid-latitudes of the Martian surface. [4] Measurements of the global distribution of hydrogen in the Martian regolith offer tantalizing indirect evidence that water may at least exist in near-surface soils. [5] Evidently, any water to be found is likely to exist as soil mixtures at levels ranging between approx.0.5% and approx.5 %.

Geochemistry of coalbed gas - a review

USGS Publications Warehouse

Clayton, J.L.

1998-01-01

Coals are both sources and reservoirs of large amounts of gas that has received increasing attention in recent years as a largely untapped potential energy resource. Coal mining operations, such as ventilation of coalbed gas from underground mines, release coalbed CH4 into the atmosphere, an important greehouse gas whose concentration in the atmosphere is increasing. Because of these energy and environmental issues, increased research attention has been focused on the geochemistry of coalbed gas in recent years. This paper presents a summary review of the main aspects of coalbed gas geochemistry and current research advances.Coals are both sources and reservoirs of large amounts of gas that has received increasing attention in recent years as a largely untapped potential energy resource. Coal mining operations, such as ventilation of coalbed gas from underground mines, release coalbed CH4 into the atmosphere, an important greenhouse gas whose concentration in the atmosphere is increasing. Because of these energy and environmental issues, increased research attention has been focused on the geochemistry of coalbed gas in recent years. This paper presents a summary review of the main aspects of coalbed gas geochemistry and current research advances.

Favorable Geochemistry from Springs and Wells in Colorado

DOE Data Explorer

Richard E. Zehner

2012-02-01

This layer contains favorable geochemistry for high-temperature geothermal systems, as interpreted by Richard "Rick" Zehner. The data is compiled from the data obtained from the USGS. The original data set combines 15,622 samples collected in the State of Colorado from several sources including 1) the original Geotherm geochemical database, 2) USGS NWIS (National Water Information System), 3) Colorado Geological Survey geothermal sample data, and 4) original samples collected by R. Zehner at various sites during the 2011 field season. These samples are also available in a separate shapefile FlintWaterSamples.shp. Data from all samples were reportedly collected using standard water sampling protocols (filtering through 0.45 micron filter, etc.) Sample information was standardized to ppm (micrograms/liter) in spreadsheet columns. Commonly-used cation and silica geothermometer temperature estimates are included.

Pore Water Arsenic Dynamics in Rice Paddies Under Projected Future Climates

NASA Astrophysics Data System (ADS)

Plaganas, M.; Wang, T.; Muehe, E. M.; Fendorf, S. E.

2016-12-01

Rice is one of the staple crops in the world, with 50% of the global population eating rice daily. Many rice-producing regions of the world are irrigated with groundwater contaminated with arsenic (As), and in particular South and Southeast Asia, where geogenic As is leached into the groundwater. Use of groundwater pervasively high in As leads to subsequent accumulation in paddy soils. Arsenic, a toxic metalloid, also decreases rice productivity and further jeopardizes food security. Hence, rice agriculture is concerned with its productivity in a climate change impacted future and the particular impacts of arsenic on yields. However, past studies do not address the prevalence of As in paddy soils or its fate in the rhizosphere and ultimate impact on the plant. The objective of our study was to determine changes in pore water As dynamics in the rhizosphere of rice plants grown on As-contaminated paddy soil under climate conditions projected for the end of the century. In order to address this objective, we designed greenhouse chambers with today's climate and projected climate conditions for the year 2100, specifically 5°C increase in temperature and doubled concentration of atmospheric CO2. We hypothesize that the effects of climate change with these conditions will increase the mobility of As in the rhizosphere, and thus, decrease rice growth in As-bearing paddies more than, so far, expected. We examined pore water geochemistry including pH and As concentrations, and correlate that to the height of the plants. Furthermore, the dynamics of other elements in the pore water such as carbon, iron, sulfur, manganese, and silica are further evaluated for their effects on rice growth. Arsenic will have an impact on rice production and conditions induced by future climatic conditions need to be considered for food security. Considering that climate change will decrease the global agricultural output, we should urgently consider adapting our agricultural practices to aid

10 CFR 960.4-2-2 - Geochemistry.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 10 Energy 4 2011-01-01 2011-01-01 false Geochemistry. 960.4-2-2 Section 960.4-2-2 Energy DEPARTMENT OF ENERGY GENERAL GUIDELINES FOR THE PRELIMINARY SCREENING OF POTENTIAL SITES FOR A NUCLEAR WASTE REPOSITORY Postclosure Guidelines § 960.4-2-2 Geochemistry. (a) Qualifying condition. The present and...

Inorganic Geochemistry of Flowback Water from the Montney Formation: Potential Sources of Elevated Ion Concentrations

NASA Astrophysics Data System (ADS)

Owen, J.; Bustin, R.

2016-12-01

concentrations, and more saline connate formation water. Geochemical modeling indicates the ion concentrations in the flowback water are a complex product of mineral precipitation/dissolution, ion exchange with the reservoir, geochemistry of the connate water and water saturation of the reservoir.

Relation between organic-wastewater compounds, groundwater geochemistry, and well characteristics for selected wells in Lansing, Michigan

USGS Publications Warehouse

Haack, Sheridan K.; Luukkonen, Carol L.

2013-01-01

In 2010, groundwater from 20 Lansing Board of Water and Light (BWL) production wells was tested for 69 organic-wastewater compounds (OWCs). The OWCs detected in one-half of the sampled wells are widely used in industrial and environmental applications and commonly occur in many wastes and stormwater. To identify factors that contribute to the occurrence of these constituents in BWL wells, the U.S. Geological Survey (USGS) interpreted the results of these analyses and related detections of OWCs to local characteristics and groundwater geochemistry. Analysis of groundwater-chemistry data collected by the BWL during routine monitoring from 1969 to 2011 indicates that the geochemistry of the BWL wells has changed over time, with the major difference being an increase in sodium and chloride. The concentrations of sodium and chloride were positively correlated to frequency of OWC detections. The BWL wells studied are all completed in the Saginaw aquifer, which consists of water-bearing sandstones of Pennsylvanian age. The Saginaw aquifer is underlain by the Parma-Bayport aquifer, and overlain by the Glacial aquifer. Two possible sources of sodium and chloride were evaluated: basin brines by way of the Parma-Bayport aquifer, and surficial sources by way of the Glacial aquifer. To determine if water from the underlying aquifer had influenced well-water geochemistry over time, the total dissolved solids concentration and changes in major ion concentrations were examined with respect to well depth, age, and pumping rate. To address a possible surficial source of sodium and chloride, 25 well, aquifer, or hydrologic characteristics, and 2 groundwater geochemistry variables that might influence whether, or the rate at which, water from the land surface could reach each well were compared to OWC detections and well chemistry. The statistical tests performed during this study, using available variables, indicated that reduced time of travel of water from the land surface to the

Relation of specific conductance in ground water to intersection of flow paths by wells, and associated major ion and nitrate geochemistry, Barton Springs Segment of the Edwards Aquifer, Austin, Texas, 1978-2003

USGS Publications Warehouse

Garner, Bradley D.; Mahler, Barbara J.

2007-01-01

Understanding of karst flow systems can be complicated by the presence of solution-enlarged conduits, which can transmit large volumes of water through the aquifer rapidly. If the geochemistry at a well can be related to streamflow or spring discharge (springflow), or both, the relations can indicate the presence of recent recharge in water at the well, which in turn might indicate that the well intersects a conduit (and thus a major flow path). Increasing knowledge of the occurrence and distribution of conduits in the aquifer can contribute to better understanding of aquifer framework and function. To that end, 26 wells in the Barton Springs segment of the Edwards aquifer, Austin, Texas, were investigated for potential intersection with conduits; 26 years of arbitrarily timed specific conductance measurements in the wells were compared to streamflow in five creeks that provide recharge to the aquifer and were compared to aquifer flow conditions as indicated by Barton Springs discharge. A nonparametric statistical test (Spearman's rho) was used to divide the 26 wells into four groups on the basis of correlation of specific conductance of well water to streamflow or spring discharge, or both. Potential relations between conduit intersection by wells and ground-water geochemistry were investigated through analysis of historical major ion and nitrate geochemistry for wells in each of the four groups. Specific conductance at nine wells was negatively correlated with both streamflow and spring discharge, or streamflow only. These correlations were interpreted as evidence of an influx of surface-water recharge during periods of high streamflow and the influence at the wells of water from a large, upgradient part of the aquifer; and further interpreted as indicating that four wells intersect major aquifer flow paths and five wells intersect minor aquifer flow paths (short, tributary conduits). Specific conductance at six wells was positively correlated with spring

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer.

PubMed

Gray, Cassie J; Engel, Annette S

2013-02-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface.

Microbial diversity and impact on carbonate geochemistry across a changing geochemical gradient in a karst aquifer

PubMed Central

Gray, Cassie J; Engel, Annette S

2013-01-01

Although microbes are known to influence karst (carbonate) aquifer ecosystem-level processes, comparatively little information is available regarding the diversity of microbial activities that could influence water quality and geological modification. To assess microbial diversity in the context of aquifer geochemistry, we coupled 16S rRNA Sanger sequencing and 454 tag pyrosequencing to in situ microcosm experiments from wells that cross the transition from fresh to saline and sulfidic water in the Edwards Aquifer of central Texas, one of the largest karst aquifers in the United States. The distribution of microbial groups across the transition zone correlated with dissolved oxygen and sulfide concentration, and significant variations in community composition were explained by local carbonate geochemistry, specifically calcium concentration and alkalinity. The waters were supersaturated with respect to prevalent aquifer minerals, calcite and dolomite, but in situ microcosm experiments containing these minerals revealed significant mass loss from dissolution when colonized by microbes. Despite differences in cell density on the experimental surfaces, carbonate loss was greater from freshwater wells than saline, sulfidic wells. However, as cell density increased, which was correlated to and controlled by local geochemistry, dissolution rates decreased. Surface colonization by metabolically active cells promotes dissolution by creating local disequilibria between bulk aquifer fluids and mineral surfaces, but this also controls rates of karst aquifer modification. These results expand our understanding of microbial diversity in karst aquifers and emphasize the importance of evaluating active microbial processes that could affect carbonate weathering in the subsurface. PMID:23151637

The dynamical crossover phenomenon in bulk water, confined water and protein hydration water.

PubMed

Mallamace, Francesco; Corsaro, Carmelo; Baglioni, Piero; Fratini, Emiliano; Chen, Sow-Hsin

2012-02-15

We discuss a phenomenon regarding water that was until recently a subject of scientific controversy, i.e. the dynamical crossover from fragile-to-strong glass-forming material, for both bulk and protein hydration water. Such a crossover is characterized by a temperature T(L) at which significant dynamical changes occur, such as violation of the Stokes-Einstein relation and changes of behaviour of homologous transport parameters such as the density relaxation time and the viscosity. In this respect we will consider carefully the dynamic properties of water-protein systems. More precisely, we will study proteins and their hydration water as far as bulk and confined water. In order to clarify the controversy we will discuss in a comparative way many previous and new experimental data that have emerged using different techniques and molecular dynamic simulation (MD). We point out the reasons for the different dynamical findings from the use of different experimental techniques.

Geochemistry of groundwater in the eastern Snake River Plain aquifer, Idaho National Laboratory and vicinity, eastern Idaho

USGS Publications Warehouse

Rattray, Gordon W.

2018-05-30

Nuclear research activities at the U.S. Department of Energy (DOE) Idaho National Laboratory (INL) in eastern Idaho produced radiochemical and chemical wastes that were discharged to the subsurface, resulting in detectable concentrations of some waste constituents in the eastern Snake River Plain (ESRP) aquifer. These waste constituents may pose risks to the water quality of the aquifer. In order to understand these risks to water quality the U.S. Geological Survey, in cooperation with the DOE, conducted a study of groundwater geochemistry to improve the understanding of hydrologic and chemical processes in the ESRP aquifer at and near the INL and to understand how these processes affect waste constituents in the aquifer.Geochemistry data were used to identify sources of recharge, mixing of water, and directions of groundwater flow in the ESRP aquifer at the INL. The geochemistry data were analyzed from 167 sample sites at and near the INL. The sites included 150 groundwater, 13 surface-water, and 4 geothermal-water sites. The data were collected between 1952 and 2012, although most data collected at the INL were collected from 1989 to 1996. Water samples were analyzed for all or most of the following: field parameters, dissolved gases, major ions, dissolved metals, isotope ratios, and environmental tracers.Sources of recharge identified at the INL were regional groundwater, groundwater from the Little Lost River (LLR) and Birch Creek (BC) valleys, groundwater from the Lost River Range, geothermal water, and surface water from the Big Lost River (BLR), LLR, and BC. Recharge from the BLR that may have occurred during the last glacial epoch, or paleorecharge, may be present at several wells in the southwestern part of the INL. Mixing of water at the INL primarily included mixing of surface water with groundwater from the tributary valleys and mixing of geothermal water with regional groundwater. Additionally, a zone of mixing between tributary valley water and

Spatial heterogeneity of high-resolution Chalk groundwater geochemistry - Underground quarry at Saint Martin-le-Noeud, France

NASA Astrophysics Data System (ADS)

Barhoum, S.; Valdès, D.; Guérin, R.; Marlin, C.; Vitale, Q.; Benmamar, J.; Gombert, P.

2014-11-01

Chalk groundwater is an important aquifer resource in France because it accounts for a production of 12 million m3 y-1 with a large proportion reserved for drinking water. Processes occurring in the unsaturated zone (UZ) and the overlying superficial formations have a high impact on Chalk groundwater geochemistry and require better understanding. The study site is a former underground Chalk quarry located near Beauvais (France) that extends over 1200 m in length, at a depth ranging from 20 to 30 m. The water table intersects the cavity creating 15 underground ;lake; that give access to the Chalk groundwater. Lakes geochemistry has been studied: water samples were collected in July 2013 and major ion concentrations were analyzed. UZ and clay-with-flints thickness above each lake were estimated qualitatively using an electromagnetic sensor (EM31) and Underground GPS. The results unexpectedly showed that groundwater quality varied widely in spatial terms for both allochthonous and autochthonous ions (e.g., HCO3- ranged from 2.03 to 4.43 meq L-1, NO3- ranged from 0.21 to 1.33 meq L-1). Principal component analysis indicated the impact of agricultural land use on water quality, with the intake of NO3- as well as SO42-, Cl- and Ca2+. Chalk groundwater geochemistry is compared with the nature and structure of the UZ. We highlight correlations (1) between thick clay-with-flints layers and the ions Mg2+ and K+, and (2) between UZ thickness and Na+. In conclusion, this paper identifies various ion sources (agriculture, clay-with-flints and Chalk) and demonstrates different processes in the UZ: dissolution, ionic exchange and solute storage.

Water geochemistry of shallow lakes from the southeastern Pampa plain, Argentina and their implications on mollusk shells preservation.

PubMed

Cristini, Paula A; Tietze, Eleonor; De Francesco, Claudio G; Martínez, Daniel E

2017-12-15

A seasonal sampling of sediments, column and interstitial water for physico-chemical analysis were performed in littoral and open water areas in three freshwater shallow lakes (Nahuel Rucá, Las Mostazas and Los Carpinchos) from Southeastern Pampa plain, Argentina. The main objective of the present study is to evaluate how the characteristics of the depositional environments could be affecting mollusk shell preservation. These lakes are very shallow (2m) and are characterized by an extensive littoral area, dominated by the emergent macrophyte Schoenoplectus californicus, which forms a complete ring around the lake, and an open water area, in general free of vegetation. Five samples of sediments in each compartment were extracted for analysis of pH, moisture, organic matter and carbonates content using a gravity corer, while five samples from column and interstitial water were extracted for chemical analysis (pH, conductivity, major ions, minor ions and hardness). Besides, calcite and aragonite saturation indices and the redox potential were calculated for each lake. The results show the significant impact of water chemistry and redox conditions on the preservation potential of freshwater mollusk and consequently in the quality of paleonvironmental reconstruction based on the biological record from the study region. The higher concentration of organic matter and lower pH registered in the littoral area, mainly during warm months (autumn and summer), suggest worst environments for mollusk preservation, compared to open waters. Moreover, water geochemistry analysis showed aragonite and calcite indices near equilibrium or slightly subsaturated in interstitial water associated with more acid pHs, while column water is strongly oversaturated related to alkaline pHs. These results suggest that carbonate remains within sediments will be subject to dissolution affecting negatively their preservation potential. However, mollusk shells in contact with the column water are not

Tidally driven water column hydro-geochemistry in a remediating acidic wetland

NASA Astrophysics Data System (ADS)

Johnston, Scott G.; Keene, Annabelle F.; Bush, Richard T.; Sullivan, Leigh A.; Wong, Vanessa N. L.

2011-10-01

SummaryManaged tidal inundation is a newly evolved technique for remediating coastal acid sulphate soil (CASS) wetlands. However, there remains considerable uncertainty regarding the hydro-geochemical pathways and spatiotemporal dynamics of residual H + and metal(loid) mobilisation into the tidal fringe surface waters of these uniquely iron-rich landscapes. Here, we examine the hydrology and water column chemistry across the intertidal slope of a remediating CASS wetland during several tide cycles. There was extreme spatial and temporal dynamism in water column chemistry, with pH fluctuating by ˜3 units (˜3.5-6.5) during a single tide cycle. Acute acidity was spatially confined to the upper intertidal slope, reflecting surface sediment properties, and tidal overtopping is an important pathway for mobilisation of residual H + and Al 3+ to the water column. Marine derived HCO3- was depleted from surface waters migrating across the intertidal slope and a strong gradient in HCO3- was observed from the tidal fringe to the adjacent tributary channel and nearby estuary. Tidal forcing generated oscillating hydraulic gradients in the shallow fringing aquifer, favouring ebb-tide seepage and driving rapid, heterogeneous advection of groundwater on the lower intertidal slope via surface connected macropores. A combination of diffusive and advective flux across the sediment-water interface led to persistent, elevated surface water Fe 2+ (˜10-1000 μM). The geochemical processes associated with Fe 2+ mobilisation displayed distinct spatial zonation, with low pH, proton-promoted desorption occurring on the upper intertidal slope, whilst circum-neutral pH, Fe(III)-reducing processes dominated the lower intertidal slope. Arsenic was also mobilised into surface waters on the lower intertidal slope under moderate pH (˜6.0) conditions and was strongly positively correlated with Fe 2+. Saturation index values for aragonite were substantially depressed (-1 to -5) and significantly

Structure and dynamics of complex liquid water: Molecular dynamics simulation

NASA Astrophysics Data System (ADS)

S, Indrajith V.; Natesan, Baskaran

2015-06-01

We have carried out detailed structure and dynamical studies of complex liquid water using molecular dynamics simulations. Three different model potentials, namely, TIP3P, TIP4P and SPC-E have been used in the simulations, in order to arrive at the best possible potential function that could reproduce the structure of experimental bulk water. All the simulations were performed in the NVE micro canonical ensemble using LAMMPS. The radial distribution functions, gOO, gOH and gHH and the self diffusion coefficient, Ds, were calculated for all three models. We conclude from our results that the structure and dynamical parameters obtained for SPC-E model matched well with the experimental values, suggesting that among the models studied here, the SPC-E model gives the best structure and dynamics of bulk water.

The Dynamics of Flowing Waters.

ERIC Educational Resources Information Center

Mattingly, Rosanna L.

1987-01-01

Describes a series of activities designed to help students understand the dynamics of flowing water. Includes investigations into determining water discharge, calculating variable velocities, utilizing flood formulas, graphing stream profiles, and learning about the water cycle. (TW)

Water dynamics in rigid ionomer networks.

PubMed

Osti, N C; Etampawala, T N; Shrestha, U M; Aryal, D; Tyagi, M; Diallo, S O; Mamontov, E; Cornelius, C J; Perahia, D

2016-12-14

The dynamics of water within ionic polymer networks formed by sulfonated poly(phenylene) (SPP), as revealed by quasi-elastic neutron scattering (QENS), is presented. These polymers are distinguished from other ionic macromolecules by their rigidity and therefore in their network structure. QENS measurements as a function of temperature as the fraction of ionic groups and humidity were varied have shown that the polymer molecules are immobile while absorbed water molecules remain dynamic. The water molecules occupy multiple sites, either bound or loosely constrained, and bounce between the two. With increasing temperature and hydration levels, the system becomes more dynamic. Water molecules remain mobile even at subzero temperatures, illustrating the applicability of the SPP membrane for selective transport over a broad temperature range.

Linking Water Table Dynamics to Carbon Cycling in Artificial Soil Column Incubations

NASA Astrophysics Data System (ADS)

Geertje, Pronk; Adrian, Mellage; Tatjana, Milojevic; Fereidoun, Rezanezhad; Cappellen Philippe, Van

2016-04-01

The biogeochemistry of wetlands soils is closely tied to their hydrology. Water table fluctuations that cause flooding and drying of these systems may lead to enhanced degradation of organic matter and release of greenhouse gasses (e.g. CO2, CH4) to the atmosphere. However, predicting the influence of water table fluctuations on the biogeochemical functioning of soils requires an understanding of the interactions of soil hydrology with biogeochemical and microbial processes. To determine the effects of water table dynamics on carbon cycling, we are carrying out state-of-the-art automated soil column experiments with fully integrated monitoring of hydro-bio-geophysical process variables under both constant and oscillating water table conditions. An artificial, homogeneous mixture consisting of minerals and organic matter is used to provide a well-defined starting material. The artificial soils are composed of quartz sand, montmorillonite, goethite and humus from a forested riparian zone, from which we also extracted the microbial inoculum added to the soil mixture. The artificial soils are packed into 60 cm high, 7.5 cm wide columns. In the currently ongoing experiment, three replicate columns are incubated while keeping the water table constant water at mid-depth, while another three columns alternate between drained and saturated conditions. Micro-sensors installed at different depths below the soil surface record time-series redox potentials (Eh) varying between oxidizing (~+700 mV) and reducing (~-200 mV) conditions. Continuous O2 levels throughout the soil columns are monitored using high-resolution, luminescence-based, Multi Fiber Optode (MuFO) microsensors. Pore waters are collected periodically with MicroRhizon samplers from different depths, and analyzed for pH, EC, dissolved inorganic and organic carbon and ion/cation compositions. These measurements allow us to track the changes in pore water geochemistry and relate them to differences in carbon cycling

Optimal Dynamics of Intermittent Water Supply

NASA Astrophysics Data System (ADS)

Lieb, Anna; Wilkening, Jon; Rycroft, Chris

2014-11-01

In many urban areas of the developing world, piped water is supplied only intermittently, as valves direct water to different parts of the water distribution system at different times. The flow is transient, and may transition between free-surface and pressurized, resulting in complex dynamical features with important consequences for water suppliers and users. These consequences include degradation of distribution system components, compromised water quality, and inequitable water availability. The goal of this work is to model the important dynamics and identify operating conditions that mitigate certain negative effects of intermittent water supply. Specifically, we will look at valve parameters occurring as boundary conditions in a network model of transient, transition flow through closed pipes. Optimization will be used to find boundary values to minimize pressure gradients and ensure equitable water availability.

Peat characteristics and groundwater geochemistry of calcareous fens in the Minnesota River Basin, U.S.A

USGS Publications Warehouse

Almendinger, J.E.; Leete, J.H.

1998-01-01

. Calcareous fens in Minnesota are spring-seepage peatlands with a distinctive flora of rare calciphilic species. Peat characteristics and groundwater geochemistry were determined for six calcareous fens in the Minnesota River Basin to better understand the physical structure and chemical processes associated with stands of rare vegetation. Onset of peat accumulation in three of the fens ranged from about 4,700 to 11,000 14C yrs BP and probably resulted from a combination of climate change and local hydrogeologic conditions. Most peat cores had a carbonate-bearing surface zone with greater than 10% carbonates (average 27%, dry wt basis), an underlying carbonate-depleted zone with 10% or less carbonates (average 4%), and a carbonate-bearing lower zone again with greater than 10% carbonates (average 42%). This carbonate zonation was hypothesized to result from the effect of water-table level on carbonate equilibria: carbonate precipitation occurs when the water table is above a critical level, and carbonate dissolution occurs when the water table is lower. Other processes that changed the major ion concentrations in upwelling groundwater include dilution by rain water, sulfate reduction or sulfide oxidation, and ion adsorption or exchange. Geochemical modeling indicated that average shallow water in the calcareous fens during the study period was groundwater mixed with about 6 to 13% rain water. Carbonate precipitation in the surface zone of calcareous fens could be decreased by a number of human activities, especially those that lower the water table. Such changes in shallow water geochemistry could alter the growing conditions that apparently sustain rare fen vegetation.

Sulfur and iron geochemistry of the dynamic sedimentary system at the Costa Rica margin, IODP Expedition 344

NASA Astrophysics Data System (ADS)

Gott, C.; Riedinger, N.; Formolo, M.; Solomon, E. A.; Torres, M. E.; Bates, S. M.; Lyons, T. W.; 344 Scientific Party, I.

2013-12-01

One of the major targets of the CRISP (Costa Rica Seismogenesis Project) was to explore diagenetic processes, including fluid flow, related to the complex sedimentary and tectonic behavior of the Costa Rica margin system. Here we present preliminary results of the iron and sulfur geochemistry from sediments collected during the IODP Expedition 344 at Holes U1413B and U1414A. Our specific goal was to investigate the impact of this dynamic system on biogeochemical processes - especially regarding the sulfur cycle - and how minerals record these processes in the geologic record. The sediments at both investigated locations display non-steady state pore water conditions. Specifically, the deposits at Hole U1413B are characterized by a shallow sulfate-methane transition zone (SMTZ; approximately 15 mbsf), where released hydrogen sulfide reacts with reactive iron minerals to form iron sulfides. At Hole U1414A pore water sulfate is present at several hundreds of meters sediment depth, while the concentration of hydrogen sulfide is low (<4 μM). The measured concentrations of solid phase iron sulfides in the sediments indicate that pyrite is the main sulfur-bearing phase, reaching concentrations of 2 and 3 wt.%, in U1413B and U1414A, respectively. Sequential extractions of iron oxides reveal the presence of reactive iron phases, although in low concentrations (total iron oxides are below 1.1 wt.%), indicating ongoing alteration of iron oxides. The occurrence of these reactive iron minerals in the deeply buried sediments at Hole U1414A has implications for the deep biosphere - as those minerals can still be utilized by the microbial community. The non-steady state condition of the sedimentary system at both locations is also mirrored in the S-isotopic signal in the pore fluids as well as solid phase. The 34S-enriched sulfate (δ34S >+60 ‰) in the deeper sediment column is reflected in the δ34S profile of the in situ formed iron sulfides - the results can have

One-carbon (bio ?) Geochemistry in Subsurface Waters of the Serpentinizing Coast Range Ophiolite

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Mccollom, Tom; Schrenk, Matt; Cardace, Dawn

2011-01-01

Serpentinization - the aqueous alteration of ultramafic rocks - typically imparts a highly reducing and alkaline character to the reacting fluids. In turn, these can influence the speciation and potential for metabolism of one-carbon compounds in the system. We examined the aqueous geochemistry and assessed the biological potential of one-carbon compounds in the subsurface of the McLaughlin Natural Reserve (Coast Range Ophiolite, California, USA). Fluids from wells sunk at depths of 25-90 meters have pH values ranging from 9.7 to 11.5 and dissolved inorganic carbon (DIC concentrations) generally below 60 micromolar. Methane is present at concentrations up to 1.3 millimolar (approximately one-atmosphere saturation), and hydrogen concentrations are below 15 nanomolar, suggesting active consumption of H2 and production of CH4. However, methane production from CO2 is thermodynamically unfavorable under these conditions. Additionally, the speciation of DIC predominantly into carbonate at these high pH values creates a problem of carbon availability for any organisms that require CO2 (or bicarbonate) for catabolism or anabolism. A potential alternative is carbon monoxide, which is present in these waters at concentrations 2000-fold higher than equilibrium with atmospheric CO. CO is utilized in a variety of metabolisms, including methanogenesis, and bioavailability is not adversely affected by pH-dependent speciation (as for DIC). Methanogenesis from CO under in situ conditions is thermodynamically favorable and would satisfy biological energy requirements with respect to both Gibbs Energy yield and power.

Geochemistry driven trends in microbial diversity and function across a temperature transect of a shallow water hydrothermal system off Milos (Greece)

NASA Astrophysics Data System (ADS)

Bühring, Solveig I.; Amend, Jan P.; Gómez Sáez, Gonzalo V.; Häusler, Stefan; Hinrichs, Kai-Uwe; Pichler, Thomas; Pop Ristova, Petra; Price, Roy E.; Santi, Ioulia; Sollich, Miriam

2014-05-01

The shallow water hydrothermal vents off Milos Island, Greece, discharge hot, slightly acidic, reduced fluids into colder, slightly alkaline, oxygenated seawater. Gradients in temperature, pH, and geochemistry are established as the two fluids mix, leading to the formation of various microbial microniches. In contrast to deep-sea hydrothermal systems, the availability of sun light allows for a combination of photo- and chemotrophic carbon fixation. Despite the comparably easy accessibility of shallow water hydrothermal systems, little is known about their microbial diversity and functioning. We present data from a shallow hydrothermal system off Milos Island, one of the most hydrothermally active regions in the Mediterranean Sea. The physico-chemical changes from ambient seafloor to hydrothermal area were investigated and documented by in situ microsensor profiling of temperature, pH, total reduced sulfur and dissolved oxygen alongside porewater geochemistry. The spatial microbial diversity was determined using a combination of gene- and lipid-based approaches, whereas microbial functioning was assessed by stable isotope probing experiments targeting lipid biomarkers. In situ microprofiles indicated an extreme environment with steep gradients, offering a variety of microniches for metabolically diverse microbial communities. We sampled a transect along a hydrothermal patch, following an increase in sediment surface temperature from background to 90°C, including five sampling points up to 20 cm sediment depth. Investigation of the bacterial diversity using ARISA revealed differences in the community structure along the geochemical gradients, with the least similarity between the ambient and highly hydrothermally impacted sites. Furthermore, using multivariate statistical analyses it was shown that variations in the community structure could be attributed to differences in the sediment geochemistry and especially the sulfide content, and only indirectly to shifts in

Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants

DOE PAGES

Roy, Santanu; Skoff, David; Perroni, Dominic V.; ...

2016-02-14

Water-mediated ion transport through functional nanoporous materials depends on the dynamics of water confined within a given nanostructured morphology. In this study, we investigate hydrogen-bonding dynamics of interfacial water within a ‘normal’ (Type I) lyotropic gyroid phase formed by a gemini dicarboxylate surfactant self-assembly using a combina- tion of 2DIR spectroscopy and molecular dynamics simulations. Experiments and simulations demonstrate that water dynamics in the normal gyroid phase is one order of magnitude slower than that in bulk water, due to specific interactions between water, the ionic surfactant headgroups, and counterions. However, the dynamics of water in the normal gyroid phasemore » are faster than those of water confined in a reverse spherical micelle of a sulfonate surfactant, given that the water pool in the reverse micelle and the water pore in the gyroid phase have roughly the same diameters. This difference in confined water dynamics likely arises from the significantly reduced curvature- induced frustration at the convex interfaces of the normal gyroid, as compared to the concave interfaces of a reverse spherical micelle. These detailed insights into confined water dynamics may guide the future design of artificial membranes that rapidly transport protons and other ions.« less

Geochemistry, biota and natural background levels in an arsenic naturally contaminated volcanic aquifer

NASA Astrophysics Data System (ADS)

Preziosi, Elisabetta; Amalfitano, Stefano; Di Lorenzo, Tiziana; Parrone, Daniele; Rossi, David; Ghergo, Stefano; Lungarini, Silvia; Zoppini, Anna Maria

2015-04-01

The tight links between chemical and ecological status are largely acknowledged as for surface water bodies, while aquifers are still considered as hidden groundwater reservoirs, rather than ecosystems to be preserved. Geochemical and biological interactions play a key role in all subterranean processes, including the dynamics of the fate of anthropogenic contaminants. Studies on groundwater dependent ecosystems (GDE) were mainly focused on karst aquifers so far, but an increased awareness on the importance of water-rock interactions and methodological improvements in microbial ecology are rapidly increasing the level of characterization of groundwater ecosystems in various hydrogeological contexts. Similarly, knowledge about groundwater biodiversity is still limited, especially if porous habitats are concerned. Yet, groundwater and GDEs are populated by a diverse and highly adapted biota, dominated by crustaceans, which provide important ecosystem services and act as biological indicators of chemical and quantitative impact on groundwater resources. In a previous research (Amalfitano et al. 2014), we reported that the microbial community heterogeneity may reflect the lithological and hydrogeological complexity within volcanic and alluvial facies transition in a groundwater body. The quantitative tracking of the microbial community structure allowed disentangling the natural biogeochemical processes evolving within the aquifer flow path. The analyses of groundwater crustaceans assemblages may contribute to shed more light upon the state and dynamics of such ecosystems. In the present research, a comprehensive study of a water table aquifer flowing through a quaternary volcanic district is being performed, including the geochemical (inorganic) composition, the microbial composition, and the analysis of crustacean assemblages . Groundwater samples are periodically collected from private wells and springs under a low anthropic impact. The key issues within the

Retardation of Bulk Water Dynamics by Disaccharide Osmolytes

NASA Astrophysics Data System (ADS)

Shukla, Nimesh; Chen, Lee; Pomarico, Enrico; Chergui, Majed; Othon, Christina

Bioprotective nature of disaccharides is hypothesized to derive from the modification of the hydrogen bonding network of water which protects biomolecules through lowered water activity at the protein interface. Using ultrafast fluorescence spectroscopy, we measured the relaxation of bulk water dynamics around the induced dipole moment of two fluorescent probes (Lucifer Yellow Ethylenediamine and Tryptophan). Our results indicate a reduction in bulk water reorganization rate of approximately 30%. We observe this retardation in the low concentration regime measured at 0.1 and 0.25 M, far below the onset of glassy dynamics. This water structuring should be significant in crowded biological systems, contributing to a global change in protein energy landscape, resulting in a significant enhancement of protein stability under environmental stress. We observed similar dynamic reduction for two disaccharide osmolytes, sucrose and trehalose, with trehalose being the more effective in reducing solvation dynamics.

Responses of Cloud Type Distributions to the Large-Scale Dynamical Circulation: Water Budget-Related Dynamical Phase Space and Dynamical Regimes

NASA Technical Reports Server (NTRS)

Wong, Sun; Del Genio, Anthony; Wang, Tao; Kahn, Brian; Fetzer, Eric J.; L'Ecuyer, Tristan S.

2015-01-01

Goals: Water budget-related dynamical phase space; Connect large-scale dynamical conditions to atmospheric water budget (including precipitation); Connect atmospheric water budget to cloud type distributions.

Dynamics of water bound to crystalline cellulose.

PubMed

O'Neill, Hugh; Pingali, Sai Venkatesh; Petridis, Loukas; He, Junhong; Mamontov, Eugene; Hong, Liang; Urban, Volker; Evans, Barbara; Langan, Paul; Smith, Jeremy C; Davison, Brian H

2017-09-19

Interactions of water with cellulose are of both fundamental and technological importance. Here, we characterize the properties of water associated with cellulose using deuterium labeling, neutron scattering and molecular dynamics simulation. Quasi-elastic neutron scattering provided quantitative details about the dynamical relaxation processes that occur and was supported by structural characterization using small-angle neutron scattering and X-ray diffraction. We can unambiguously detect two populations of water associated with cellulose. The first is "non-freezing bound" water that gradually becomes mobile with increasing temperature and can be related to surface water. The second population is consistent with confined water that abruptly becomes mobile at ~260 K, and can be attributed to water that accumulates in the narrow spaces between the microfibrils. Quantitative analysis of the QENS data showed that, at 250 K, the water diffusion coefficient was 0.85 ± 0.04 × 10 -10  m 2 sec -1 and increased to 1.77 ± 0.09 × 10 -10  m 2 sec -1 at 265 K. MD simulations are in excellent agreement with the experiments and support the interpretation that water associated with cellulose exists in two dynamical populations. Our results provide clarity to previous work investigating the states of bound water and provide a new approach for probing water interactions with lignocellulose materials.

Dynamics of water bound to crystalline cellulose

DOE Office of Scientific and Technical Information (OSTI.GOV)

O’Neill, Hugh; Pingali, Sai Venkatesh; Petridis, Loukas

Interactions of water with cellulose are of both fundamental and technological importance. Here, we characterize the properties of water associated with cellulose using deuterium labeling, neutron scattering and molecular dynamics simulation. Quasi-elastic neutron scattering provided quantitative details about the dynamical relaxation processes that occur and was supported by structural characterization using small-angle neutron scattering and X-ray diffraction. We can unambiguously detect two populations of water associated with cellulose. The first is “non-freezing bound” water that gradually becomes mobile with increasing temperature and can be related to surface water. The second population is consistent with confined water that abruptly becomes mobilemore » at ~260 K, and can be attributed to water that accumulates in the narrow spaces between the microfibrils. Quantitative analysis of the QENS data showed that, at 250 K, the water diffusion coefficient was 0.85 ± 0.04 × 10-10 m2sec-1 and increased to 1.77 ± 0.09 × 10-10 m2sec-1 at 265 K. MD simulations are in excellent agreement with the experiments and support the interpretation that water associated with cellulose exists in two dynamical populations. Our results provide clarity to previous work investigating the states of bound water and provide a new approach for probing water interactions with lignocellulose materials.« less

The Dynamic Surface Tension of Water

PubMed Central

2017-01-01

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m–1) than under equilibrium conditions (∼72 mN m–1) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments. PMID:28301160

The Dynamic Surface Tension of Water.

PubMed

Hauner, Ines M; Deblais, Antoine; Beattie, James K; Kellay, Hamid; Bonn, Daniel

2017-04-06

The surface tension of water is an important parameter for many biological or industrial processes, and roughly a factor of 3 higher than that of nonpolar liquids such as oils, which is usually attributed to hydrogen bonding and dipolar interactions. Here we show by studying the formation of water drops that the surface tension of a freshly created water surface is even higher (∼90 mN m -1 ) than under equilibrium conditions (∼72 mN m -1 ) with a relaxation process occurring on a long time scale (∼1 ms). Dynamic adsorption effects of protons or hydroxides may be at the origin of this dynamic surface tension. However, changing the pH does not significantly change the dynamic surface tension. It also seems unlikely that hydrogen bonding or dipole orientation effects play any role at the relatively long time scale probed in the experiments.

Geochemistry and the understanding of ground-water systems

NASA Astrophysics Data System (ADS)

Glynn, Pierre D.; Plummer, L. Niel

2005-03-01

Geochemistry has contributed significantly to the understanding of ground-water systems over the last 50 years. Historic advances include development of the hydrochemical facies concept, application of equilibrium theory, investigation of redox processes, and radiocarbon dating. Other hydrochemical concepts, tools, and techniques have helped elucidate mechanisms of flow and transport in ground-water systems, and have helped unlock an archive of paleoenvironmental information. Hydrochemical and isotopic information can be used to interpret the origin and mode of ground-water recharge, refine estimates of time scales of recharge and ground-water flow, decipher reactive processes, provide paleohydrological information, and calibrate ground-water flow models. Progress needs to be made in obtaining representative samples. Improvements are needed in the interpretation of the information obtained, and in the construction and interpretation of numerical models utilizing hydrochemical data. The best approach will ensure an optimized iterative process between field data collection and analysis, interpretation, and the application of forward, inverse, and statistical modeling tools. Advances are anticipated from microbiological investigations, the characterization of natural organics, isotopic fingerprinting, applications of dissolved gas measurements, and the fields of reaction kinetics and coupled processes. A thermodynamic perspective is offered that could facilitate the comparison and understanding of the multiple physical, chemical, and biological processes affecting ground-water systems. La géochimie a contribué de façon importante à la compréhension des systèmes d'eaux souterraines pendant les 50 dernières années. Les avancées ont portées sur le développement du concept des faciès hydrochimiques, sur l'application de la théorie des équilibres, l'étude des processus d'oxydoréduction, et sur la datation au radiocarbone. D'autres concepts, outils et

Rethinking early Earth phosphorus geochemistry

PubMed Central

Pasek, Matthew A.

2008-01-01

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO32−), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks. PMID:18195373

Rethinking early Earth phosphorus geochemistry.

PubMed

Pasek, Matthew A

2008-01-22

Phosphorus is a key biologic element, and a prebiotic pathway leading to its incorporation into biomolecules has been difficult to ascertain. Most potentially prebiotic phosphorylation reactions have relied on orthophosphate as the source of phosphorus. It is suggested here that the geochemistry of phosphorus on the early Earth was instead controlled by reduced oxidation state phosphorus compounds such as phosphite (HPO(3)(2-)), which are more soluble and reactive than orthophosphates. This reduced oxidation state phosphorus originated from extraterrestrial material that fell during the heavy bombardment period or was produced during impacts, and persisted in the mildly reducing atmosphere. This alternate view of early Earth phosphorus geochemistry provides an unexplored route to the formation of pertinent prebiotic phosphorus compounds, suggests a facile reaction pathway to condensed phosphates, and is consistent with the biochemical usage of reduced oxidation state phosphorus compounds in life today. Possible studies are suggested that may detect reduced oxidation state phosphorus compounds in ancient Archean rocks.

Coal Formation and Geochemistry

NASA Astrophysics Data System (ADS)

Orem, W. H.; Finkelman, R. B.

2003-12-01

Coal is one of the most complex and challenging natural materials to analyze and to understand. Unlike most rocks, which consist predominantly of crystalline mineral grains, coal is largely an assemblage of amorphous, degraded plant remains metamorphosed to various degrees and intermixed with a generous sprinkling of minute syngenetic, diagenetic, epigenetic, and detrital mineral grains, and containing within its structure various amounts of water, oils, and gases. Each coal is unique, having been derived from different plant sources over geologic time, having experienty -45ced different thermal histories, and having been exposed to varying geologic processes. This diversity presents a challenge to constructing a coherent picture of coal geochemistry and the processes that influence the chemical composition of coal.Despite the challenge coal presents to geochemists, a thorough understanding of the chemistry and geology of this complex natural substance is essential because of its importance to our society. Coal is, and will remain for sometime, a crucial source of energy for the US and for many other countries (Figure 1). In the USA, more than half of the electricity is generated by coal-fired power plants, and almost 90% of the coal mined in the USA is sold for electricity generation (Pierce et al., 1996). It is also an important source of coke for steel production, chemicals, pharmaceuticals, and even perfumes ( Schobert, 1987). It may also, in some cases, be an economic source of various mineral commodities. The utilization of coal through mining, transport, storage, combustion, and the disposal of the combustion by-products, also presents a challenge to geochemists because of the wide range of environmental and human health problems arising from these activities. The sound and effective use of coal as a natural resource requires a better understanding of the geochemistry of coal, i.e., the chemical and mineralogical characteristics of the coal that control its

Global water dynamics: issues for the 21st century.

PubMed

Simonovic, Slobodan P

2002-01-01

The WorldWater system dynamics model has been developed for modeling the global world water balance and capturing the dynamic character of the main variables affecting water availability and use in the future. Despite not being a novel approach, system dynamics offers a new way of addressing complex systems. WorldWater simulations are clearly demonstrating the strong feedback relation between water availability and different aspects of world development. Results of numerous simulations are contradictory to the assumption made by many global modelers that water is not an issue on the global scale. Two major observations can be made from early simulations: (a) the use of clean water for dilution and transport of wastewater, if not dealt with in other ways, imposes a major stress on the global world water balance; and (b) water use by different sectors is demonstrating quite different dynamics than predicted by classical forecasting tools and other water-models. Inherent linkages between water quantity and quality sectors with food, industry, persistent pollution, technology, and non-renewable resources sectors of the model create shoot and collapse behavior in water use dynamics. This paper discusses a number of different water-related scenarios and their implications on the global water balance. In particular, two extreme scenarios (business as usual - named "Chaos", and unlimited desalination - named "Ocean") are presented in the paper. Based on the conclusions derived from these two extreme cases a set of more moderate and realistic scenarios (named "Conservation") is proposed and their consequences on the global water balance are evaluated.

The Medical Geochemistry of Dusts, Soils, and Other Earth Materials

NASA Astrophysics Data System (ADS)

Plumlee, G. S.; Ziegler, T. L.

2003-12-01

"Town clenched in suffocating grip of asbestos"USA Today, article on Libby,Montana, February, 2000"Researchers find volcanoes are bad for your health… long after they finish erupting"University of WarwickPress Release, 1999"Toxic soils plague city - arsenic, lead in 5 neighborhoods could imperil 17,000 residents"Denver Post, 2002"Ill winds - dust storms ferry toxic agents between countries and even continents"Science News, 2002A quick scan of newspapers, television, science magazines, or the internet on any given day has a fairly high likelihood of encountering a story (usually accompanied by a creative headline such as those above) regarding human health concerns linked to dusts, soils, or other earth materials. Many such concerns have been recognized and studied for decades, but new concerns arise regularly.Earth scientists have played significant roles in helping the medical community understand some important links between earth materials and human health, such as the role of asbestos mineralogy in disease (Skinner et al., 1988; Ross, 1999; Holland and Smith, 2001), and the role of dusts generated by the 1994 Northridge, California, earthquake in an outbreak of Valley Fever ( Jibson et al., 1998; Schneider et al., 1997).Earth science activities tied to health issues are growing (Skinner and Berger, 2003), and are commonly classified under the emerging discipline of medical geology (Finkelman et al., 2001; Selinus and Frank, 2000; Selinus, in press).Medical geochemistry (also referred to as environmental geochemistry and health: Smith and Huyck (1999), Appleton et al. (1996)) can be considered as a diverse subdiscipline of medical geology that deals with human and animal health in the context of the Earth's geochemical cycle ( Figure 1). Many medical geochemistry studies have focused on how chemical elements in rocks, soils, and sediments are transmitted via water or vegetation into the food chain, and how regional geochemical variations can result in disease

Geochemistry of sulfur in the Florida Everglades; 1994 through 1999

USGS Publications Warehouse

Bates, Anne L.; Orem, W.H.; Harvey, J.W.; Spiker, E. C.

2000-01-01

In this report, we present data on the geochemistry of sulfur in sediments and in surface water, groundwater, and rainwater in the Everglades region in south Florida. The results presented here are part of a larger study intended to determine the roles played by the cycling of carbon, nitrogen, phosphorus, and sulfur in the ecology of the south Florida wetlands. The geochemistry of sulfur in the region is particularly important because of its link to the production of toxic methylmercury through processes mediated by sulfate reducing bacteria. Sediment cores were collected from the Everglades Agricultural Area (EAA), Water Conservation Areas (WCAs) 1A and 2A, from Lake Okeechobee, and from Taylor Slough in the southern Everglades. Water collection was more widespread and includes surface water from WCAs 1A, 2A, 3A, 2B, the EAA, Taylor Slough, Lake Okeechobee, and the Kissimmee River. Groundwater was collected from The Everglades Nutrient Removal Area (ENR) and from WCA 2A. Rainwater was collected at two month intervals over a period of one year from the ENR and from WCA 2A. Water was analyzed for sulfate concentration and sulfate sulfur stable isotopic ratio (34S/32S). Sediment cores were analyzed for total sulfur concentration and/or for concentrations of sulfur species (sulfate, organic sulfur, disulfides, and acid volatile sulfides (AVS)) and for their stable sulfur isotopic ratio. Results show a decrease in total sulfur content (1.57 to 0.61 percent dry weight) with depth in two sediment cores collected in WCA 2A, indicating that there has been an increase in total sulfur content in recent times. A sediment core from the center of Lake Okeechobee shows a decrease in total sulfur content with depth (0.28 to 0.08 percent dry weight). A core from the periphery of the lake (South Bay) likewise shows a decrease in total sulfur content with depth (1.00 to 0.69 percent dry weight), however, the overall sulfur content is greater than that near the center at all depths

Arsenic geochemistry of alluvial sediments and pore waters affected by mine tailings along the Belle Fourche and Cheyenne River floodplains

USGS Publications Warehouse

Pfeifle, Bryce D.; Stamm, John F.; Stone, James J.

2018-01-01

Gold mining operations in the northern Black Hills of South Dakota resulted in the discharge of arsenopyrite-bearing mine tailings into Whitewood Creek from 1876 to 1977. Those tailings were transported further downstream along the Belle Fourche River, the Cheyenne River, and the Missouri River. An estimated 110 million metric tons of tailings remain stored in alluvial deposits of the Belle Fourche and Cheyenne Rivers. Pore-water dialysis samplers were deployed in the channel and backwaters of the Belle Fourche and Cheyenne Rivers to determine temporal and seasonal changes in the geochemistry of groundwater in alluvial sediments. Alluvial sediment adjacent to the dialysis samplers were cored for geochemical analysis. In comparison to US Environmental Protection Agency drinking water standards and reference concentrations of alluvial sediment not containing mine tailings, the Belle Fourche River sites had elevated concentrations of arsenic in pore water (2570 μg/L compared to 10 μg/L) and sediment (1010 ppm compared to < 34 ppm), respectively. Pore water arsenic concentration was affected by dissolution of iron oxyhydroxides under reducing conditions. Sequential extraction of iron and arsenic from sediment cores indicates that substantial quantities of soluble metals were present. Dissolution of arsenic sorbed to alluvial sediment particles appears to be affected by changing groundwater levels that cause shifts in redox conditions. Bioreductive processes did not appear to be a substantial transport pathway but could affect speciation of arsenic, especially at the Cheyenne River sampling sites where microbial activity was determined to be greater than at Belle Fourche sampling sites.

Water dynamics in protein hydration shells: the molecular origins of the dynamical perturbation.

PubMed

Fogarty, Aoife C; Laage, Damien

2014-07-17

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra.

Water Dynamics in Protein Hydration Shells: The Molecular Origins of the Dynamical Perturbation

PubMed Central

2014-01-01

Protein hydration shell dynamics play an important role in biochemical processes including protein folding, enzyme function, and molecular recognition. We present here a comparison of the reorientation dynamics of individual water molecules within the hydration shell of a series of globular proteins: acetylcholinesterase, subtilisin Carlsberg, lysozyme, and ubiquitin. Molecular dynamics simulations and analytical models are used to access site-resolved information on hydration shell dynamics and to elucidate the molecular origins of the dynamical perturbation of hydration shell water relative to bulk water. We show that all four proteins have very similar hydration shell dynamics, despite their wide range of sizes and functions, and differing secondary structures. We demonstrate that this arises from the similar local surface topology and surface chemical composition of the four proteins, and that such local factors alone are sufficient to rationalize the hydration shell dynamics. We propose that these conclusions can be generalized to a wide range of globular proteins. We also show that protein conformational fluctuations induce a dynamical heterogeneity within the hydration layer. We finally address the effect of confinement on hydration shell dynamics via a site-resolved analysis and connect our results to experiments via the calculation of two-dimensional infrared spectra. PMID:24479585

Pollution source localization in an urban water supply network based on dynamic water demand.

PubMed

Yan, Xuesong; Zhu, Zhixin; Li, Tian

2017-10-27

Urban water supply networks are susceptible to intentional, accidental chemical, and biological pollution, which pose a threat to the health of consumers. In recent years, drinking-water pollution incidents have occurred frequently, seriously endangering social stability and security. The real-time monitoring for water quality can be effectively implemented by placing sensors in the water supply network. However, locating the source of pollution through the data detection obtained by water quality sensors is a challenging problem. The difficulty lies in the limited number of sensors, large number of water supply network nodes, and dynamic user demand for water, which leads the pollution source localization problem to an uncertainty, large-scale, and dynamic optimization problem. In this paper, we mainly study the dynamics of the pollution source localization problem. Previous studies of pollution source localization assume that hydraulic inputs (e.g., water demand of consumers) are known. However, because of the inherent variability of urban water demand, the problem is essentially a fluctuating dynamic problem of consumer's water demand. In this paper, the water demand is considered to be stochastic in nature and can be described using Gaussian model or autoregressive model. On this basis, an optimization algorithm is proposed based on these two dynamic water demand change models to locate the pollution source. The objective of the proposed algorithm is to find the locations and concentrations of pollution sources that meet the minimum between the analogue and detection values of the sensor. Simulation experiments were conducted using two different sizes of urban water supply network data, and the experimental results were compared with those of the standard genetic algorithm.

Dynamics of Water in Gemini Surfactant-Based Lyotropic Liquid Crystals

DOE PAGES

McDaniel, Jesse G.; Mantha, Sriteja; Yethiraj, Arun

2016-09-26

The dynamics of water confined to nanometer-sized domains is important in a variety of applications ranging from proton exchange membranes to crowding effects in biophysics. In this work we study the dynamics of water in gemini surfactant-based lyotropic liquid crystals (LLCs) using molecular dynamics simulations. These systems have well characterized morphologies, e.g., hexagonal, gyroid, and lamellar, and the surfaces of the confining regions can be controlled by modifying the headgroup of the surfactants. This allows one to study the effect of topology, functionalization, and interfacial curvature on the dynamics of confined water. Through analysis of the translational diffusion and rotationalmore » relaxation we conclude that the hydration level and resulting confinement lengthscale is the predominate determiner of the rates of water dynamics, and other effects, namely surface functionality and curvature, are largely secondary. In conclusion, this novel analysis of the water dynamics in these LLC systems provides an important comparison for previous studies of water dynamics in lipid bilayers and reverse micelles.« less

Water dynamics at neutral and ionic interfaces

PubMed Central

Fenn, Emily E.; Wong, Daryl B.; Fayer, M. D.

2009-01-01

The orientational dynamics of water at a neutral surfactant reverse micelle interface are measured with ultrafast infrared spectroscopy of the hydroxyl stretch, and the results are compared to orientational relaxation of water interacting with an ionic interface. The comparison provides insights into the influence of a neutral vs. ionic interface on hydrogen bond dynamics. Measurements are made and analyzed for large nonionic surfactant Igepal CO-520reverse micelles (water nanopool with a 9-nm diameter). The results are compared with those from a previous study of reverse micelles of the same size formed with the ionic surfactant Aerosol-OT (AOT). The results demonstrate that the orientational relaxation times for interfacial water molecules in the two types of reverse micelles are very similar (13 ps for Igepal and 18 ps for AOT) and are significantly slower than that of bulk water (2.6 ps). The comparison of water orientational relaxation at neutral and ionic interfaces shows that the presence of an interface plays the dominant role in determining the hydrogen bond dynamics, whereas the chemical nature of the interface plays a secondary role. PMID:19706895

How proteins modify water dynamics

NASA Astrophysics Data System (ADS)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Much of biology happens at the protein-water interface, so all dynamical processes in this region are of fundamental importance. Local structural fluctuations in the hydration layer can be probed by 17O magnetic relaxation dispersion (MRD), which, at high frequencies, measures the integral of a biaxial rotational time correlation function (TCF)—the integral rotational correlation time. Numerous 17O MRD studies have demonstrated that this correlation time, when averaged over the first hydration shell, is longer than in bulk water by a factor 3-5. This rotational perturbation factor (RPF) has been corroborated by molecular dynamics simulations, which can also reveal the underlying molecular mechanisms. Here, we address several outstanding problems in this area by analyzing an extensive set of molecular dynamics data, including four globular proteins and three water models. The vexed issue of polarity versus topography as the primary determinant of hydration water dynamics is resolved by establishing a protein-invariant exponential dependence of the RPF on a simple confinement index. We conclude that the previously observed correlation of the RPF with surface polarity is a secondary effect of the correlation between polarity and confinement. Water rotation interpolates between a perturbed but bulk-like collective mechanism at low confinement and an exchange-mediated orientational randomization (EMOR) mechanism at high confinement. The EMOR process, which accounts for about half of the RPF, was not recognized in previous simulation studies, where only the early part of the TCF was examined. Based on the analysis of the experimentally relevant TCF over its full time course, we compare simulated and measured RPFs, finding a 30% discrepancy attributable to force field imperfections. We also compute the full 17O MRD profile, including the low-frequency dispersion produced by buried water molecules. Computing a local RPF for each hydration shell, we find that the

Modulators of heterogeneous protein surface water dynamics

NASA Astrophysics Data System (ADS)

Han, Songi

The hydration water that solvates proteins is a major factor in driving or enabling biological events, including protein-protein and protein-ligand interactions. We investigate the role of the protein surface in modulating the hydration water fluctuations on both the picosecond and nanosecond timescale with an emerging experimental NMR technique known as Overhauser Dynamic Nuclear Polarization (ODNP). We carry out site-specific ODNP measurements of the hydration water fluctuations along the surface of Chemotaxis Y (CheY), and correlate the measured fluctuations to hydropathic and topological properties of the CheY surface as derived from molecular dynamics (MD) simulation. Furthermore, we compare hydration water fluctuations measured on the CheY surface to that of other globular proteins, as well as intrinsically disordered proteins, peptides, and liposome surfaces to systematically test characteristic effects of the biomolecular surface on the hydration water dynamics. Our results suggest that the labile (ps) hydration water fluctuations are modulated by the chemical nature of the surface, while the bound (ns) water fluctuations are present on surfaces that feature a rough topology and chemical heterogeneity such as the surface of a folded and structured protein. In collaboration with: Ryan Barnes, Dept of Chemistry and Biochemistry, University of California Santa Barbara

Questa Baseline and Pre-Mining Ground-Water Quality Investigation. 25. Summary of Results and Baseline and Pre-Mining Ground-Water Geochemistry, Red River Valley, Taos County, New Mexico, 2001-2005

USGS Publications Warehouse

Nordstrom, D. Kirk

2008-01-01

-sediment chemistry; geomorphology and its effect on ground-water flow; geophysical studies on depth to ground-water table and depth to bedrock; bedrock fractures and their potential influence on ground-water flow; leaching studies of scars and waste-rock piles; mineralogy and mineral chemistry and their effect on ground-water quality; debris-flow hazards; hydrology and water balance for the Red River Valley; ground-water geochemistry of selected wells undisturbed by mining in the Red River Valley; and quality assurance and quality control of water analyses. Studies aimed specifically at the Straight Creek natural-analog site include electrical surveys; high-resolution seismic survey; age-dating with tritium/helium; water budget; ground-water hydrology and geochemistry; and comparison of mineralogy and lithology to that of the mine site. The highly mineralized and hydrothermally altered volcanic rocks of the Red River Valley contain several percent pyrite in the quartz-sericite-pyrite (QSP) alteration zone, which weather naturally to acid-sulfate surface and ground waters that discharge to the Red River. Weathering of waste-rock piles containing pyrite also contributes acid water that eventually discharges into the Red River. These acid discharges are neutralized by circumneutral-pH, carbonate-buffered surface and ground waters of the Red River. The buffering capacity of the Red River, however, decreases from the town of Red River to the U.S. Geological Survey (USGS) gaging station near Questa. During short, but intense, storm events, the buffering capacity is exceeded and the river becomes acid from the rapid flushing of acidic materials from natural scar areas. The lithology, mineralogy, elevation, and hydrology of the Straight Creek proximal analog site were found to closely approximate those of the mine site with the exception of the mine site?s Sulphur Gulch catchment. Sulphur Gulch contains three subcatchments?upper Sulphur Gulch, Blind Gulch, and Spring Gulc

Nonlinear Dynamic Characteristics of Oil-in-Water Emulsions

NASA Astrophysics Data System (ADS)

Yin, Zhaoqi; Han, Yunfeng; Ren, Yingyu; Yang, Qiuyi; Jin, Ningde

2016-08-01

In this article, the nonlinear dynamic characteristics of oil-in-water emulsions under the addition of surfactant were experimentally investigated. Firstly, based on the vertical upward oil-water two-phase flow experiment in 20 mm inner diameter (ID) testing pipe, dynamic response signals of oil-in-water emulsions were recorded using vertical multiple electrode array (VMEA) sensor. Afterwards, the recurrence plot (RP) algorithm and multi-scale weighted complexity entropy causality plane (MS-WCECP) were employed to analyse the nonlinear characteristics of the signals. The results show that the certainty is decreasing and the randomness is increasing with the increment of surfactant concentration. This article provides a novel method for revealing the nonlinear dynamic characteristics, complexity, and randomness of oil-in-water emulsions with experimental measurement signals.

Climate and geochemistry as drivers of eucalypt diversification in Australia.

PubMed

Bui, E N; Thornhill, A H; González-Orozco, C E; Knerr, N; Miller, J T

2017-05-01

Eucalypts cover most of Australia. Here, we investigate the relative contribution of climate and geochemistry to the distribution and diversity of eucalypts. Using geostatistics, we estimate major element concentrations, pH, and electrical conductivity at sites where eucalypts have been recorded. We compare the median predicted geochemistry and reported substrate for individual species that appear associated with extreme conditions; this provides a partial evaluation of the predictions. We generate a site-by-species matrix by aggregating observations to the centroids of 100-km-wide grid cells, calculate diversity indices, and use numerical ecology methods (ordination, variation partitioning) to investigate the ecology of eucalypts and their response to climatic and geochemical gradients. We find that β-diversity coincides with variations in climatic and geochemical patterns. Climate and geochemistry together account for less than half of the variation in eucalypt species assemblages across Australia but for greater than 80% in areas of high species richness. Climate is more important than geochemistry in explaining eucalypts species distribution and change in assemblages across Australia as a whole but there are correlations between the two sets of environmental variables. Many individual eucalypt species and entire taxonomic sections (Aromatica, Longistylus of subgenus Eucalyptus, Dumaria, and Liberivalvae of subgenus Symphyomyrtus) have distributions affected strongly by geochemistry. We conclude that eucalypt diversity is driven by steep geochemical gradients that have arisen as climate patterns have fluctuated over Australia over the Cenozoic, generally aridifying since the Miocene. The diversification of eucalypts across Australia is thus an excellent example of co-evolution of landscapes and biota in space and time and challenges accepted notions of macroecology. © 2017 John Wiley & Sons Ltd.

Statistical analysis of major ion and trace element geochemistry of water, 1986-2006, at seven wells transecting the freshwater/saline-water interface of the Edwards Aquifer, San Antonio, Texas

USGS Publications Warehouse

Mahler, Barbara J.

2008-01-01

The statistical analyses taken together indicate that the geochemistry at the freshwater-zone wells is more variable than that at the transition-zone wells. The geochemical variability at the freshwater-zone wells might result from dilution of ground water by meteoric water. This is indicated by relatively constant major ion molar ratios; a preponderance of positive correlations between SC, major ions, and trace elements; and a principal components analysis in which the major ions are strongly loaded on the first principal component. Much of the variability at three of the four transition-zone wells might result from the use of different laboratory analytical methods or reporting procedures during the period of sampling. This is reflected by a lack of correlation between SC and major ion concentrations at the transition-zone wells and by a principal components analysis in which the variability is fairly evenly distributed across several principal components. The statistical analyses further indicate that, although the transition-zone wells are less well connected to surficial hydrologic conditions than the freshwater-zone wells, there is some connection but the response time is longer. 

Molecular Dynamics Analysis of Lysozyme Protein in Ethanol- Water Mixed Solvent

DTIC Science & Technology

2012-01-01

molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different concentrations of water-ethanol mixtures as...understood. This work focuses on detailed molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different...using GROMACS molecular dynamics simulation (MD) code. Compared to water environment, the lysozyme structure showed remarkable changes in water

Geochemistry, Comparative Analysis, and Physical and Chemical Characteristics of the Thermal Waters East of Hot Springs National Park, Arkansas, 2006-09

USGS Publications Warehouse

Kresse, Timothy M.; Hays, Phillip D.

2009-01-01

rock collapse for uncased wells completed in highly fractured rock. However, the propagation of newly formed large fractures that potentially could damage well structures or result in pirating of water from production wells appears to be of limited possibility based on review of relevant studies. Characteristics of hydraulic conductivity, storage, and fracture porosity were interpreted from flow rates observed in individual wells completed in the Bigfork Chert and Stanley Shale; from hydrographs produced from continuous measurements of water levels in wells completed in the Arkansas Novaculite, the Bigfork Chert, and Stanley Shale; and from a potentiometric-surface map constructed using water levels in wells throughout the study area. Data gathered from these three separate exercises showed that fracture porosity is much greater in the Bigfork Chert relative to that in the Stanley Shale, shallow groundwater flows from elevated recharge areas with exposures of Bigfork Chert along and into streams within the valleys formed on exposures of the Stanley Shale, and there was no evidence of interbasin transfer of groundwater within the shallow flow system. Fifteen shallow wells and two cold-water springs were sampled from the various exposed formations in the study area to characterize the water quality and geochemistry for the shallow groundwater system and for comparison to the geochemistry of the hot springs in Hot Springs National Park. For the quartz formations (novaculite, chert, and sandstone formations), total dissolved solids concentrations were very low with a median concentration of 23 milligrams per liter, whereas the median concentration for groundwater from the shale formations was 184 milligrams per liter. Ten hot springs in Hot Springs National Park were sampled for the study. Several chemical constituents for the hot springs, including pH, total dissolved solids, major cations and anions, and trace metals, show similarity with the shale formations

Isotope Geochemistry for Comparative Planetology of Exoplanets

NASA Technical Reports Server (NTRS)

Mandt, K. E.; Atreya, S.; Luspay-Kuti, A.; Mousis, O.; Simon, A.; Hofstadter, M. D.

2017-01-01

Isotope geochemistry has played a critical role in understanding processes at work in and the history of solar system bodies. Application of these techniques to exoplanets would be revolutionary and would allow comparative planetology with the formation and evolution of exoplanet systems. The roadmap for comparative planetology of the origins and workings of exoplanets involves isotopic geochemistry efforts in three areas: (1) technology development to expand observations of the isotopic composition of solar system bodies and expand observations to isotopic composition of exoplanet atmospheres; (2) theoretical modeling of how isotopes fractionate and the role they play in evolution of exoplanetary systems, atmospheres, surfaces and interiors; and (3) laboratory studies to constrain isotopic fractionation due to processes at work throughout the solar system.

Glasslike dynamical behavior of the plastocyanin hydration water

NASA Astrophysics Data System (ADS)

Bizzarri, Anna Rita; Paciaroni, Alessandro; Cannistraro, Salvatore

2000-09-01

The dynamical behavior of water around plastocyanin has been investigated in a wide temperature range by molecular dynamics simulation. The mean square displacements of water oxygen atoms show, at long times, a tα trend for all temperatures. Below 150 K, α is constant and equal to 1; at higher temperatures it drops to a value significantly smaller than 1, and thereafter decreases with increasing temperature. The occurrence of such an anomalous diffusion matches the onset of the dynamical transition observed in the protein. The intermediate scattering function of water is characterized, at high temperature, by a stretched exponential decay evolving, at low temperature, toward a two step relaxation behavior, which becomes more evident on increasing the exchanged wave vector q. Both the mean square displacements and the intermediate scattering functions show, beyond the ballistic regime, a plateau, which progressively extends for longer times as long as the temperature is lowered, such behavior reflecting trapping of water molecules within a cage formed by the nearest neighbors. At low temperature, a low frequency broad inelastic peak is observed in the dynamical structure factor of hydration water; such an excess of vibrational modes being reminiscent of the boson peak, characteristic of disordered, amorphous systems. All these features, which are typical of complex systems, can be traced back to the glassy character of the hydration water and suggest a dynamical coupling occurring at the macromolecule-solvent interface.

PREFACE: Dynamic crossover phenomena in water and other glass-forming liquids Dynamic crossover phenomena in water and other glass-forming liquids

NASA Astrophysics Data System (ADS)

Chen, Sow-Hsin; Baglioni, Piero

2012-02-01

This special section has been inspired by the workshop on Dynamic Crossover Phenomena in Water and Other Glass-Forming Liquids, held during November 11-13, 2010 at Pensione Bencistà, Fiesole, Italy, a well-preserved 14th century Italian villa tucked high in the hills overlooking Florence. The meeting, an assembly of world renowned scientists, was organized as a special occasion to celebrate the 75th birthday of Professor Sow-Hsin Chen of MIT, a pioneer in several aspects of complex fluids and soft matter physics. The workshop covered a large variety of experimental and theoretical research topics of current interest related to dynamic crossover phenomena in water and, more generally, in other glass-forming liquids. The 30 invited speakers/lecturers and approximately 60 participants were a select group of prominent physicists and chemists from the USA, Europe, Asia and Mexico, who are actively working in the field. Some highlights of this special issue include the following works. Professor Yamaguchi's group and their collaborators present a neutron spin echo study of the coherent intermediate scattering function of heavy water confined in cylindrical pores of MCM-41-C10 silica material in the temperature range 190-298 K. They clearly show that a fragile-to-strong (FTS) dynamic crossover occurs at about 225 K. They attribute the FTS dynamic crossover to the formation of a tetrahedral-like structure, which is preserved in the bulk-like water confined to the central part of the cylindrical pores. Mamontov and Kolesnikov et al study the collective excitations in an aqueous solution of lithium chloride over a temperature range of 205-270 K using neutron and x-ray Rayleigh-Brillouin (coherent) scattering. They detect both the low-frequency and the high-frequency sounds known to exist in pure bulk water above the melting temperature. They also perform neutron (incoherent) and x-ray (coherent) elastic intensity scan measurements. Clear evidence of the crossover in the

Online analysis: Deeper insights into water quality dynamics in spring water.

PubMed

Page, Rebecca M; Besmer, Michael D; Epting, Jannis; Sigrist, Jürg A; Hammes, Frederik; Huggenberger, Peter

2017-12-01

We have studied the dynamics of water quality in three karst springs taking advantage of new technological developments that enable high-resolution measurements of bacterial load (total cell concentration: TCC) as well as online measurements of abiotic parameters. We developed a novel data analysis approach, using self-organizing maps and non-linear projection methods, to approximate the TCC dynamics using the multivariate data sets of abiotic parameter time-series, thus providing a method that could be implemented in an online water quality management system for water suppliers. The (TCC) data, obtained over several months, provided a good basis to study the microbiological dynamics in detail. Alongside the TCC measurements, online abiotic parameter time-series, including spring discharge, turbidity, spectral absorption coefficient at 254nm (SAC254) and electrical conductivity, were obtained. High-density sampling over an extended period of time, i.e. every 45min for 3months, allowed a detailed analysis of the dynamics in karst spring water quality. Substantial increases in both the TCC and the abiotic parameters followed precipitation events in the catchment area. Differences between the parameter fluctuations were only apparent when analyzed at a high temporal scale. Spring discharge was always the first to react to precipitation events in the catchment area. Lag times between the onset of precipitation and a change in discharge varied between 0.2 and 6.7h, depending on the spring and event. TCC mostly reacted second or approximately concurrent with turbidity and SAC254, whereby the fastest observed reaction in the TCC time series occurred after 2.3h. The methodological approach described here enables a better understanding of bacterial dynamics in karst springs, which can be used to estimate risks and management options to avoid contamination of the drinking water. Copyright © 2017 Elsevier B.V. All rights reserved.

Occurrence and geochemistry of radium in water from principal drinking-water aquifer systems of the United States

USGS Publications Warehouse

Szabo, Z.; dePaul, V.T.; Fischer, J.M.; Kraemer, T.F.; Jacobsen, E.

2012-01-01

competing ions Ca, Mg, Ba and Sr, and occasionally of dissolved solids, K, SO 4 and HCO 3. The other water type to frequently contain elevated concentrations of the Ra radioisotopes was acidic (low pH), and had in places, high concentrations of NO 3 and other acid anions, and on occasion, of the competing divalent cations, Mn and Al. One or the other of these broad water types was commonly present in each of the PAs in which elevated concentrations of combined Ra occurred. Concentrations of 226Ra or 228Ra or combined Ra correlated significantly with those of the above listed water-quality constituents (on the basis of the non-parametric Spearman correlation technique) and loaded on principal components describing the above water types from the entire data set and for samples from the PAs with the highest combined Ra concentrations.Concentrations of 224Ra and 226Ra were significantly correlated to those of 228Ra (Spearman's rank correlation coefficient, +0.236 and +0.326, respectively). Activity ratios of 224Ra/ 228Ra in the water samples were mostly near 1 when concentrations of both isotopes were greater than or equal to 0.037Bq/L (1pCi/L), the level above which analytical results were most reliable. Co-occurrence among these highest concentrations of the Ra radionuclides was most likely in those PAs where chemical conditions are most conducive to Ra mobility (e.g. acidic North Atlantic Coastal Plain). The concentrations of 224Ra were occasionally greater than 0.037Bq/L and the ratios of 224Ra/ 228Ra were generally highest in the PAs composed of alluvial sands and Cretaceous/Tertiary sandstones from the western USA, likely because concentrations of 224Ra are enhanced in solution relative to those of 228Ra by alpha recoil from the aquifer matrix. Rapid adsorption of the two Ra isotopes (controlled by the alkaline and oxic aquifer geochemistry) combined with preferential faster recoil of 224Ra generates a 224Ra/ 228Ra ratio much greater than

Hydration water dynamics and instigation of protein structuralrelaxation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Russo, Daniela; Hura, Greg; Head-Gordon, Teresa

2003-09-01

Until a critical hydration level is reached, proteins do not function. This critical level of hydration is analogous to a similar lack of protein function observed for temperatures below a dynamical temperature range of 180-220K that also is connected to the dynamics of protein surface water. Restoration of some enzymatic activity is observed in partially hydrated protein powders, sometimes corresponding to less than a single hydration layer on the protein surface, which indicates that the dynamical and structural properties of the surface water is intimately connected to protein stability and function. Many elegant studies using both experiment and simulation havemore » contributed important information about protein hydration structure and timescales. The molecular mechanism of the solvent motion that is required to instigate the protein structural relaxation above a critical hydration level or transition temperature has yet to be determined. In this work we use experimental quasi-elastic neutron scattering (QENS) and molecular dynamics simulation to investigate hydration water dynamics near a greatly simplified protein system. We consider the hydration water dynamics near the completely deuterated N-acetyl-leucine-methylamide (NALMA) solute, a hydrophobic amino acid side chain attached to a polar blocked polypeptide backbone, as a function of concentration between 0.5M-2.0M under ambient conditions. We note that roughly 50-60% of a folded protein's surface is equally distributed between hydrophobic and hydrophilic domains, domains whose lengths are on the order of a few water diameters, that justify our study of hydration dynamics of this simple model protein system. The QENS experiment was performed at the NIST Center for Neutron Research, using the disk chopper time of flight spectrometer (DCS). In order to separate the translational and rotational components in the spectra, two sets of experiments were carried out using different incident neutron

Structure and dynamics of water inside hydrophobic and hydrophilic nanotubes

NASA Astrophysics Data System (ADS)

Köhler, Mateus Henrique; Bordin, José Rafael; da Silva, Leandro B.; Barbosa, Marcia C.

2018-01-01

We have used Molecular Dynamics simulations to investigate the structure and dynamics of TIP4P/2005 water confined inside nanotubes. The nanotubes have distinct sizes and were built with hydrophilic or hydrophobic sites, and we compare the water behavior inside each nanotube. Our results shows that the structure and dynamics are strongly influenced by polarity inside narrow nanotubes, where water layers were observed, and the influence is negligible for wider nanotubes, where the water has a bulk-like density profile. As well, we show that water at low density can have a smaller diffusion inside nanotubes than water at higher densities. This result is a consequence of water diffusion anomaly.

Dynamical properties of water in living cells

NASA Astrophysics Data System (ADS)

Piazza, Irina; Cupane, Antonio; Barbier, Emmanuel L.; Rome, Claire; Collomb, Nora; Ollivier, Jacques; Gonzalez, Miguel A.; Natali, Francesca

2018-02-01

With the aim of studying the effect of water dynamics on the properties of biological systems, in this paper, we present a quasi-elastic neutron scattering study on three different types of living cells, differing both in their morphological and tumor properties. The measured scattering signal, which essentially originates from hydrogen atoms present in the investigated systems, has been analyzed using a global fitting strategy using an optimized theoretical model that considers various classes of hydrogen atoms and allows disentangling diffusive and rotational motions. The approach has been carefully validated by checking the reliability of the calculation of parameters and their 99% confidence intervals. We demonstrate that quasi-elastic neutron scattering is a suitable experimental technique to characterize the dynamics of intracellular water in the angstrom/picosecond space/time scale and to investigate the effect of water dynamics on cellular biodiversity.

Ca isotopic geochemistry of an Antarctic aquatic system

USGS Publications Warehouse

Lyons, W. Berry; Bullen, Thomas D.; Welch, Kathleen A.

2017-01-01

The McMurdo Dry Valleys, Antarctica, are a polar desert ecosystem. The hydrologic system of the dry valleys is linked to climate with ephemeral streams that flow from glacial melt during the austral summer. Past climate variations have strongly influenced the closed-basin, chemically stratified lakes on the valley floor. Results of previous work point to important roles for both in-stream processes (e.g., mineral weathering, precipitation and dissolution of salts) and in-lake processes (e.g., mixing with paleo-seawater and calcite precipitation) in determining the geochemistry of these lakes. These processes have a significant influence on calcium (Ca) biogeochemistry in this aquatic ecosystem, and thus variations in Ca stable isotope compositions of the waters can aid in validating the importance of these processes. We have analyzed the Ca stable isotope compositions of streams and lakes in the McMurdo Dry Valleys. The results validate the important roles of weathering of aluminosilicate minerals and/or CaCO3 in the hyporheic zone of the streams, and mixing of lake surface water with paleo-seawater and precipitation of Ca-salts during cryo-concentration events to form the deep lake waters. The lakes in the McMurdo Dry Valleys evolved following different geochemical pathways, evidenced by their unique, nonsystematic Ca isotope signatures.

Geochemistry of and radioactivity in ground water of the Highland Rim and Central Basin aquifer systems, Hickman and Maury counties, Tennessee

USGS Publications Warehouse

Hileman, G.E.; Lee, R.W.

1993-01-01

A reconnaissance of the geochemistry of and radioactivity in ground water from the Highland Rim and Central Basin aquifer systems in Hickman and Maury Counties, Tennessee, was conducted in 1989. Water in both aquifer systems typically is of the calcium or calcium magnesium bicarbonate type, but concentrations of calcium, magnesium, sodium, potassium, chloride, and sulfate are greater in water of the Central Basin system; differences in the concentrations are statistically significant. Dissolution of calcite, magnesium-calcite, dolomite, and gypsum are the primary geochemical processes controlling ground-water chemistry in both aquifer systems. Saturation-state calculations using the computer code WATEQF indicated that ground water from the Central Basin system is more saturated with respect to calcite, dolomite, and gypsum than water from the Highland Rim system. Geochemical environments within each aquifer system are somewhat different with respect to dissolution of magnesium-bearing minerals. Water samples from the Highland Rim system had a fairly constant calcium to magnesium molar ratio, implying congruent dissolution of magnesium-bearing minerals, whereas water samples from the Central Basin system had highly variable ratios, implying either incongruent dissolution or heterogeneity in soluble constituents of the aquifer matrix. Concentrations of radionuclides in water were low and not greatly different between aquifer systems. Median gross alpha activities were 0.54 picocuries per liter in water from each system; median gross beta activities were 1.1 and 2.3 picocuries per liter in water from the Highland Rim and Central Basin systems, respectively. Radon-222 concentrations were 559 and 422 picocuries per liter, respectively. Concentrations of gross alpha and radium in all samples were substantially less than Tennessee?s maximum permissible levels for community water-supply systems. The data indicated no relations between concentrations of dissolved

A simplified model to predict diurnal water temperature dynamics in a shallow tropical water pool.

PubMed

Paaijmans, Krijn P; Heusinkveld, Bert G; Jacobs, Adrie F G

2008-11-01

Water temperature is a critical regulator in the growth and development of malaria mosquito immatures, as they are poikilothermic. Measuring or estimating the diurnal temperature ranges to which these immatures are exposed is of the utmost importance, as these immatures will develop into adults that can transmit malaria. Recent attempts to predict the daily water temperature dynamics in mosquito breeding sites in Kenya have been successful. However, the developed model may be too complex, as the sophisticated equipment that was used for detailed meteorological observations is not widely distributed in Africa, making it difficult to predict the daily water temperature dynamics on a local scale. Therefore, we compared two energy budget models with earlier made observations of the daily water temperature dynamics in a small, shallow and clear water pool (diameter 0.96 m, depth 0.32 m) in Kenya. This paper describes (1) a complex 1-Dimensional model, and (2) a simplified second model, and (3) shows that both models mimic the water temperature dynamics in the water pool accurately. The latter model has the advantage that it only needs common weather data (air temperature, air humidity, wind speed and cloud cover) to estimate the diurnal temperature dynamics in breeding sites of African malaria mosquitoes.

Hydrogen-bond dynamics at the bio-water interface in hydrated proteins: a molecular-dynamics study.

PubMed

Nandi, Prithwish K; English, Niall J; Futera, Zdenek; Benedetto, Antonio

2016-12-21

Water is fundamental to the biochemistry of enzymes. It is well known that without a minimum amount of water, enzymes are not biologically active. Bare minimal solvation for biological function corresponds to about a single layer of water covering enzymes' surfaces. Many contradictory studies on protein-hydration-water-coupled dynamics have been published in recent decades. Following prevailing wisdom, a dynamical crossover in hydration water (at around 220 K for hydrated lysozymes) can trigger larger-amplitude motions of the protein, activating, in turn, biological functions. Here, we present a molecular-dynamics-simulation study on a solvated model protein (hen egg-white lysozyme), in which we determine, inter alia, the relaxation dynamics of the hydrogen-bond network between the protein and its hydration water molecules on a residue-per-residue basis. Hydrogen-bond breakage/formation kinetics is rather heterogeneous in temperature dependence (due to the heterogeneity of the free-energy surface), and is driven by the magnitude of thermal motions of various different protein residues which provide enough thermal energy to overcome energy barriers to rupture their respective hydrogen bonds with water. In particular, arginine residues exhibit the highest number of such hydrogen bonds at low temperatures, losing almost completely such bonding above 230 K. This suggests that hydration water's dynamical crossover, observed experimentally for hydrated lysozymes at ∼220 K, lies not at the origin of the protein residues' larger-amplitude motions, but rather arises as a consequence thereof. This highlights the need for new experimental investigations, and new interpretations to link protein dynamics to functions, in the context of key interrelationships with the solvation layer.

Efficient dynamic scarcity pricing in urban water supply

NASA Astrophysics Data System (ADS)

Lopez-Nicolas, Antonio; Pulido-Velazquez, Manuel; Rougé, Charles; Harou, Julien J.; Escriva-Bou, Alvar

2017-04-01

Water pricing is a key instrument for water demand management. Despite the variety of existing strategies for urban water pricing, urban water rates are often far from reflecting the real value of the resource, which increases with water scarcity. Current water rates do not bring any incentive to reduce water use in water scarcity periods, since they do not send any signal to the users of water scarcity. In California, the recent drought has spurred the implementation of drought surcharges and penalties to reduce residential water use, although it is not a common practice yet. In Europe, the EU Water Framework Directive calls for the implementation of new pricing policies that assure the contribution of water users to the recovery of the cost of water services (financial instrument) while providing adequate incentives for an efficient use of water (economic instrument). Not only financial costs should be recovered but also environmental and resource (opportunity) costs. A dynamic pricing policy is efficient if the prices charged correspond to the marginal economic value of water, which increases with water scarcity and is determined by the value of water for all alternative uses in the basin. Therefore, in the absence of efficient water markets, measuring the opportunity costs of scarce water can only be achieved through an integrated basin-wide hydroeconomic simulation approach. The objective of this work is to design a dynamic water rate for urban water supply accounting for the seasonal marginal value of water in the basin, related to water scarcity. The dynamic pricing policy would send to the users a signal of the economic value of the resource when water is scarce, therefore promoting more efficient water use. The water rate is also designed to simultaneously meet the expected basic requirements for water tariffs: revenue sufficiency (cost recovery) and neutrality, equity and affordability, simplicity and efficiency. A dynamic increasing block rate (IBR

Atomistic details of protein dynamics and the role of hydration water

DOE PAGES

Khodadadi, Sheila; Sokolov, Alexei P.

2016-05-04

The importance of protein dynamics for their biological activity is nowwell recognized. Different experimental and computational techniques have been employed to study protein dynamics, hierarchy of different processes and the coupling between protein and hydration water dynamics. But, understanding the atomistic details of protein dynamics and the role of hydration water remains rather limited. Based on overview of neutron scattering, molecular dynamic simulations, NMR and dielectric spectroscopy results we present a general picture of protein dynamics covering time scales from faster than ps to microseconds and the influence of hydration water on different relaxation processes. Internal protein dynamics spread overmore » a wide time range fromfaster than picosecond to longer than microseconds. We suggest that the structural relaxation in hydrated proteins appears on the microsecond time scale, while faster processes present mostly motion of side groups and some domains. Hydration water plays a crucial role in protein dynamics on all time scales. It controls the coupled protein-hydration water relaxation on 10 100 ps time scale. Our process defines the friction for slower protein dynamics. Analysis suggests that changes in amount of hydration water affect not only general friction, but also influence significantly the protein's energy landscape.« less

Atomistic details of protein dynamics and the role of hydration water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khodadadi, Sheila; Sokolov, Alexei P.

The importance of protein dynamics for their biological activity is nowwell recognized. Different experimental and computational techniques have been employed to study protein dynamics, hierarchy of different processes and the coupling between protein and hydration water dynamics. But, understanding the atomistic details of protein dynamics and the role of hydration water remains rather limited. Based on overview of neutron scattering, molecular dynamic simulations, NMR and dielectric spectroscopy results we present a general picture of protein dynamics covering time scales from faster than ps to microseconds and the influence of hydration water on different relaxation processes. Internal protein dynamics spread overmore » a wide time range fromfaster than picosecond to longer than microseconds. We suggest that the structural relaxation in hydrated proteins appears on the microsecond time scale, while faster processes present mostly motion of side groups and some domains. Hydration water plays a crucial role in protein dynamics on all time scales. It controls the coupled protein-hydration water relaxation on 10 100 ps time scale. Our process defines the friction for slower protein dynamics. Analysis suggests that changes in amount of hydration water affect not only general friction, but also influence significantly the protein's energy landscape.« less

Water Dynamics in the Hydration Shells of Biomolecules

PubMed Central

2017-01-01

The structure and function of biomolecules are strongly influenced by their hydration shells. Structural fluctuations and molecular excitations of hydrating water molecules cover a broad range in space and time, from individual water molecules to larger pools and from femtosecond to microsecond time scales. Recent progress in theory and molecular dynamics simulations as well as in ultrafast vibrational spectroscopy has led to new and detailed insight into fluctuations of water structure, elementary water motions, electric fields at hydrated biointerfaces, and processes of vibrational relaxation and energy dissipation. Here, we review recent advances in both theory and experiment, focusing on hydrated DNA, proteins, and phospholipids, and compare dynamics in the hydration shells to bulk water. PMID:28248491

U.S. National Committee for Geochemistry

ERIC Educational Resources Information Center

Geotimes, 1974

1974-01-01

Reports highlights of the April, 1973 meeting of the U.S. National Committee for Geochemistry. Some of the topics reported on were: The Geophysics Research Board, deep drilling, exchange of geochemists with China and the activities of the Subcommittee on Geochemical Environment in Relation to Health and Disease. (BR)

Impacts of retrogressive thaw slumps on the geochemistry of permafrost catchments, Stony Creek Watershed, NWT

NASA Astrophysics Data System (ADS)

Malone, Laura

Retrogressive thaw slumps are one of the most dramatic thermokarst landforms in periglacial regions. This thesis investigates the impacts of two of the largest hillslope thaw slumps on the geochemistry of periglacial streams on the Peel Plateau, Northwest Territories. It aims to describe the inorganic geochemistry of runoff across active mega-slumps, impacted and pristine tundra streams, as well as that of the ice-rich permafrost exposed in the slump headwalls. Slump runoff is characterized by elevated suspended sediments (911 g/L), high conductivity (2700 microS/cm), and high SO42- (up to 2078 ppm). The runoff originates as a solute-rich meltwater near the slump headwall, and leaches and re-dissolves soluble salts (e.g., gypsum) as it flows along the mudflow. Conductivity increases until the runoff mixes with pristine tundra streams, diluting the slump runoff signal. SO4 2-/Cl- is used as a tracer to isolate the slump runoff signal in impacted waters, and suggests that the contribution of slump runoff to the Peel River has been increasing since the 1960s.

Groundwater geochemistry in the Seminole Well Field, Cedar Rapids, Iowa

USGS Publications Warehouse

Boyd, Robert A.

1999-01-01

The City of Cedar Rapids obtains its municipal water supply from four well fields in an alluvial aquifer along the Cedar River in east-central Iowa. Since 1992, the City and the U.S. Geological Survey have cooperatively studied the groundwater-flow system and water chemistry near the well fields. The geochemistry in the alluvial aquifer near the Seminole Well Field was assessed to identify potentially reactive minerals and possible chemical reactions that produce observed changes in water chemistry. Calcite, dolomite, ferrihydrite, quartz, rhodochrosite, and siderite were identified as potentially reactive minerals by calculating saturation indexes. Aluminosiicate minerals including albite, Ca-montmorillonite, gibbsite, illite, K-feldspar, and kaolinite were identified as potentially reactive minerals using hypothetical saturation indexes calculated with an assumed dissolved aluminum concentration of 1 microgram per liter. Balanced chemical equations derived from inverse-modeling techniques were used to assess chemical reactions as precipitation percolates to the water table. Calcite dissolution was predominate, but aluminosilicate weathering, cation exchange, and redox reactions also likely occurred. Microbial-catalyzed redox reactions altered the chemical composition of water infiltrating from the Cedar River into the alluvial aquifer by consuming dissolved oxygen, reducing nitrate, and increasing dissolved iron and manganese concentrations. Nitrate reduction only occurred in relatively shallow (3 to 7 meters below land surface) groundwater near the Cedar River and did not occur in water infiltrating to deeper zones of the alluvial aquifer.

Water Dynamics at Protein-Protein Interfaces: Molecular Dynamics Study of Virus-Host Receptor Complexes.

PubMed

Dutta, Priyanka; Botlani, Mohsen; Varma, Sameer

2014-12-26

The dynamical properties of water at protein-water interfaces are unlike those in the bulk. Here we utilize molecular dynamics simulations to study water dynamics in interstitial regions between two proteins. We consider two natural protein-protein complexes, one in which the Nipah virus G protein binds to cellular ephrin B2 and the other in which the same G protein binds to ephrin B3. While the two complexes are structurally similar, the two ephrins share only a modest sequence identity of ∼50%. X-ray crystallography also suggests that these interfaces are fairly extensive and contain exceptionally large amounts of waters. We find that while the interstitial waters tend to occupy crystallographic sites, almost all waters exhibit residence times of less than hundred picoseconds in the interstitial region. We also find that while the differences in the sequence of the two ephrins result in quantitative differences in the dynamics of interstitial waters, the trends in the shifts with respect to bulk values are similar. Despite the high wetness of the protein-protein interfaces, the dynamics of interstitial waters are considerably slower compared to the bulk-the interstitial waters diffuse an order of magnitude slower and have 2-3 fold longer hydrogen bond lifetimes and 2-1000 fold slower dipole relaxation rates. To understand the role of interstitial waters, we examine how implicit solvent models compare against explicit solvent models in producing ephrin-induced shifts in the G conformational density. Ephrin-induced shifts in the G conformational density are critical to the allosteric activation of another viral protein that mediates fusion. We find that in comparison with the explicit solvent model, the implicit solvent model predicts a more compact G-B2 interface, presumably because of the absence of discrete waters at the G-B2 interface. Simultaneously, we find that the two models yield strikingly different induced changes in the G conformational density, even

Precambrian organic geochemistry - Preservation of the record

NASA Technical Reports Server (NTRS)

Hayes, J. M.; Wedeking, K. W.; Kaplan, I. R.

1983-01-01

A review of earlier studies is presented, and new results in Precambrian organic geochemistry are discussed. It is pointed out that two lines of evidence can be developed. One is based on structural organic chemistry, while the other is based on isotopic analyses. In the present investigation, the results of both structural and isotopic investigations of Precambrian organic matter are discussed. Processes and products related to organic geochemistry are examined, taking into account the carbon cycle, an approximate view of the principal pathways of carbon cycling associated with organic matter in the present global ecosystem, processes affecting sedimentary organic matter, and distribution and types of organic matter. Attention is given to chemical fossils in Precambrian sediments, kerogen analyses, the determination of the structural characteristics of kerogen, and data concerning the preservation of the Precambrian organic geochemical record.

Insights into Igneous Geochemistry from Trace Element Partitioning

NASA Technical Reports Server (NTRS)

Jones, J. H.; Hanson, B. Z.

2001-01-01

Partitioning of trivalent elements into olivine are used to explore basic issues relevant to igneous geochemistry, such as Henry's law. Additional information is contained in the original extended abstract.

Molecular dynamics simulation of water at mineral surfaces: Structure, dynamics, energetics and hydrogen bonding

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Wang, J.; Kirkpatrick, R.

2006-05-01

Fundamental molecular-level understanding of the properties of aqueous mineral interfaces is of great importance for many geochemical and environmental systems. Interaction between water and mineral surfaces substantially affects the properties of both phases, including the reactivity and functionality of the substrate surface, and the structure, dynamics, and energetics of the near surface aqueous phase. Experimental studies of interfacial water structure and dynamics using surface-sensitive techniques such as sum-frequency vibrational spectroscopy or X-ray and neutron reflectivity are not always possible for many practically important substrates, and their results often require interpretation concerning the atomistic mechanisms responsible for the observed behavior. Molecular computer simulations can provide new insight into the underlying molecular- level relationships between the inorganic substrate structure and composition and the structure, ordering, and dynamics of interfacial water. We have performed a series of molecular dynamics (MD) computer simulations of aqueous interfaces with several silicates (quartz, muscovite, and talc) and hydroxides (brucite, portlandite, gibbsite, Ca/Al and Mg/Al double hydroxides) to quantify the effects of the substrate mineral structure and composition on the structural, transport, and thermodynamic properties of water on these mineral surfaces. Due to the prevalent effects of the development of well-interconnected H-bonding networks across the mineral- water interfaces, all the hydroxide surfaces (including a fully hydroxylated quartz surface) show very similar H2O density profiles perpendicular to the interface. However, the predominant orientations of the interfacial H2O molecules and their detailed 2-dimensional near-surface structure and dynamics parallel to the interface are quite different reflecting the differences in the substrate structural charge distribution and the density and orientations of the surface OH

Rock geochemistry related to mineralization processes in geothermal areas

NASA Astrophysics Data System (ADS)

Kausar, A. Al; Indarto, S.; Setiawan, I.

2018-02-01

Abundant geothermal systems in Indonesia suggest high heat and mass transfer associated with recent or paleovolcanic arcs. In the active geothermal system, the upflow of mixed fluid between late stage hydrothermal and meteoric water might contain mass of minerals associated with epithermal mineralisation process as exemplified at Lihir gold mine in Papua New Guinea. In Indonesia, there is a lack of study related to the precious metals occurrence within active geothermal area. Therefore, in this paper, we investigate the possibility of mineralization process in active geothermal area of Guci, Central Java by using geochemical analysis. There are a lot of conducted geochemical analysis of water, soil and gas by mapping the temperature, pH, Hg and CO2 distribution, and estimating subsurface temperature based on geothermometry approach. Then we also apply rock geochemistry to find minerals that indicate the presence of mineralization. The result from selected geothermal area shows the presence of pyrite and chalcopyrite minerals on the laharic breccias at Kali Putih, Sudikampir. Mineralization is formed within host rock and the veins are associated with gold polymetallic mineralization.

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

DOE PAGES

Chen, Ying; Bylaska, Eric J.; Weare, John H.

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Ying; Bylaska, Eric J.; Weare, John H.

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite (α-Fe(OOH). Ab-initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Here, several exchange correlation functionals were employed (PBE96, PBE96+Grimme, and PBE0) in the simulations of a (3 x 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a=30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick).

Protein dynamics in organic media at varying water activity studied by molecular dynamics simulation.

PubMed

Wedberg, Rasmus; Abildskov, Jens; Peters, Günther H

2012-03-01

In nonaqueous enzymology, control of enzyme hydration is commonly approached by fixing the thermodynamic water activity of the medium. In this work, we present a strategy for evaluating the water activity in molecular dynamics simulations of proteins in water/organic solvent mixtures. The method relies on determining the water content of the bulk phase and uses a combination of Kirkwood-Buff theory and free energy calculations to determine corresponding activity coefficients. We apply the method in a molecular dynamics study of Candida antarctica lipase B in pure water and the organic solvents methanol, tert-butyl alcohol, methyl tert-butyl ether, and hexane, each mixture at five different water activities. It is shown that similar water activity yields similar enzyme hydration in the different solvents. However, both solvent and water activity are shown to have profound effects on enzyme structure and flexibility.

Teaching Environmental Geochemistry: An Authentic Inquiry Approach

ERIC Educational Resources Information Center

Koretsky, Carla M.; Petcovic, Heather L.; Rowbotham, Katherine L.

2012-01-01

A field-based environmental geochemistry course was developed at Western Michigan University for undergraduate geosciences and environmental studies students to (1) improve student understanding of complex environmental systems, specifically targeting lake systems; (2) facilitate student development of professional-level, field- and…

A coupled human-water system from a systems dynamics perspective

NASA Astrophysics Data System (ADS)

Kuil, Linda; Blöschl, Günter; Carr, Gemma

2013-04-01

Traditionally, models used in hydrological studies have frequently assumed stationarity. Moreover, human-induced water resources management activities are often included as external forcings in water cycle dynamics. However, considering humans' current impact on the water cycle in terms of a growing population, river basins increasingly being managed and a climate considerably changing, it has recently been questioned whether this is still correct. Furthermore, research directed at the evolution of water resources and society has shown that the components constituting the human-water system are changing interdependently. Goal of this study is therefore to approach water cycle dynamics from an integrated perspective in which humans are considered as endogenous forces to the system. The method used to model a coupled, urban human-water system is system dynamics. In system dynamics, particular emphasis is placed on feedback loops resulting in dynamic behavior. Time delays and non-linearity can relatively easily be included, making the method appropriate for studying complex systems that change over time. The approach of this study is as follows. First, a conceptual model is created incorporating the key components of the urban human-water system. Subsequently, only those components are selected that are both relevant and show causal loop behavior. Lastly, the causal narratives are translated into mathematical relationships. The outcome will be a simple model that shows only those characteristics with which we are able to explore the two-way coupling between the societal behavior and the water system we depend on.

Molecular dynamics studies of interfacial water at the alumina surface.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Argyris, Dr. Dimitrios; Ho, Thomas; Cole, David

2011-01-01

Interfacial water properties at the alumina surface were investigated via all-atom equilibrium molecular dynamics simulations at ambient temperature. Al-terminated and OH-terminated alumina surfaces were considered to assess the structural and dynamic behavior of the first few hydration layers in contact with the substrates. Density profiles suggest water layering up to {approx}10 {angstrom} from the solid substrate. Planar density distribution data indicate that water molecules in the first interfacial layer are organized in well-defined patterns dictated by the atomic terminations of the alumina surface. Interfacial water exhibits preferential orientation and delayed dynamics compared to bulk water. Water exhibits bulk-like behavior atmore » distances greater than {approx}10 {angstrom} from the substrate. The formation of an extended hydrogen bond network within the first few hydration layers illustrates the significance of water?water interactions on the structural properties at the interface.« less

Lake Qinghai sediment geochemistry linked to hydroclimate variability since the last glacial

NASA Astrophysics Data System (ADS)

Jin, Zhangdong; An, Zhisheng; Yu, Jimin; Li, Fuchun; Zhang, Fei

2015-08-01

Geochemistry of basin sediments from semi-arid regions is valuable to understand past hydroclimatic changes. Here, we investigate the links of sedimentary geochemistry (Rb, Sr, Ca/Zr, TOC, and %CaCO3), carbonate mineralogy and ostracod shell δ18O of Lake Qinghai, a basin proximal to major dust production centers at mid-latitudes of the Northern Hemisphere, to changes in depositional conditions and hydroclimate during the past 32 ka. Surface lacustrine sediments are characterized by low-Rb, high-Sr, low-Rb/Sr, high-%CaCO3 and high-Ca/Zr values, in contrast to the chemical compositions of eolian loess (high-Rb, low-Sr, high-Rb/Sr, low-%CaCO3, and low-Ca/Zr). A direct comparison of soluble Ca and Sr in two short cores with instrumental water discharge data suggests that lacustrine precipitates in Lake Qinghai are dominated by authigenic aragonite formed under Ca2+-limited water conditions, and that the accumulation rate of aragonite dominantly depends on solute fluxes into the lake during the rainy seasons (late May to September). Our high-resolution down-core records show that sediments during the last glacial (∼32-19.8 ka) had high-Rb, low-Sr, low-%CaCO3, and low-Ca/Zr, indicating eolian dust (loess) accumulation in a desiccated basin under dry glacial conditions, further supported by grain size and pollen results. This type of sedimentation was maintained during the last deglacial (∼19.8-11.5 ka), but interrupted by episodic lacustrine precipitates with high-Sr, high-%CaCO3, high-Ca/Zr, and low-Rb. At ∼11.5 ka, sedimentary Rb/Sr, Ca/Zr, %CaCO3 and TOC show dramatic and permanent changes, implying an abrupt shift in the atmospheric circulation at the onset of the Holocene in the Lake Qinghai region. Lacustrine precipitates have persisted throughout the Holocene with a maximum during the early to mid-Holocene (∼10.5-8.0 ka). Since ∼8.0 ka, the gradual and significant decreases in aragonite and Sr accumulations in tandem with increasing dust deposit and

Factors affecting the geochemistry of a thick, subbituminous coal bed in the Powder River Basin: volcanic, detrital, and peat-forming processes

USGS Publications Warehouse

Crowley, S.S.; Ruppert, L.F.; Belkin, H.E.; Stanton, R.W.; Moore, T.A.

1993-01-01

The inorganic geochemistry and mineralogy of three cores from the Anderson-Dietz 1 coal bed, a 15.2-m-thick subbituminous coal bed in the Tongue River Member (Paleocene) of the Fort Union Formation, were examined (1) to determine if the cores could be correlated by geochemical composition alone over a total distance of 2 km and (2) to identify the major factors that influenced the geochemistry of the coal bed. Chemical data (46 elements on a coal-ash basis) for 81 coal samples and 4 carbonaceous rock samples, with most samples representing a 0.6-m-thick (2-ft) interval of core, were grouped into compositional clusters by means of cluster analysis. Seven major clusters were produced; two of these clusters can be used to correlate the coal bed throughout the study area. Data from scanning electron and optical microscope analyses indicate that several factors influenced the geochemistry of the Anderson-Dietz 1 coal bed. The majority of mineral grains in the coal bed are interpreted to be detrital (water borne); evidence includes the presence of rounded to subrounded quartz grains having two-phase, aqueous fluid inclusions characteristic of hydrothermal or low-to-moderate grade metamorphic quartz. These quartz grains are found throughout the coal bed but are most abundant in samples from the midpart of the bed, which was influenced by detrital input associated with the deposition of the clastic rocks that form the split between the Anderson and Dietz 1 coal beds 900 m to the east of the study area. In addition to the detrital minerals mentioned above, volcanic ash that was fluvially transported to the sites of peat deposition or possibly deposited as air-fall volcanic ash also affected the geochemistry of the coal bed. For example, crandallite(?), a mineral reported to form as an alteration product of volcanic ash, is found in seven samples from the coal bed. The presence of quartz grains containing silicate-melt inclusions in eight samples from the coal bed

Geochemistry of Peralkaline Melts at Kone Volcanic Complex, Main Ethiopian Rift

NASA Astrophysics Data System (ADS)

Iddon, F. E.; Edmonds, M.; Jackson, C.; Hutchison, W.; Mather, T. A.; Fontijn, K.; Pyle, D. M.

2016-12-01

The East Africa rift system (EARS) is the archetypal example of continental rifting, with the Main Ethiopian rift (MER) segment offering a unique opportunity to examine the dynamics of peralkaline magmas; the development of central volcanoes; melt distribution and transport in the crust; the volatile budgets of rift magmas and their implications for the formation of ore deposits. The alkali- and halogen-rich magmas of the MER differ from their calc-alkaline counterparts in other settings due to their lower viscosities and higher volatile contents, which have important implications for magma transport, reservoir dynamics and eruptive hazards. The high halogen contents of the magmas give rise to halogen-rich vapor which has the capacity to transport and concentrate metals and REE. The Kone Volcanic complex is one of the lesser studied Quaternary peralkaline centres, located on the axial portion of the MER. It comprises two superimposed calderas, surrounded by ignimbrite deposits and unwelded felsic pyroclastic material, small basaltic vents and rhyolitic domes. Unusually for the central volcanoes of the MER, the caldera has refilled with basaltic lava, not pyroclastic material. We use whole rock and micro-analysis to characterize a range of Kone tephras, glasses, crystal phases and melt inclusions in terms of major, trace and volatile element abundances, alongside detailed textural analysis using QEMSCAN and SEM. The whole rock geochemistry reflects the clear peralkaline nature of the suite, with a distinct compositional gap between 50 wt% and 65 wt% SiO2, controlled largely by fractional crystallization. Trace element systematics illustrate that trachytes entrain alkali feldspars, with the crystal cargo of the entire suite reflecting the structure of the magma reservoir at depth, with liquid-rich lenses and regions of syenitic mush. Melt inclusion geochemistry allows reconstruction of complex, multiphase differentiation processes and the exsolution of both a vapor

Evaluating Water Conservation and Reuse Policies Using a Dynamic Water Balance Model

NASA Astrophysics Data System (ADS)

Qaiser, Kamal; Ahmad, Sajjad; Johnson, Walter; Batista, Jacimaria R.

2013-02-01

A dynamic water balance model is created to examine the effects of different water conservation policies and recycled water use on water demand and supply in a region faced with water shortages and significant population growth, the Las Vegas Valley (LVV). The model, developed using system dynamics approach, includes an unusual component of the water system, return flow credits, where credits are accrued for returning treated wastewater to the water supply source. In LVV, Lake Mead serves as, both the drinking water source and the receiving body for treated wastewater. LVV has a consumptive use allocation from Lake Mead but return flow credits allow the water agency to pull out additional water equal to the amount returned as treated wastewater. This backdrop results in a scenario in which conservation may cause a decline in the available water supply. Current water use in LVV is 945 lpcd (250 gpcd), which the water agency aims to reduce to 752 lpcd (199 gpcd) by 2035, mainly through water conservation. Different conservation policies focused on indoor and outdoor water use, along with different population growth scenarios, are modeled for their effects on the water demand and supply. Major contribution of this study is in highlighting the importance of outdoor water conservation and the effectiveness of reducing population growth rate in addressing the future water shortages. The water agency target to decrease consumption, if met completely through outdoor conservation, coupled with lower population growth rate, can potentially satisfy the Valley's water demands through 2035.

Evaluating water conservation and reuse policies using a dynamic water balance model.

PubMed

Qaiser, Kamal; Ahmad, Sajjad; Johnson, Walter; Batista, Jacimaria R

2013-02-01

A dynamic water balance model is created to examine the effects of different water conservation policies and recycled water use on water demand and supply in a region faced with water shortages and significant population growth, the Las Vegas Valley (LVV). The model, developed using system dynamics approach, includes an unusual component of the water system, return flow credits, where credits are accrued for returning treated wastewater to the water supply source. In LVV, Lake Mead serves as, both the drinking water source and the receiving body for treated wastewater. LVV has a consumptive use allocation from Lake Mead but return flow credits allow the water agency to pull out additional water equal to the amount returned as treated wastewater. This backdrop results in a scenario in which conservation may cause a decline in the available water supply. Current water use in LVV is 945 lpcd (250 gpcd), which the water agency aims to reduce to 752 lpcd (199 gpcd) by 2035, mainly through water conservation. Different conservation policies focused on indoor and outdoor water use, along with different population growth scenarios, are modeled for their effects on the water demand and supply. Major contribution of this study is in highlighting the importance of outdoor water conservation and the effectiveness of reducing population growth rate in addressing the future water shortages. The water agency target to decrease consumption, if met completely through outdoor conservation, coupled with lower population growth rate, can potentially satisfy the Valley's water demands through 2035.

Interaction of Land Management Intensity and Micro-topography Controls on Geochemistry of Raindrop-Liberated/Mobilized Soil Particles

NASA Astrophysics Data System (ADS)

Hou, T.; Filley, T. R.; Berry, T.; Singh, S.; Hughes, M.; Tong, Y.; Papanicolaou, T.; Wacha, K.; Wilson, C. G.; Chaubey, I.

2017-12-01

The dynamics of raindrop-induced breakdown of soil aggregates, a critical factor in the initial process of surface erosion and lateral redistribution of soil, are strongly tied to land use intensity. What is unclear however is the relative control of rain and mechanical disturbance on the development of landscape-level heterogeneity in surface soil geochemistry. We used artificial rainfall simulated experiments including an aggregate stability test and time course rainfall-erosional test to evaluate the role of management intensity and micro-topography on the geochemistry of raindrop-liberated/mobilized particles from landscapes in southeastern Iowa. Comparing restored prairie, conservation tillage, and conventional tillage sites we found, and with a trend toward increasing tillage intensity, a decrease in aggregate stability and raindrop-liberated particles that were lower in organic carbon, nitrogen, and plant-derived biopolymers, while containing higher proportions of microbially-processed nitrogen than the raindrop stable aggregates. Time evolution of the geochemistry (e.g. elemental, stable isotope, and biopolymer composition) of transported soil particles exhibited distinct patterns based upon both position of the hillslope and oriented soil roughness. Additionally, in the restored prairie, raindrop liberated particles had identical geochemical composition to the raindrop stable aggregates. Our results demonstrate that agricultural sites under intensive tillage have not only a greater potential to liberate and mobilize soil particles during storms, but the mobilized particles will have a distinct chemical character based on tillage intensity, hillslope position and oriented roughness thus lead to a greater potential for landscape level heterogeneity in surface and buried soil chemistry upon mobilization and burial.

Dynamic Stabilization of Metal Oxide–Water Interfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

McBriarty, Martin E.; von Rudorff, Guido Falk; Stubbs, Joanne E.

2017-02-08

The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (1102) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locationsmore » and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pKa prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide–water interfaces.« less

Thermodynamics and dynamics of supercooled water

NASA Astrophysics Data System (ADS)

Stokely, Kevin C.

This thesis utilizes the methods of statistical physics and computer simulation to study the thermodynamic and dynamic behavior of liquid water at supercooled temperatures. The behavior of water deviates from that of a simple liquid in a number of remarkable ways, many of which become more apparent as the liquid is supercooled below its equilibrium freezing temperature. Yet, due to nucleation to the crystalline state, a large region of the phase diagram of the supercooled liquid remains unexplored. We make use of a simple model for liquid water to shed light on the behavior of real water in the experimentally inaccessible region. The model predicts a line of phase transitions in the pressure—temperature plane, between high- and low-density forms of liquid water, ending in a liquid-liquid critical point (LLCP). Such a LLCP provides a thermodynamic origin for one of liquid water's anomalies—the rapid rise, and extrapolated divergence, of thermodynamic response functions upon cooling. We find one such response function, the isobaric specific heat, CP, displays two distinct maxima as a function of temperature T in the supercooled region. One maximum is a consequence of the directional nature of hydrogen (H) bonding among molecules; the other is a consequence of the cooperative nature of H bonding. With pressurization, these two maxima move closer in T, finally coinciding at the LLCP. This suggests that measurement of CP far from any LLCP could provide evidence for the existence of water's LLCP. Recent experiments find that the T-dependence of the characteristic time for H bond rearrangement displays three distinct regimes. Our observed behavior of CP, combined with Adam-Gibbs theory, allows for a thermodynamic interpretation of this feature of water's dynamics. The dynamics of the model are also measured directly by a Monte Carlo procedure, and are found in agreement with experiment. Further, the model allows the directional and cooperative components of the H bond

Modeling the Dynamics of Soil Structure and Water in Agricultural Soil

NASA Astrophysics Data System (ADS)

Weller, U.; Lang, B.; Rabot, E.; Stössel, B.; Urbanski, L.; Vogel, H. J.; Wiesmeier, M.; Wollschlaeger, U.

2017-12-01

The impact of agricultural management on soil functions is manifold and severe. It has both positive and adverse influence. Our goal is to develop model tools quantifying the agricultural impact on soil functions based on a mechanistic understanding of soil processes to support farmers and decision makers. The modeling approach is based on defining relevant soil components, i.e. soil matrix, macropores, organisms, roots and organic matter. They interact and form the soil's macroscopic properties and functions including water and gas dynamics, and biochemical cycles. Based on existing literature information we derive functional interaction processes and combine them in a network of dynamic soil components. In agricultural soils, a major issue is linked to changes in soil structure and their influence on water dynamics. Compaction processes are well studied in literature, but for the resilience due to root growth and activity of soil organisms the information is scarcer. We implement structural dynamics into soil water and gas simulations using a lumped model that is both coarse enough to allow extensive model runs while still preserving some important, yet rarely modeled phenomenons like preferential flow, hysteretic and dynamic behavior. For simulating water dynamics, at each depth, the model assumes water at different binding energies depending on soil structure, i.e. the pore size distribution. Non-equilibrium is postulated, meaning that free water may occur even if the soil is not fully saturated. All energy levels are interconnected allowing water to move, both within a spatial node, and between neighboring nodes (adding gravity). Structure dynamics alters the capacity of this water compartments, and the conductance of its connections. Connections are switched on and off depending on whether their sources contain water or their targets have free capacity. This leads to piecewise linear system behavior that allows fast calculation for extended time steps. Based

Modelling soil-water dynamics in the rootzone of structured and water-repellent soils

NASA Astrophysics Data System (ADS)

Brown, Hamish; Carrick, Sam; Müller, Karin; Thomas, Steve; Sharp, Joanna; Cichota, Rogerio; Holzworth, Dean; Clothier, Brent

2018-04-01

In modelling the hydrology of Earth's critical zone, there are two major challenges. The first is to understand and model the processes of infiltration, runoff, redistribution and root-water uptake in structured soils that exhibit preferential flows through macropore networks. The other challenge is to parametrise and model the impact of ephemeral hydrophobicity of water-repellent soils. Here we have developed a soil-water model, which is based on physical principles, yet possesses simple functionality to enable easier parameterisation, so as to predict soil-water dynamics in structured soils displaying time-varying degrees of hydrophobicity. Our model, WEIRDO (Water Evapotranspiration Infiltration Redistribution Drainage runOff), has been developed in the APSIM Next Generation platform (Agricultural Production Systems sIMulation). The model operates on an hourly time-step. The repository for this open-source code is https://github.com/APSIMInitiative/ApsimX. We have carried out sensitivity tests to show how WEIRDO predicts infiltration, drainage, redistribution, transpiration and soil-water evaporation for three distinctly different soil textures displaying differing hydraulic properties. These three soils were drawn from the UNSODA (Unsaturated SOil hydraulic Database) soils database of the United States Department of Agriculture (USDA). We show how preferential flow process and hydrophobicity determine the spatio-temporal pattern of soil-water dynamics. Finally, we have validated WEIRDO by comparing its predictions against three years of soil-water content measurements made under an irrigated alfalfa (Medicago sativa L.) trial. The results provide validation of the model's ability to simulate soil-water dynamics in structured soils.

Dynamics of water absorption through superabsorbent polymer

NASA Astrophysics Data System (ADS)

Chang, Sooyoung; Kim, Wonjung

2017-11-01

Superabsorbent polymers (SAPs) consist of hydrophilic cross-linked polymer networks that can absorb and retain a great amount of water relative to their own mass, so that they are widely used for disposable diapers and holding soil moisture in agriculture. SAPs are typically available in the form of submillimeter-sized particles, and the water absorption is driven by capillary flows between particles as well as diffusion that entail swelling. Although the control of water absorption of SAPs is important in engineering applications, but the dynamics of water absorption in SAP particles has not been fully understood. We examine the dynamics of the water absorption of sodium polyacrylate, one of the most common SAP. We experimentally measured the water absorption of sodium polyacrylate particles in one-dimensional confined channel. The water flows through the particles were analyzed by capillarity dominant at the early stage and by diffusion involving volume expansion critical at a later stage. The results provide a quantitative basis of the hydrodynamic analysis of the water flow through SAP particles from a macroscopic point of view, facilitating the prediction of water uptake of SAPs in hygienic and agricultural applications. This work was supported by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP) (No.2015R1A2A2A04006181).

Interventions and Interactions: Understanding Coupled Human-Water Dynamics for Improved Water Resources Management in the Himalayas

NASA Astrophysics Data System (ADS)

Crootof, A.

2017-12-01

Understanding coupled human-water dynamics offers valuable insights to address fundamental water resources challenges posed by environmental change. With hydropower reshaping human-water interactions in mountain river basins, there is a need for a socio-hydrology framework—which examines two-way feedback loops between human and water systems—to more effectively manage water resources. This paper explores the cross-scalar interactions and feedback loops between human and water systems in river basins affected by run-of-the-river hydropower and highlights the utility of a socio-hydrology perspectives to enhance water management in the face of environmental change. In the Himalayas, the rapid expansion of run-of-the-river hydropower—which diverts streamflow for energy generation—is reconfiguring the availability, location, and timing of water resources. This technological intervention in the river basin not only alters hydrologic dyanmics but also shapes social outcomes. Using hydropower development in the highlands of Uttarakhand, India as a case study, I first illustrate how run-of-the-river projects transform human-water dynamics by reshaping the social and physical landscape of a river basin. Second, I emphasize how examining cross-scalar feedbacks among structural dynamics, social outcomes, and values and norms in this coupled human-water system can inform water management. Third, I present hydrological and social literature, raised separately, to indicate collaborative research needs and knowledge gaps for coupled human-water systems affected by run-of-the-river hydropower. The results underscore the need to understand coupled human-water dynamics to improve water resources management in the face of environmental change.

Sedimentary basin geochemistry and fluid/rock interactions workshop

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1991-12-31

Fundamental research related to organic geochemistry, fluid-rock interactions, and the processes by which fluids migrate through basins has long been a part of the U.S. Department of Energy Geosciences program. Objectives of this program were to emphasize those principles and processes which would be applicable to a wide range of problems associated with petroleum discovery, occurrence and extraction, waste disposal of all kinds, and environmental management. To gain a better understanding of the progress being made in understanding basinal fluids, their geochemistry and movement, and related research, and to enhance communication and interaction between principal investigators and DOE and othermore » Federal program managers interested in this topic, this workshop was organized by the School of Geology and Geophysics and held in Norman, Oklahoma in November, 1991.« less

Structure and dynamics of protein waters revealed by radiolysis and mass spectrometry

PubMed Central

Gupta, Sayan; D’Mello, Rhijuta; Chance, Mark R.

2012-01-01

Water is critical for the structure, stability, and functions of macromolecules. Diffraction and NMR studies have revealed structure and dynamics of bound waters at atomic resolution. However, localizing the sites and measuring the dynamics of bound waters, particularly on timescales relevant to catalysis and macromolecular assembly, is quite challenging. Here we demonstrate two techniques: first, temperature-dependent radiolytic hydroxyl radical labeling with a mass spectrometry (MS)-based readout to identify sites of bulk and bound water interactions with surface and internal residue side chains, and second, H218O radiolytic exchange coupled MS to measure the millisecond dynamics of bound water interactions with various internal residue side chains. Through an application of the methods to cytochrome c and ubiquitin, we identify sites of water binding and measure the millisecond dynamics of bound waters in protein crevices. As these MS-based techniques are very sensitive and not protein size limited, they promise to provide unique insights into protein–water interactions and water dynamics for both small and large proteins and their complexes. PMID:22927377

The data of geochemistry

USGS Publications Warehouse

Clarke, Frank Wigglesworth

1924-01-01

Upon the subject of geochemistry a vast literature exists, but it is widely scattered and portions of it are difficult of access. The general treatises, like the classical works of Bischof and of Koth, are not recent, and great masses of modern data are as yet uncorrelated. The American material alone is singularly rich, but most of it has been accumulated since Roth's treatise was published. The science of chemistry, moreover, has undergone great changes during the last 25 years, and many subjects now appear under new and generally unfamiliar aspects. The methods and principles of physical chemistry are being more and more applied to the solution of geochemical problems,1 as is shown by the well-known researches of Van't Hoff upon the Stassfurt salts and the magmatic studies of Vogt, Doelter, and others. The great work in progress at the geophysical laboratory of the Carnegie Institution is another illustration of the change now taking place in geochemical investigation. To bring some of the data together, to formulate a few of the problems and to present certain general conclusions in their modern form are the purposes of this memoir. It is not an exhaustive monograph upon geochemistry, but rather a critical summary of what is now known, and a guide to the more important literature of the subject. If it does no more than to make existing data available to the reader, its preparation will be justified.

Phase transitions and dynamics of bulk and interfacial water.

PubMed

Franzese, G; Hernando-Martínez, A; Kumar, P; Mazza, M G; Stokely, K; Strekalova, E G; de los Santos, F; Stanley, H E

2010-07-21

New experiments on water at the surface of proteins at very low temperature display intriguing dynamic behaviors. The extreme conditions of these experiments make it difficult to explore the wide range of thermodynamic state points needed to offer a suitable interpretation. Detailed simulations suffer from the same problem, where equilibration times at low temperature become extremely long. We show how Monte Carlo simulations and mean field calculations using a tractable model of water help interpret the experimental results. Here we summarize the results for bulk water and investigate the thermodynamic and dynamic properties of supercooled water at an interface.

Structure and Dynamics of Water Confined in Imogolite Nanotubes.

PubMed

Scalfi, Laura; Fraux, Guillaume; Boutin, Anne; Coudert, François-Xavier

2018-06-12

We have studied the properties of water adsorbed inside nanotubes of hydrophilic imogolite, an aluminum silicate clay mineral, by means of molecular simulations. We used a classical force field to describe the water and the flexible imogolite nanotube and validated it against the data obtained from first-principles molecular dynamics. With it, we observe a strong structuration of the water confined in the nanotube, with specific adsorption sites and a distribution of hydrogen bond patterns. The combination of number of adsorption sites, their geometry, and the preferential tetrahedral hydrogen bonding pattern of water leads to frustration and disorder. We further characterize the dynamics of the water, as well as the hydrogen bonds formed between water molecules and the nanotube, which is found to be more than 1 order of magnitude longer than water-water hydrogen bonds.

Efficacy of Biostimulation for Uranium Sequestration: Coupled Effects Sediment/Groundwater Geochemistry and Microbiology

NASA Astrophysics Data System (ADS)

Xu, J.; Veeramani, H.; Qafoku, N. P.; Singh, G.; Pruden, A.; Kukkadapu, R. K.; Hochella, M. F., Jr.

2015-12-01

effectively achieved under predominantly sulfate-reducing conditions in sediment microenvironments when bioavailable iron (III) (oxyhydr)oxides are mostly depleted, and provide insight into the integrated roles of sediment geochemistry, mineralogy, and bacterial population dynamics.

10 CFR 960.4-2-2 - Geochemistry.

Code of Federal Regulations, 2010 CFR

2010-01-01

... REPOSITORY Postclosure Guidelines § 960.4-2-2 Geochemistry. (a) Qualifying condition. The present and... future, not affect or would favorably affect the ability of the geologic repository to isolate the waste... subjected to expected repository conditions, would remain unaltered or would alter to mineral assemblages...

Petrology and Geochemistry of the NWA 3368 Eucrite

NASA Astrophysics Data System (ADS)

Gardner, K. G.; Lauretta, D. S.; Hill, D. H.; Goreva, J. S.; Domanik, K. J.; Franchi, I. A.; Drake, M. J.

2006-03-01

We report the petrology and geochemistry of NWA 3368, a new non-cumulate, monomict eucrite breccia with a variety of clast sizes and a pink-tinted matrix. Analytical techniques include electron microprobe, INAA, and ICP-MS.

Water, gravity and trees: Relationship of tree-ring widths and total water storage dynamics

NASA Astrophysics Data System (ADS)

Creutzfeldt, B.; Heinrich, I.; Merz, B.; Blume, T.; Güntner, A.

2012-04-01

Water stored in the subsurface as groundwater or soil moisture is the main fresh water source not only for drinking water and food production but also for the natural vegetation. In a changing environment water availability becomes a critical issue in many different regions. Long-term observations of the past are needed to improve the understanding of the hydrological system and the prediction of future developments. Tree ring data have repeatedly proved to be valuable sources for reconstructing long-term climate dynamics, e.g. temperature, precipitation and different hydrological variables. In water-limited environments, tree growth is primarily influenced by total water stored in the subsurface and hence, tree-ring records usually contain information about subsurface water storage. The challenge is to retrieve the information on total water storage from tree rings, because a training dataset of water stored in the sub-surface is required for calibration against the tree-ring series. However, measuring water stored in the subsurface is notoriously difficult. We here present high-precision temporal gravimeter measurements which allow for the depth-integrated quantification of total water storage dynamics at the field scale. In this study, we evaluate the relationship of total water storage change and tree ring growth also in the context of the complex interactions of other meteorological forcing factors. A tree-ring chronology was derived from a Norway spruce stand in the Bavarian Forest, Germany. Total water storage dynamics were measured directly by the superconducting gravimeter of the Geodetic Observatory Wettzell for a 9-years period. Time series were extended to 63-years period by a hydrological model using gravity data as the only calibration constrain. Finally, water storage changes were reconstructed based on the relationship between the hydrological model and the tree-ring chronology. Measurement results indicate that tree-ring growth is primarily

Subseabed Disposal Project annual report, FY85 to termination of project: Physical Oceanography and Water Column Geochemistry Studies, October 1984 through May 1986

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kupferman, S.L.

This report covers the work of the Physical Oceanography and Water Column Geochemistry (POWCG) Studies Group of the Subseabed Disposal Project (SDP) from October 1984 to termination of the project in May 1986. The overview of the work includes an introduction, general descriptions of the activities, and a summary. Detailed discussions are included as appendices. During the period of this report the POWCG Studies Group held a meeting to develop a long-term research plan for the Nares Abyssal Plain, which was recently designated as a study area for the Environmental Study Group of the SDP. The POWCG Studies Group hasmore » also planned and participated in two interdisciplinary oceanographic missions to the Nares which have resulted in the acquisition of data and samples which can be used to begin to understand the workings of the ecosystem at the site, and for developing a preliminary site assessment. The papers in the appendices have been processed for inclusion in the Energy Data Base.« less

Geochemistry in Action: Watch a Dripstone Grow!

ERIC Educational Resources Information Center

Schmidkonz, Bertram

2017-01-01

Learning how cave formations, such as dripstone, take shape can be a valuable pedagogical tool in chemistry and geochemistry. Grasping the underlying processes requires students to synthesize knowledge of several different topical areas. The activity presented here uses an innovative experiment to connect chemistry concepts with an interesting…

Estimating Biofuel Feedstock Water Footprints Using System Dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inman, Daniel; Warner, Ethan; Stright, Dana

Increased biofuel production has prompted concerns about the environmental tradeoffs of biofuels compared to petroleum-based fuels. Biofuel production in general, and feedstock production in particular, is under increased scrutiny. Water footprinting (measuring direct and indirect water use) has been proposed as one measure to evaluate water use in the context of concerns about depleting rural water supplies through activities such as irrigation for large-scale agriculture. Water footprinting literature has often been limited in one or more key aspects: complete assessment across multiple water stocks (e.g., vadose zone, surface, and ground water stocks), geographical resolution of data, consistent representation of manymore » feedstocks, and flexibility to perform scenario analysis. We developed a model called BioSpatial H2O using a system dynamics modeling and database framework. BioSpatial H2O could be used to consistently evaluate the complete water footprints of multiple biomass feedstocks at high geospatial resolutions. BioSpatial H2O has the flexibility to perform simultaneous scenario analysis of current and potential future crops under alternative yield and climate conditions. In this proof-of-concept paper, we modeled corn grain (Zea mays L.) and soybeans (Glycine max) under current conditions as illustrative results. BioSpatial H2O links to a unique database that houses annual spatially explicit climate, soil, and plant physiological data. Parameters from the database are used as inputs to our system dynamics model for estimating annual crop water requirements using daily time steps. Based on our review of the literature, estimated green water footprints are comparable to other modeled results, suggesting that BioSpatial H2O is computationally sound for future scenario analysis. Our modeling framework builds on previous water use analyses to provide a platform for scenario-based assessment. BioSpatial H2O's system dynamics is a flexible and user

Silicate and carbonate mineral weathering in soil profiles developed on Pleistocene glacial drift (Michigan, USA): Mass balances based on soil water geochemistry

NASA Astrophysics Data System (ADS)

Jin, Lixin; Williams, Erika L.; Szramek, Kathryn J.; Walter, Lynn M.; Hamilton, Stephen K.

2008-02-01

Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition. Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO 2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg 2+/Ca 2+ ratio of 0.4. Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca 2+ and Mg 2+ in natural waters. Dolomite dissolution appears to be a major process

Anomalous Dynamics of Water Confined in Protein-Protein and Protein-DNA Interfaces.

PubMed

Chong, Song-Ho; Ham, Sihyun

2016-10-06

Confined water often exhibits anomalous properties not observable in the bulk phase. Although water in hydrophobic confinement has been the focus of intense investigation, the behavior of water confined between hydrophilic surfaces, which are more frequently found in biological systems, has not been fully explored. Here, we investigate using molecular dynamics simulations dynamical properties of the water confined in hydrophilic protein-protein and protein-DNA interfaces. We find that the interfacial water exhibits glassy slow relaxations even at 300 K. In particular, the rotational dynamics show a logarithmic decay that was observed in glass-forming liquids at deeply supercooled states. We argue that such slow water dynamics are indeed induced by the hydrophilic binding surfaces, which is in opposition to the picture that the hydration water slaves protein motions. Our results will significantly impact the view on the role of water in biomolecular interactions.

Structured Ionomer Thin Films at Water Interface: Molecular Dynamics Simulation Insight

DOE PAGES

Aryal, Dipak; Agrawal, Anupriya; Perahia, Dvora; ...

2017-08-23

Controlling the structure and dynamics of thin films of ionizable polymers at water interfaces is critical to their many applications. As the chemical diversity within one polymer is increased, controlling the structure and dynamics of the polymer, which is a key to their use, becomes a challenge. Here molecular dynamics simulations (MD) are used to obtain molecular insight into the structure and dynamics of thin films of one such macromolecule at the interface with water. The polymer consists of an ABCBA topology with randomly sulfonated polystyrene (C), tethered symmetrically to flexible poly(ethylene- r-propylene) blocks (B), and end-capped by a poly(more » t-butylstyrene) block (A). The compositions of the interfacial and bulk regions of thin films of the ABCBA polymers are followed as a function of exposure time to water. We find that interfacial rearrangements take place where buried ionic segments migrate toward the water interface. The hydrophobic blocks collapse and rearrange to minimize their exposure to water. In conclusion, the water that initially drives interfacial reengagements breaks the ionic clusters within the film, forming a dynamic hydrophilic internal network within the hydrophobic segments.« less

Proton dynamics and the phase diagram of dense water ice.

PubMed

Hernandez, J-A; Caracas, R

2018-06-07

All the different phases of water ice between 2 GPa and several megabars are based on a single body-centered cubic sub-lattice of oxygen atoms. They differ only by the behavior of the hydrogen atoms. In this study, we investigate the dynamics of the H atoms at high pressures and temperatures in water ice from first-principles molecular dynamics simulations. We provide a detailed analysis of the O-H⋯O bonding dynamics over the entire stability domain of the body-centered cubic (bcc) water ices and compute transport properties and vibrational density-of-states. We report the first ab initio evidence for a plastic phase of water and we propose a coherent phase diagram for bcc water ices compatible with the two groups of melting curves and with the multiple anomalies reported in ice VII around 15 GPa.

Geochemistry of Permian rocks from the margins of the Phosphoria Basin

USGS Publications Warehouse

Perkins, Robert B.; McIntyre, Brandie; Hein, James R.; Piper, David Z.

2003-01-01

The Permian Phosphoria Formation and interbedded units of the Park City Formation and Shedhorn Sandstone in western Wyoming represent deposition along a carbonate ramp at the eastern margin of the Phosphoria Basin, with portions of the Phosphoria units reflecting periods of upwelling and widespread phosphogenesis. Thickness-weighted slab-samples of these units were collected at a maximum interval of 3 m along an 80+ m-length of unweathered core and analyzed for major-, minor-, and trace-element contents. Interpretations of geochemistry were made within the confines of a previously recognized sequence stratigraphy framework. Major shifts in element ratios characteristic of terrigenous debris that occur at sequence boundaries at the base of the Meade Peak and Retort Members of the Phosphoria Formation are attributed to changing sediment sources. Inter-element relationships in the marine fraction indicate that bottom waters of the Phosphoria Basin were predominantly denitrifying during deposition of the Ervay, Grandeur, and Phosphoria sediments, although sulfate-reducing conditions may have existed during deposition of the lower Meade Peak sediments. Oxic conditions were prevalent during deposition of a large part of the Franson Member, which represents sedimentation in a shallow, inner- to back-ramp setting. Variations in sediment facies and organic matter and trace element contents largely reflect changes in Permian sea level. Changes in sea level in basin-margin areas, such as represented by the study section, may have affected the oxidation of settling organic matter, the foci of intersection of upwelling bottom waters with the photic zone, the rate of terrigenous sedimentation, and, ultimately, the overall environment of deposition. Our study suggests that phosphogenesis can occur under lowstand, transgressive, and highstand conditions in marginal areas, assuming water depths sufficient for upwelling to occur. Formation of phosphorite layers under upwelling

Water dynamics in different biochar fractions.

PubMed

Conte, Pellegrino; Nestle, Nikolaus

2015-09-01

Biochar is a carbonaceous porous material deliberately applied to soil to improve its fertility. The mechanisms through which biochar acts on fertility are still poorly understood. The effect of biochar texture size on water dynamics was investigated here in order to provide information to address future research on nutrient mobility towards plant roots as biochar is applied as soil amendment. A poplar biochar has been stainless steel fractionated in three different textured fractions (1.0-2.0 mm, 0.3-1.0 mm and <0.3 mm, respectively). Water-saturated fractions were analyzed by fast field cycling (FFC) NMR relaxometry. Results proved that 3D exchange between bound and bulk water predominantly occurred in the coarsest fraction. However, as porosity decreased, water motion was mainly associated to a restricted 2D diffusion among the surface-site pores and the bulk-site ones. The X-ray μ-CT imaging analyses on the dry fractions revealed the lowest surface/volume ratio for the coarsest fraction, thereby corroborating the 3D water exchange mechanism hypothesized by FFC NMR relaxometry. However, multi-micrometer porosity was evidenced in all the samples. The latter finding suggested that the 3D exchange mechanism cannot even be neglected in the finest fraction as previously excluded only on the basis of NMR relaxometry results. X-ray μ-CT imaging showed heterogeneous distribution of inorganic materials inside all the fractions. The mineral components may contribute to the water relaxation mechanisms by FFC NMR relaxometry. Further studies are needed to understand the role of the inorganic particles on water dynamics. Copyright © 2015 John Wiley & Sons, Ltd.

Incorporating human-water dynamics in a hyper-resolution land surface model

NASA Astrophysics Data System (ADS)

Vergopolan, N.; Chaney, N.; Wanders, N.; Sheffield, J.; Wood, E. F.

2017-12-01

The increasing demand for water, energy, and food is leading to unsustainable groundwater and surface water exploitation. As a result, the human interactions with the environment, through alteration of land and water resources dynamics, need to be reflected in hydrologic and land surface models (LSMs). Advancements in representing human-water dynamics still leave challenges related to the lack of water use data, water allocation algorithms, and modeling scales. This leads to an over-simplistic representation of human water use in large-scale models; this is in turn leads to an inability to capture extreme events signatures and to provide reliable information at stakeholder-level spatial scales. The emergence of hyper-resolution models allows one to address these challenges by simulating the hydrological processes and interactions with the human impacts at field scales. We integrated human-water dynamics into HydroBlocks - a hyper-resolution, field-scale resolving LSM. HydroBlocks explicitly solves the field-scale spatial heterogeneity of land surface processes through interacting hydrologic response units (HRUs); and its HRU-based model parallelization allows computationally efficient long-term simulations as well as ensemble predictions. The implemented human-water dynamics include groundwater and surface water abstraction to meet agricultural, domestic and industrial water demands. Furthermore, a supply-demand water allocation scheme based on relative costs helps to determine sectoral water use requirements and tradeoffs. A set of HydroBlocks simulations over the Midwest United States (daily, at 30-m spatial resolution for 30 years) are used to quantify the irrigation impacts on water availability. The model captures large reductions in total soil moisture and water table levels, as well as spatiotemporal changes in evapotranspiration and runoff peaks, with their intensity related to the adopted water management strategy. By incorporating human-water dynamics in

Combine the soil water assessment tool (SWAT) with sediment geochemistry to evaluate diffuse heavy metal loadings at watershed scale.

PubMed

Jiao, Wei; Ouyang, Wei; Hao, Fanghua; Huang, Haobo; Shan, Yushu; Geng, Xiaojun

2014-09-15

Assessing the diffuse pollutant loadings at watershed scale has become increasingly important when formulating effective watershed water management strategies, but the process was seldom achieved for heavy metals. In this study, the overall temporal-spatial variability of particulate Pb, Cu, Cr and Ni losses within an agricultural watershed was quantitatively evaluated by combining SWAT with sediment geochemistry. Results showed that the watershed particulate heavy metal loadings displayed strong variability in the simulation period 1981-2010, with an obvious increasing trend in recent years. The simulated annual average loadings were 20.21 g/ha, 21.75 g/ha, 47.35 g/ha and 21.27 g/ha for Pb, Cu, Cr and Ni, respectively. By comparison, these annual average values generally matched the estimated particulate heavy metal loadings at field scale. With spatial interpolation of field loadings, it was found that the diffuse heavy metal pollution mainly came from the sub-basins dominated with cultivated lands, accounting for over 70% of total watershed loadings. The watershed distribution of particulate heavy metal losses was very similar to that of soil loss but contrary to that of heavy metal concentrations in soil, highlighting the important role of sediment yield in controlling the diffuse heavy metal loadings. Copyright © 2014 Elsevier B.V. All rights reserved.

Coupling of the hydration water dynamics and the internal dynamics of actin detected by quasielastic neutron scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujiwara, Satoru, E-mail: fujiwara.satoru@jaea.go.jp; Plazanet, Marie; Oda, Toshiro

2013-02-15

Highlights: ► Quasielastic neutron scattering spectra of F-actin and G-actin were measured. ► Analysis of the samples in D{sub 2}O and H{sub 2}O provided the spectra of hydration water. ► The first layer hydration water around F-actin is less mobile than around G-actin. ► This difference in hydration water is in concert with the internal dynamics of actin. ► Water outside the first layer behaves bulk-like but influenced by the first layer. -- Abstract: In order to characterize dynamics of water molecules around F-actin and G-actin, quasielastic neutron scattering experiments were performed on powder samples of F-actin and G-actin, hydratedmore » either with D{sub 2}O or H{sub 2}O, at hydration ratios of 0.4 and 1.0. By combined analysis of the quasielastic neutron scattering spectra, the parameter values characterizing the dynamics of the water molecules in the first hydration layer and those of the water molecules outside of the first layer were obtained. The translational diffusion coefficients (D{sub T}) of the hydration water in the first layer were found to be 1.2 × 10{sup −5} cm{sup 2}/s and 1.7 × 10{sup −5} cm{sup 2}/s for F-actin and G-actin, respectively, while that for bulk water was 2.8 × 10{sup −5} cm{sup 2}/s. The residence times were 6.6 ps and 5.0 ps for F-actin and G-actin, respectively, while that for bulk water was 0.62 ps. These differences between F-actin and G-actin, indicating that the hydration water around G-actin is more mobile than that around F-actin, are in concert with the results of the internal dynamics of F-actin and G-actin, showing that G-actin fluctuates more rapidly than F-actin. This implies that the dynamics of the hydration water is coupled to the internal dynamics of the actin molecules. The D{sub T} values of the water molecules outside of the first hydration layer were found to be similar to that of bulk water though the residence times are strongly affected by the first hydration layer. This supports

Structure from Dynamics: Vibrational Dynamics of Interfacial Water as a Probe of Aqueous Heterogeneity

PubMed Central

2018-01-01

The structural heterogeneity of water at various interfaces can be revealed by time-resolved sum-frequency generation spectroscopy. The vibrational dynamics of the O–H stretch vibration of interfacial water can reflect structural variations. Specifically, the vibrational lifetime is typically found to increase with increasing frequency of the O–H stretch vibration, which can report on the hydrogen-bonding heterogeneity of water. We compare and contrast vibrational dynamics of water in contact with various surfaces, including vapor, biomolecules, and solid interfaces. The results reveal that variations in the vibrational lifetime with vibrational frequency are very typical, and can frequently be accounted for by the bulk-like heterogeneous response of interfacial water. Specific interfaces exist, however, for which the behavior is less straightforward. These insights into the heterogeneity of interfacial water thus obtained contribute to a better understanding of complex phenomena taking place at aqueous interfaces, such as photocatalytic reactions and protein folding. PMID:29490138

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

DOE PAGES

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; ...

2015-11-03

We studied the dynamics of water in polyethylene oxide (PEO)/LiCl solution with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. Furthermore, the measured diffusion coefficient of interfacial water remained 5–10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li +. Detailed analysis of MD trajectories suggests that Li + is favorably found at the surface of the hydration layer, and the probability to find the caged Li + configuration formed by themore » PEO is lower than for the noncaged Li +-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li + hydration complexes. Moreover, performing the MD simulation with different ions (Na + and K +) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.« less

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O.; Jalarvo, Niina H.; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S.; Do, Changwoo

2015-11-01

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li+ . Detailed analysis of MD trajectories suggests that Li+ is favorably found at the surface of the hydration layer, and the probability to find the caged Li+ configuration formed by the PEO is lower than for the noncaged Li+-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li+ hydration complexes. Performing the MD simulation with different ions (Na+ and K+ ) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Dynamics of Water Associated with Lithium Ions Distributed in Polyethylene Oxide.

PubMed

Zhang, Zhe; Ohl, Michael; Diallo, Souleymane O; Jalarvo, Niina H; Hong, Kunlun; Han, Youngkyu; Smith, Gregory S; Do, Changwoo

2015-11-06

The dynamics of water in polyethylene oxide (PEO)/LiCl solution has been studied with quasielastic neutron scattering experiments and molecular dynamics (MD) simulations. Two different time scales of water diffusion representing interfacial water and bulk water dynamics have been identified. The measured diffusion coefficient of interfacial water remained 5-10 times smaller than that of bulk water, but both were slowed by approximately 50% in the presence of Li(+). Detailed analysis of MD trajectories suggests that Li(+) is favorably found at the surface of the hydration layer, and the probability to find the caged Li(+) configuration formed by the PEO is lower than for the noncaged Li(+)-PEO configuration. In both configurations, however, the slowing down of water molecules is driven by reorienting water molecules and creating water-Li(+) hydration complexes. Performing the MD simulation with different ions (Na(+) and K(+)) revealed that smaller ionic radius of the ions is a key factor in disrupting the formation of PEO cages by allowing spaces for water molecules to come in between the ion and PEO.

Short time dynamics of water coalescence on a flat water pool

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lim, Su Jin; Gim, Bopil; Fezzaa, Kamel

2016-12-01

Coalescence is an important hydrodynamic event that frequently takes place in nature as well as in industry. Here we provide an experimental study on short time dynamics of water coalescence, particularly when a water droplet comes in contact with a flat water surface, by utilizing high-resolution high-penetration ultrafast X-ray microscopy. Our results demonstrate a possibility that an extreme curvature difference between a drop and a flat surface can significantly modify the hydrodynamics of water coalescence, which is unexpected in the existing theory. We suggest a plausible explanation for why coalescence can be modified by an extreme curvature difference.

Dynamics of confined reactive water in smectite clay-zeolite composites.

PubMed

Pitman, Michael C; van Duin, Adri C T

2012-02-15

The dynamics of water confined to mesoporous regions in minerals such as swelling clays and zeolites is fundamental to a wide range of resource management issues impacting many processes on a global scale, including radioactive waste containment, desalination, and enhanced oil recovery. Large-scale atomic models of freely diffusing multilayer smectite particles at low hydration confined in a silicalite cage are used to investigate water dynamics in the composite environment with the ReaxFF reactive force field over a temperature range of 300-647 K. The reactive capability of the force field enabled a range of relevant surface chemistry to emerge, including acid/base equilibria in the interlayer calcium hydrates and silanol formation on the edges of the clay and inner surface of the zeolite housing. After annealing, the resulting clay models exhibit both mono- and bilayer hydration structures. Clay surface hydration redistributed markedly and yielded to silicalite water loading. We find that the absolute rates and temperature dependence of water dynamics compare well to neutron scattering data and pulse field gradient measures from relevant samples of Ca-montmorillonite and silicalite, respectively. Within an atomistic, reactive context, our results distinguish water dynamics in the interlayer Ca(OH)(2)·nH(2)O environment from water flowing over the clay surface, and from water diffusing within silicalite. We find that the diffusion of water when complexed to Ca hydrates is considerably slower than freely diffusing water over the clay surface, and the reduced mobility is well described by a difference in the Arrhenius pre-exponential factor rather than a change in activation energy.

Insights into structural and dynamical features of water at halloysite interfaces probed by DFT and classical molecular dynamics simulations.

PubMed

Presti, Davide; Pedone, Alfonso; Mancini, Giordano; Duce, Celia; Tiné, Maria Rosaria; Barone, Vincenzo

2016-01-21

Density functional theory calculations and classical molecular dynamics simulations have been used to investigate the structure and dynamics of water molecules on kaolinite surfaces and confined in the interlayer of a halloysite model of nanometric dimension. The first technique allowed us to accurately describe the structure of the tetrahedral-octahedral slab of kaolinite in vacuum and in interaction with water molecules and to assess the performance of two widely employed empirical force fields to model water/clay interfaces. Classical molecular dynamics simulations were used to study the hydrogen bond network structure and dynamics of water adsorbed on kaolinite surfaces and confined in the halloysite interlayer. The results are in nice agreement with the few experimental data available in the literature, showing a pronounced ordering and reduced mobility of water molecules at the hydrophilic octahedral surfaces of kaolinite and confined in the halloysite interlayer, with respect to water interacting with the hydrophobic tetrahedral surfaces and in the bulk. Finally, this investigation provides new atomistic insights into the structural and dynamical properties of water-clay interfaces, which are of fundamental importance for both natural processes and industrial applications.

The study of dynamic force acted on water strider leg departing from water surface

NASA Astrophysics Data System (ADS)

Sun, Peiyuan; Zhao, Meirong; Jiang, Jile; Zheng, Yelong

2018-01-01

Water-walking insects such as water striders can skate on the water surface easily with the help of the hierarchical structure on legs. Numerous theoretical and experimental studies show that the hierarchical structure would help water strider in quasi-static case such as load-bearing capacity. However, the advantage of the hierarchical structure in the dynamic stage has not been reported yet. In this paper, the function of super hydrophobicity and the hierarchical structure was investigated by measuring the adhesion force of legs departing from the water surface at different lifting speed by a dynamic force sensor. The results show that the adhesion force decreased with the increase of lifting speed from 0.02 m/s to 0.4 m/s, whose mechanic is investigated by Energy analysis. In addition, it can be found that the needle shape setae on water strider leg can help them depart from water surface easily. Thus, it can serve as a starting point to understand how the hierarchical structure on the legs help water-walking insects to jump upward rapidly to avoid preying by other insects.

Dynamics of Hydration Water in Sugars and Peptides Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perticaroli, Stefania; Nakanishi, Masahiro; Pashkovski, Eugene

2013-01-01

We analyzed solute and solvent dynamics of sugars and peptides aqueous solutions using extended epolarized light scattering (EDLS) and broadband dielectric spectroscopies (BDS). Spectra measured with both techniques reveal the same mechanism of rotational diffusion of peptides molecules. In the case of sugars, this solute reorientational relaxation can be isolated by EDLS measurements, whereas its ontribution to the dielectric spectra is almost negligible. In the presented analysis, we characterize the hydration water in terms of hydration number and retardation ratio between relaxation times of hydration and bulk water. Both techniques provide similar estimates of . The retardation imposed on themore » hydration water by sugars is 3.3 1.3 and involves only water molecules hydrogen-bonded (HB) to solutes ( 3 water molecules per sugar OH-group). In contrast, polar peptides cause longer range erturbations beyond the first hydration shell, and between 2.8 and 8, increasing with the number of chemical groups engaged in HB formation. We demonstrate that chemical heterogeneity and specific HB interactions play a crucial role in hydration dynamics around polar solutes. The obtained results help to disentangle the role of excluded volume and enthalpic contributions in dynamics of hydration water at the interface with biological molecules.« less

Integration of inorganic and isotopic geochemistry with endocrine disruption activity assays to assess risks to water resources near unconventional oil and gas development in Garfield County, CO.

NASA Astrophysics Data System (ADS)

Harkness, J.; Kassotis, C.; Cornelius, J.; Nagel, S.; Vengosh, A.

2016-12-01

The rise of hydraulic fracturing in the United States has sparked a debate about the impact of oil and gas development on the quality of water resources. Wastewater associated with hydraulic fracturing includes injection fluid that is a mixture of sand, freshwater and synthetic organic chemicals, flowback water that is a mixture of injection fluid and formation brine, and produced water that is primarily brine. The fluids range in salinity and chemical composition that can have different environmental impacts. We analyzed the inorganic and isotope geochemistry of 58 surface and groundwater samples near and away from unconventional oil and gas operations (UOG), along with hormonal profiles via bioassays. Cl (0.12 to 198 mg/L), Na (1.2 to 518 mg/L) and Sr (1.4 to 2410 ug/L) were higher in both groundwater and surface water near UOG wells. Four surface waters and one groundwater had Br/Cl indicative of brine contamination (>1.5x10-3). Three of the SW samples also had 87Sr/86Sr ratios similar to values found in produced or flowback water (0.7118 and 0.7158, respectively) from the Williams-Fork formation and elevated compared to background ratios (0.71062 to 0.7115). Increased progestogenic activity was observed in groundwater near UOG operations and inncreased estrogenic, androgenic, progestogenic, anti-androgenic, anti-progestogenic, and anti-glucocorticoid activities in surface water near UOG operations. The association of increased EDCs with inorganic and isotopic indicators of UOG wastewater provides evidence for possible environmental and health impacts from drilling activity.

Distinguishing the Source of Natural Gas Accumulations with a Combined Gas and Co-produced Formation Water Geochemical Approach: a Case Study from the Appalachian Basin

EPA Pesticide Factsheets

The purpose of this study is to discuss the use of gas and co-produced formation water geochemistry for identifying the source of natural gas and present gas geochemistry for the northern Appalachian Basin.

Molecular dynamics simulation of nonlinear spectroscopies of intermolecular motions in liquid water.

PubMed

Yagasaki, Takuma; Saito, Shinji

2009-09-15

Water is the most extensively studied of liquids because of both its ubiquity and its anomalous thermodynamic and dynamic properties. The properties of water are dominated by hydrogen bonds and hydrogen bond network rearrangements. Fundamental information on the dynamics of liquid water has been provided by linear infrared (IR), Raman, and neutron-scattering experiments; molecular dynamics simulations have also provided insights. Recently developed higher-order nonlinear spectroscopies open new windows into the study of the hydrogen bond dynamics of liquid water. For example, the vibrational lifetimes of stretches and a bend, intramolecular features of water dynamics, can be accurately measured and are found to be on the femtosecond time scale at room temperature. Higher-order nonlinear spectroscopy is expressed by a multitime correlation function, whereas traditional linear spectroscopy is given by a one-time correlation function. Thus, nonlinear spectroscopy yields more detailed information on the dynamics of condensed media than linear spectroscopy. In this Account, we describe the theoretical background and methods for calculating higher order nonlinear spectroscopy; equilibrium and nonequilibrium molecular dynamics simulations, and a combination of both, are used. We also present the intermolecular dynamics of liquid water revealed by fifth-order two-dimensional (2D) Raman spectroscopy and third-order IR spectroscopy. 2D Raman spectroscopy is sensitive to couplings between modes; the calculated 2D Raman signal of liquid water shows large anharmonicity in the translational motion and strong coupling between the translational and librational motions. Third-order IR spectroscopy makes it possible to examine the time-dependent couplings. The 2D IR spectra and three-pulse photon echo peak shift show the fast frequency modulation of the librational motion. A significant effect of the translational motion on the fast frequency modulation of the librational motion is

Dynamics of Biofilm Regrowth in Drinking Water Distribution Systems.

PubMed

Douterelo, I; Husband, S; Loza, V; Boxall, J

2016-07-15

The majority of biomass within water distribution systems is in the form of attached biofilm. This is known to be central to drinking water quality degradation following treatment, yet little understanding of the dynamics of these highly heterogeneous communities exists. This paper presents original information on such dynamics, with findings demonstrating patterns of material accumulation, seasonality, and influential factors. Rigorous flushing operations repeated over a 1-year period on an operational chlorinated system in the United Kingdom are presented here. Intensive monitoring and sampling were undertaken, including time-series turbidity and detailed microbial analysis using 16S rRNA Illumina MiSeq sequencing. The results show that bacterial dynamics were influenced by differences in the supplied water and by the material remaining attached to the pipe wall following flushing. Turbidity, metals, and phosphate were the main factors correlated with the distribution of bacteria in the samples. Coupled with the lack of inhibition of biofilm development due to residual chlorine, this suggests that limiting inorganic nutrients, rather than organic carbon, might be a viable component in treatment strategies to manage biofilms. The research also showed that repeat flushing exerted beneficial selective pressure, giving another reason for flushing being a viable advantageous biofilm management option. This work advances our understanding of microbiological processes in drinking water distribution systems and helps inform strategies to optimize asset performance. This research provides novel information regarding the dynamics of biofilm formation in real drinking water distribution systems made of different materials. This new knowledge on microbiological process in water supply systems can be used to optimize the performance of the distribution network and to guarantee safe and good-quality drinking water to consumers. Copyright © 2016 Douterelo et al.

Dynamics of Biofilm Regrowth in Drinking Water Distribution Systems

PubMed Central

Husband, S.; Loza, V.; Boxall, J.

2016-01-01

ABSTRACT The majority of biomass within water distribution systems is in the form of attached biofilm. This is known to be central to drinking water quality degradation following treatment, yet little understanding of the dynamics of these highly heterogeneous communities exists. This paper presents original information on such dynamics, with findings demonstrating patterns of material accumulation, seasonality, and influential factors. Rigorous flushing operations repeated over a 1-year period on an operational chlorinated system in the United Kingdom are presented here. Intensive monitoring and sampling were undertaken, including time-series turbidity and detailed microbial analysis using 16S rRNA Illumina MiSeq sequencing. The results show that bacterial dynamics were influenced by differences in the supplied water and by the material remaining attached to the pipe wall following flushing. Turbidity, metals, and phosphate were the main factors correlated with the distribution of bacteria in the samples. Coupled with the lack of inhibition of biofilm development due to residual chlorine, this suggests that limiting inorganic nutrients, rather than organic carbon, might be a viable component in treatment strategies to manage biofilms. The research also showed that repeat flushing exerted beneficial selective pressure, giving another reason for flushing being a viable advantageous biofilm management option. This work advances our understanding of microbiological processes in drinking water distribution systems and helps inform strategies to optimize asset performance. IMPORTANCE This research provides novel information regarding the dynamics of biofilm formation in real drinking water distribution systems made of different materials. This new knowledge on microbiological process in water supply systems can be used to optimize the performance of the distribution network and to guarantee safe and good-quality drinking water to consumers. PMID:27208119

Structural and dynamical characterization of water on the Au (100) and graphene surfaces: A molecular dynamics simulation approach

NASA Astrophysics Data System (ADS)

Foroutan, Masumeh; Darvishi, Mehdi; Fatemi, S. Mahmood

2017-09-01

The positioning, adsorption, and movement of water on substrates is dependent upon the chemical nature and arrangement of the atoms of the surface. Therefore the behavior of water molecules on a substrate is a reflection of properties of the surface. Based on this premise, graphene and gold substrates were chosen to study this subject from a molecular perspective. In this work, the structural and dynamical behaviors of a water nanodroplet on Au (100) and the graphene interfaces have been studied by molecular dynamics simulation. The results have shown how the structural and dynamical behaviors of water molecules at the interface reflect the characteristics of these surfaces. The results have demonstrated that residence time and hydrogen bonds' lifetime at the water-Au (100) interface are bigger than at the water-graphene interface. Energy contour map analysis indicates a more uniform surface energy on graphene than on the gold surface. The obtained results illustrate that water clusters on gold and graphene form tetramer and hexamer structures, respectively. Furthermore, the water molecules are more ordered on the gold surface than on graphene. The study of hydrogen bonds showed that the order, stability, and the number of hydrogen bonds is higher on the gold surface. The positioning pattern of water molecules is also similar to the arrangement of gold atoms while no regularity was observed on graphene. The study of dynamical behavior of water molecules revealed that the movement of water on gold is much less than on graphene which is in agreement with the strong water-gold interaction in comparison to the water-graphene interaction.

Water dynamics in glass ionomer cements

NASA Astrophysics Data System (ADS)

Berg, M. C.; Jacobsen, J.; Momsen, N. C. R.; Benetti, A. R.; Telling, M. T. F.; Seydel, T.; Bordallo, H. N.

2016-07-01

Glass ionomer cements (GIC) are an alternative for preventive dentistry. However, these dental cements are complex systems where important motions related to the different states of the hydrogen atoms evolve in a confined porous structure. In this paper, we studied the water dynamics of two different liquids used to prepare either conventional or resin-modified glass ionomer cement. By combining thermal analysis with neutron scattering data we were able to relate the water structure in the liquids to the materials properties.

Observation of Water-Protein Interaction Dynamics with Broadband Two-Dimensional Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

De Marco, Luigi; Haky, Andrew; Tokmakoff, Andrei

Two-dimensional infrared (2D IR) spectroscopy has proven itself an indispensable tool for studying molecular dynamics and intermolecular interactions on ultrafast timescales. Using a novel source of broadband mid-IR pulses, we have collected 2D IR spectra of protein films at varying levels of hydration. With 2D IR, we can directly observe coupling between water's motions and the protein's. Protein films provide us with the ability to discriminate hydration waters from bulk water and thus give us access to studying water dynamics along the protein backbone, fluctuations in the protein structure, and the interplay between the molecular dynamics of the two. We present two representative protein films: poly-L-proline (PLP) and hen egg-white lysozyme (HEWL). Having no N-H groups, PLP allows us to look at water dynamics without interference from resonant energy transfer between the protein N-H stretch and the water O-H stretch. We conclude that at low hydration levels water-protein interactions dominate, and the water's dynamics are tied to those of the protein. In HEWL films, we take advantage of the robust secondary structure to partially deuterate the film, allowing us to spectrally distinguish the protein core from the exterior. From this, we show that resonant energy transfer to water provides an effective means of dissipating excess energy within the protein, while maintaining the structure. These methods are general and can easily be extended to studying specific protein-water interactions.

Structural Interpretation of the Large Slowdown of Water Dynamics at Stacked Phospholipid Membranes for Decreasing Hydration Level: All-Atom Molecular Dynamics

DOE PAGES

Calero, Carles; Stanley, H.; Franzese, Giancarlo

2016-04-27

Hydration water determines the stability and function of phospholipid membranes as well as the interaction of membranes with other molecules. Experiments and simulations have shown that water dynamics slows down dramatically as the hydration decreases, suggesting that the interfacial water that dominates the average dynamics at low hydration is slower than water away from the membrane. Here, based on all-atom molecular dynamics simulations, we provide an interpretation of the slowdown of interfacial water in terms of the structure and dynamics of water–water and water–lipid hydrogen bonds (HBs). We calculate the rotational and translational slowdown of the dynamics of water confinedmore » in stacked phospholipid membranes at different levels of hydration, from completely hydrated to poorly hydrated membranes. For all hydrations, we analyze the distribution of HBs and find that water–lipids HBs last longer than water–water HBs and that at low hydration most of the water is in the interior of the membrane. We also show that water–water HBs become more persistent as the hydration is lowered. We attribute this effect (i) to HBs between water molecules that form, in turn, persistent HBs with lipids; (ii) to the hindering of the H-bonding switching between water molecules due to the lower water density at the interface; and (iii) to the higher probability of water–lipid HBs as the hydration decreases. Lastly, our interpretation of the large dynamic slowdown in water under dehydration is potentially relevant in understanding membrane biophysics at different hydration levels.« less

Water circulation and global mantle dynamics: Insight from numerical modeling

NASA Astrophysics Data System (ADS)

Nakagawa, Takashi; Nakakuki, Tomoeki; Iwamori, Hikaru

2015-05-01

We investigate water circulation and its dynamical effects on global-scale mantle dynamics in numerical thermochemical mantle convection simulations. Both dehydration-hydration processes and dehydration melting are included. We also assume the rheological properties of hydrous minerals and density reduction caused by hydrous minerals. Heat transfer due to mantle convection seems to be enhanced more effectively than water cycling in the mantle convection system when reasonable water dependence of viscosity is assumed, due to effective slab dehydration at shallow depths. Water still affects significantly the global dynamics by weakening the near-surface oceanic crust and lithosphere, enhancing the activity of surface plate motion compared to dry mantle case. As a result, including hydrous minerals, the more viscous mantle is expected with several orders of magnitude compared to the dry mantle. The average water content in the whole mantle is regulated by the dehydration-hydration process. The large-scale thermochemical anomalies, as is observed in the deep mantle, is found when a large density contrast between basaltic material and ambient mantle is assumed (4-5%), comparable to mineral physics measurements. Through this study, the effects of hydrous minerals in mantle dynamics are very important for interpreting the observational constraints on mantle convection.

Molecular environmental geochemistry

NASA Astrophysics Data System (ADS)

O'Day, Peggy A.

1999-05-01

The chemistry, mobility, and bioavailability of contaminant species in the natural environment are controlled by reactions that occur in and among solid, aqueous, and gas phases. These reactions are varied and complex, involving changes in chemical form and mass transfer among inorganic, organic, and biochemical species. The field of molecular environmental geochemistry seeks to apply spectroscopic and microscopic probes to the mechanistic understanding of environmentally relevant chemical processes, particularly those involving contaminants and Earth materials. In general, empirical geochemical models have been shown to lack uniqueness and adequate predictive capability, even in relatively simple systems. Molecular geochemical tools, when coupled with macroscopic measurements, can provide the level of chemical detail required for the credible extrapolation of contaminant reactivity and bioavailability over ranges of temperature, pressure, and composition. This review focuses on recent advances in the understanding of molecular chemistry and reaction mechanisms at mineral surfaces and mineral-fluid interfaces spurred by the application of new spectroscopies and microscopies. These methods, such as synchrotron X-ray absorption and scattering techniques, vibrational and resonance spectroscopies, and scanning probe microscopies, provide direct chemical information that can elucidate molecular mechanisms, including element speciation, ligand coordination and oxidation state, structural arrangement and crystallinity on different scales, and physical morphology and topography of surfaces. Nonvacuum techniques that allow examination of reactions in situ (i.e., with water or fluids present) and in real time provide direct links between molecular structure and reactivity and measurements of kinetic rates or thermodynamic properties. Applications of these diverse probes to laboratory model systems have provided fundamental insight into inorganic and organic reactions at

Seeing real-space dynamics of liquid water through inelastic x-ray scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Iwashita, Takuya; Wu, Bin; Chen, Wei-Ren

Water is ubiquitous on earth, but we know little about the real-space motion of molecules in liquid water. We demonstrate that high-resolution inelastic x-ray scattering measurement over a wide range of momentum and energy transfer makes it possible to probe real-space, real-time dynamics of water molecules through the so-called Van Hove function. Water molecules are found to be strongly correlated in space and time with coupling between the first and second nearest-neighbor molecules. The local dynamic correlation of molecules observed here is crucial to a fundamental understanding of the origin of the physical properties of water, including viscosity. The resultsmore » also suggest that the quantum-mechanical nature of hydrogen bonds could influence its dynamics. Finally, the approach used here offers a powerful experimental method for investigating real-space dynamics of liquids.« less

Seeing real-space dynamics of liquid water through inelastic x-ray scattering

DOE PAGES

Iwashita, Takuya; Wu, Bin; Chen, Wei-Ren; ...

2017-12-22

Water is ubiquitous on earth, but we know little about the real-space motion of molecules in liquid water. We demonstrate that high-resolution inelastic x-ray scattering measurement over a wide range of momentum and energy transfer makes it possible to probe real-space, real-time dynamics of water molecules through the so-called Van Hove function. Water molecules are found to be strongly correlated in space and time with coupling between the first and second nearest-neighbor molecules. The local dynamic correlation of molecules observed here is crucial to a fundamental understanding of the origin of the physical properties of water, including viscosity. The resultsmore » also suggest that the quantum-mechanical nature of hydrogen bonds could influence its dynamics. Finally, the approach used here offers a powerful experimental method for investigating real-space dynamics of liquids.« less

Seeing real-space dynamics of liquid water through inelastic x-ray scattering.

PubMed

Iwashita, Takuya; Wu, Bin; Chen, Wei-Ren; Tsutsui, Satoshi; Baron, Alfred Q R; Egami, Takeshi

2017-12-01

Water is ubiquitous on earth, but we know little about the real-space motion of molecules in liquid water. We demonstrate that high-resolution inelastic x-ray scattering measurement over a wide range of momentum and energy transfer makes it possible to probe real-space, real-time dynamics of water molecules through the so-called Van Hove function. Water molecules are found to be strongly correlated in space and time with coupling between the first and second nearest-neighbor molecules. The local dynamic correlation of molecules observed here is crucial to a fundamental understanding of the origin of the physical properties of water, including viscosity. The results also suggest that the quantum-mechanical nature of hydrogen bonds could influence its dynamics. The approach used here offers a powerful experimental method for investigating real-space dynamics of liquids.

Cosolvent effect on the dynamics of water in aqueous binary mixtures

NASA Astrophysics Data System (ADS)

Zhang, Xia; Zhang, Lu; Jin, Tan; Zhang, Qiang; Zhuang, Wei

2018-04-01

Water rotational dynamics in the mixtures of water and amphiphilic molecules, such as acetone and dimethyl sulfoxide (DMSO), measured by femtosecond infrared, often vary non-monotonically as the amphiphilic molecule's molar fraction changes from 0 to 1. Recent study has attributed the non-ideal water rotation with concentration in DMSO-water mixtures to different microscopic hydrophilic-hydrophobic segregation structure in water-rich and water-poor mixtures. Interestingly, the acetone molecule has very similar molecular structure to DMSO, but the extremum of the water rotational time in the DMSO-water mixtures significantly shifts to lower concentration and the rotation of water is much faster than those in acetone-water mixtures. The simulation results here shows that the non-ideal rotational dynamics of water in both mixtures are due to the frame rotation during the interval of hydrogen bond (HB) switchings. A turnover of the frame rotation with concentration takes place as the structure transition of mixture from the hydrogen bond percolation structure to the hydrophobic percolation structure. The weak acetone-water hydrogen bond strengthens the hydrophobic aggregation and accelerates the relaxation of the hydrogen bond, so that the structure transition takes places at lower concentration and the rotation of water is faster in acetone-water mixture than in DMSO-water mixture. A generally microscopic picture on the mixing effect on the water dynamics in binary aqueous mixtures is presented here.

Non-Equilibrium Water-Glassy Polymer Dynamics

NASA Astrophysics Data System (ADS)

Davis, Eric; Minelli, Matteo; Baschetti, Marco; Sarti, Giulio; Elabd, Yossef

2012-02-01

For many applications (e.g., medical implants, packaging), an accurate assessment and fundamental understanding of the dynamics of water-glassy polymer interactions is of great interest. In this study, sorption and diffusion of pure water in several glassy polymers films, such as poly(styrene) (PS), poly(methyl methacrylate) (PMMA), poly(lactide) (PLA), were measured over a wide range of vapor activities and temperatures using several experimental techniques, including quartz spring microbalance (QSM), quartz crystal microbalance (QCM), and time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian behavior (diffusion-relaxation phenomena) was observed by all three techniques, while FTIR-ATR spectroscopy also provides information about the distribution of the states of water and water transport mechanisms on a molecular-level. Specifically, the states of water are significantly different in PS compared to PMMA and PLA. Additionally, a purely predictive non-equilibrium lattice fluid (NELF) model was applied to predict the sorption isotherms of water in these glassy polymers.

Structure and dynamics of water inside endohedrally functionalized carbon nanotubes.

PubMed

Paul, Sanjib; Abi, T G; Taraphder, Srabani

2014-05-14

We have carried out classical molecular dynamics simulations on the formation of extended water chains inside single-walled carbon nanotubes (SWCNTs) in water in the presence of selected functional groups covalently attached to the inner wall of the tube. Analogues of polar amino acid sidechains have been chosen to carry out the endohedral functionalization of SWCNTs. Our results show a spontaneous and asymmetric filling of the nanotube with dynamical water chains in all the cases studied. The presence of Asp- and Glu-like sidechains is found to result in the formation of well-ordered water chains across the tube having the maximum number of water molecules being retained within the core with the largest residence times. The presence of methyl or methylene groups along the suspended chain is observed to disrupt the formation of water chains with higher length and/or longer residence times. The importance of hydrogen bonding in forming these water chains is assessed in terms of the relaxations of different hydrogen bond correlation functions. For a given dimension of the hydrophobic nanopore, we thus obtain a scale comparing the ability of carboxylic, alcohol, and imidazole groups in controlling the structure and dynamics of water in it. Our results also suggest that SWCNTs of varying lengths, endohedrally functionalized with Asp- and Glu-like sidechains, may be used as design templates in CNT-based water storage devices.

Unusual dynamic properties of water near the ice-binding plane of hyperactive antifreeze protein

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kuffel, Anna; Czapiewski, Dariusz; Zielkiewicz, Jan, E-mail: jaz@chem.pg.gda.pl

2015-10-07

The dynamical properties of solvation water of hyperactive antifreeze protein from Choristoneura fumiferana (CfAFP) are analyzed and discussed in context of its antifreeze activity. The protein comprises of three well-defined planes and one of them binds to the surface of ice. The dynamical properties of solvation water around each of these planes were analyzed separately; the results are compared with the dynamical properties of solvation water of ice around its two crystallographic planes: basal and prism. Three main conclusions are inferred from our investigations. The first one is that the solvation shell of CfAFP does not seem to be particularlymore » far-ranged, at least not beyond what is usually observed for proteins that do not interact with ice. Therefore, it does not appear to us that the antifreeze activity is enhanced by a long-ranged retardation of water mobility. Also the correlation between the collective mobility of water and the collective mobility of protein atoms highly resembles the one measured for the protein that does not interact with ice. Our second conclusion is that the dynamical properties of solvation water of CfAFP are non-uniform. The dynamics of solvation water of ice-binding plane is, in some respects, different from the dynamics of solvation water of the two remaining planes. The feature that distinguishes the dynamics of solvation water of the three planes is the activation energy of diffusion process. The third conclusion is that—from the three analyzed solvation shells of CfAFP—the dynamical properties of solvation water of the ice-binding plane resemble the most the properties of solvation water of ice; note, however, that these properties still clearly differ from the dynamic properties of solvation water of ice.« less

Hydrology and geochemistry of a surface coal mine in northwestern Colorado

USGS Publications Warehouse

Williams, R.S.; Clark, G.M.

1994-01-01

The hydrology and geochemistry of a reclaimed coal mine in northwestern Colorado were monitored during water years 1988 and 1989. Some data also were collected in water years 1987 and 1990. This report describes (1) the sources of hydrologic recharge to and discharge from reclaimed spoil, (2) the relative contributions of recharge to the reclaimed spoil aquifer from identified source waters and the rate of water movement from those sources to the reclaimed spoil, and (3) the geochemical reactions that control water quality in reclaimed spoil. The study area was at a dip-slope coal mine encompassing about 7 square miles with land slopes of varying aspect. The area was instrumented and monitored at five sites; two sites had unmined and reclaimed- spoil areas adjacent to each other and three sites were unmined. The mined areas had been reclaimed. Instrumentation at the study sites included 1 climate station, 3 rain gages, 19 soil-water access tubes, 2 lysimeters, 18 wells completed in bedrock, 7 wells completed in reclaimed spoil, and 2 surface- water gaging stations. The results of the study indicate that the reclaimed spoil is recharged from surface recharge and underburden aquifers. Discharge, as measured by lysimeters, was about 3 inches per year and occurred during and after snowmelt. Hydraulic-head measurements indicated a potential for ground-water movement from deeper to shallower aquifers. Water levels rose in the reclaimed-spoil aquifer and spring discharge at the toe of the spoil slopes increased rapidly in response to snowmelt. Water chemistry, stable isotopes, geochemical models, and mass-balance calculations indicate that surface recharge and the underburden aquifers each contribute about 50 percent of the water to the reclaimed-spoil aquifers. Geochemical information indicates that pyrite oxidation and dissolution of carbonate and efflorescent sulfate minerals control the water chemistry of the reclaimed-spoil aquifer.

Dynamics of water confined in lyotropic liquid crystals: Molecular dynamics simulations of the dynamic structure factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mantha, Sriteja; Yethiraj, Arun

2016-02-24

The properties of water under confinement are of practical and fundamental interest. Here in this work we study the properties of water in the self-assembled lyotropic phases of gemini surfactants with a focus on testing the standard analysis of quasi-elastic neutron scattering (QENS) experiments. In QENS experiments the dynamic structure factor is measured and fit to models to extract the translational diffusion constant, D T , and rotational relaxation time, τ R. We test this procedure by using simulation results for the dynamic structure factor, extracting the dynamic parameters from the fit as is typically done in experiments, and comparingmore » the values to those directly measured in the simulations. We find that the decoupling approximation, where the intermediate scattering function is assumed to be a product of translational and rotational contributions, is quite accurate. The jump-diffusion and isotropic rotation models, however, are not accurate when the degree of confinement is high. In particular, the exponential approximations for the intermediate scattering function fail for highly confined water and the values of D T and τ R can differ from the measured value by as much as a factor of two. Other models have more fit parameters, however, and with the range of energies and wave-vectors accessible to QENS, the typical analysis appears to be the best choice. In the most confined lamellar phase, the dynamics are sufficiently slow that QENS does not access a large enough time scale and neutron spin echo measurements would be a valuable technique in addition to QENS.« less

Lunar carbon chemistry - Relations to and implications for terrestrial organic geochemistry.

NASA Technical Reports Server (NTRS)

Eglinton, G.; Maxwell, J. R.; Pillinger, C. T.

1972-01-01

Survey of the various ways in which studies of lunar carbon chemistry have beneficially affected terrestrial organic geochemistry. A lunar organic gas-analysis operating system is cited as the most important instrumental development in relation to terrestrial organic geochemistry. Improved methods of analysis and handling of organic samples are cited as another benefit derived from studies of lunar carbon chemistry. The problem of controlling contamination and minimizing organic vapors is considered, as well as the possibility of analyzing terrestrial samples by the techniques developed for lunar samples. A need for new methods of analyzing carbonaceous material which is insoluble in organic solvents is indicated.

Temperature Dynamics in Very Shallow Water Bodies: the Role of Heat Fluxes at the Soil-Water Interface

NASA Astrophysics Data System (ADS)

Pivato, M.; Carniello, L.; Silvestri, S.; Marani, M.; Gardner, J.

2016-12-01

Water temperature represents one of the crucial factors driving the ecological processes in water bodies. Many contributions are available in the literature that describe temperature dynamics in deep basins as lakes or seas. Those basins are typically stratified which makes important to represent the vertical profile of the water temperature. Dealing with shallow water bodies, such as rivers, shallow lakes and lagoons, simplifies the problem because the water temperature can be assumed uniform in the water column. Conversely, the heat exchange at the soil-water interface assumes an important role in the water temperature dynamics. Notwithstanding, very few studies and data about this process are available in the literature. In order to provide more insight on the soil contribution to water temperature dynamics, we performed ad hoc field measurements in the Venice lagoon,. We selected a location on a tidal flat in the northern part of the lagoon, close to the Sant'Erasmo Island, where we measured the temperature within the water column and the first 1.5 m of the soil. Data collection started in July 2015 and is still ongoing. We used the data to characterize the heat flux at the water-soil interface in different periods of the year and to develop a "point" model for describing the evolution of the temperature in the water column. The insight on the process provided by the data and by the point model: i) enabled us to determine the soil thermal properties (diffusivity and heat capacity); ii) confirms the uniform profile of the water temperature in the water column; iii) demonstrates that the heat flux at the soil-water interface is comparable with other fluxes at the air-water interface and iv) highlights the important role exerted by advective water fluxes. The latter will be accounted for developing a module for describing the dynamic of the temperature to be coupled with an already existing 2D hydrodynamic model of the Venice lagoon.

Method of analysis and quality-assurance practices by the U.S. Geological Survey Organic Geochemistry Research Group; determination of geosmin and methylisoborneol in water using solid-phase microextraction and gas chromatography/mass spectrometry

USGS Publications Warehouse

Zimmerman, L.R.; Ziegler, A.C.; Thurman, E.M.

2002-01-01

A method for the determination of two common odor-causing compounds in water, geosmin and 2-methylisoborneol, was modified and verified by the U.S. Geological Survey's Organic Geochemistry Research Group in Lawrence, Kansas. The optimized method involves the extraction of odor-causing compounds from filtered water samples using a divinylbenzene-carboxen-polydimethylsiloxane cross-link coated solid-phase microextraction (SPME) fiber. Detection of the compounds is accomplished using capillary-column gas chromatography/mass spectrometry (GC/MS). Precision and accuracy were demonstrated using reagent-water, surface-water, and ground-water samples. The mean accuracies as percentages of the true compound concentrations from water samples spiked at 10 and 35 nanograms per liter ranged from 60 to 123 percent for geosmin and from 90 to 96 percent for 2-methylisoborneol. Method detection limits were 1.9 nanograms per liter for geosmin and 2.0 nanograms per liter for 2-methylisoborneol in 45-milliliter samples. Typically, concentrations of 30 and 10 nanograms per liter of geosmin and 2-methylisoborneol, respectively, can be detected by the general public. The calibration range for the method is equivalent to concentrations from 5 to 100 nanograms per liter without dilution. The method is valuable for acquiring information about the production and fate of these odor-causing compounds in water.

Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics.

PubMed

Nagata, Yuki; Ohto, Tatsuhiko; Backus, Ellen H G; Bonn, Mischa

2016-04-28

Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems.

Seasonal hyporheic dynamics control coupled microbiology and geochemistry in Colorado River sediments

DOE PAGES

Danczak, Robert E.; Sawyer, Audrey H.; Williams, Kenneth H.; ...

2016-12-03

Riverbed microbial communities play an oversized role in many watershed ecosystem functions, including the processing of organic carbon, cycling of nitrogen, and alterations to metal mobility. The structure and activity of microbial assemblages depend in part on geochemical conditions set by river-groundwater exchange or hyporheic exchange. In order to assess how seasonal changes in river-groundwater mixing affect these populations in a snowmelt-dominated fluvial system, vertical sediment and pore water profiles were sampled at three time points at one location in the hyporheic zone of the Colorado River and analyzed by using geochemical measurements, 16S rRNA gene sequencing, and ecological modeling.more » Oxic river water penetrated deepest into the subsurface during peak river discharge, while under base flow conditions, anoxic groundwater dominated shallower depths. Over a 70 cm thick interval, riverbed sediments were therefore exposed to seasonally fluctuating redox conditions and hosted microbial populations statistically different from those at both shallower and deeper locations. Additionally, microbial populations within this zone were shown to be the most dynamic across sampling time points, underlining the critical role that hyporheic mixing plays in constraining microbial abundances. Given such mixing effects, we anticipate that future changes in river discharge in mountainous, semiarid western U.S. watersheds may affect microbial community structure and function in riverbed environments, with potential implications for biogeochemical processes in riparian regions.« less

Seasonal hyporheic dynamics control coupled microbiology and geochemistry in Colorado River sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Danczak, Robert E.; Sawyer, Audrey H.; Williams, Kenneth H.

Riverbed microbial communities play an oversized role in many watershed ecosystem functions, including the processing of organic carbon, cycling of nitrogen, and alterations to metal mobility. The structure and activity of microbial assemblages depend in part on geochemical conditions set by river-groundwater exchange or hyporheic exchange. In order to assess how seasonal changes in river-groundwater mixing affect these populations in a snowmelt-dominated fluvial system, vertical sediment and pore water profiles were sampled at three time points at one location in the hyporheic zone of the Colorado River and analyzed by using geochemical measurements, 16S rRNA gene sequencing, and ecological modeling.more » Oxic river water penetrated deepest into the subsurface during peak river discharge, while under base flow conditions, anoxic groundwater dominated shallower depths. Over a 70 cm thick interval, riverbed sediments were therefore exposed to seasonally fluctuating redox conditions and hosted microbial populations statistically different from those at both shallower and deeper locations. Additionally, microbial populations within this zone were shown to be the most dynamic across sampling time points, underlining the critical role that hyporheic mixing plays in constraining microbial abundances. Given such mixing effects, we anticipate that future changes in river discharge in mountainous, semiarid western U.S. watersheds may affect microbial community structure and function in riverbed environments, with potential implications for biogeochemical processes in riparian regions.« less

Seasonal hyporheic dynamics control coupled microbiology and geochemistry in Colorado River sediments

NASA Astrophysics Data System (ADS)

Danczak, Robert E.; Sawyer, Audrey H.; Williams, Kenneth H.; Stegen, James C.; Hobson, Chad; Wilkins, Michael J.

2016-12-01

Riverbed microbial communities play an oversized role in many watershed ecosystem functions, including the processing of organic carbon, cycling of nitrogen, and alterations to metal mobility. The structure and activity of microbial assemblages depend in part on geochemical conditions set by river-groundwater exchange or hyporheic exchange. To assess how seasonal changes in river-groundwater mixing affect these populations in a snowmelt-dominated fluvial system, vertical sediment and pore water profiles were sampled at three time points at one location in the hyporheic zone of the Colorado River and analyzed by using geochemical measurements, 16S rRNA gene sequencing, and ecological modeling. Oxic river water penetrated deepest into the subsurface during peak river discharge, while under base flow conditions, anoxic groundwater dominated shallower depths. Over a 70 cm thick interval, riverbed sediments were therefore exposed to seasonally fluctuating redox conditions and hosted microbial populations statistically different from those at both shallower and deeper locations. Additionally, microbial populations within this zone were shown to be the most dynamic across sampling time points, underlining the critical role that hyporheic mixing plays in constraining microbial abundances. Given such mixing effects, we anticipate that future changes in river discharge in mountainous, semiarid western U.S. watersheds may affect microbial community structure and function in riverbed environments, with potential implications for biogeochemical processes in riparian regions.

Molecular dynamics approach to water structure of HII mesophase of monoolein

NASA Astrophysics Data System (ADS)

Kolev, Vesselin; Ivanova, Anela; Madjarova, Galia; Aserin, Abraham; Garti, Nissim

2012-02-01

The goal of the present work is to study theoretically the structure of water inside the water cylinder of the inverse hexagonal mesophase (HII) of glyceryl monooleate (monoolein, GMO), using the method of molecular dynamics. To simplify the computational model, a fixed structure of the GMO tube is maintained. The non-standard cylindrical geometry of the system required the development and application of a novel method for obtaining the starting distribution of water molecules. A predictor-corrector schema is employed for generation of the initial density of water. Molecular dynamics calculations are performed at constant volume and temperature (NVT ensemble) with 1D periodic boundary conditions applied. During the simulations the lipid structure is kept fixed, while the dynamics of water is unrestrained. Distribution of hydrogen bonds and density as well as radial distribution of water molecules across the water cylinder show the presence of water structure deep in the cylinder (about 6 Å below the GMO heads). The obtained results may help understanding the role of water structure in the processes of insertion of external molecules inside the GMO/water system. The present work has a semi-quantitative character and it should be considered as the initial stage of more comprehensive future theoretical studies.

Water dynamics in large and small reverse micelles: From two ensembles to collective behavior

PubMed Central

Moilanen, David E.; Fenn, Emily E.; Wong, Daryl; Fayer, Michael D.

2009-01-01

The dynamics of water in Aerosol-OT reverse micelles are investigated with ultrafast infrared spectroscopy of the hydroxyl stretch. In large reverse micelles, the dynamics of water are separable into two ensembles: slow interfacial water and bulklike core water. As the reverse micelle size decreases, the slowing effect of the interface and the collective nature of water reorientation begin to slow the dynamics of the core water molecules. In the smallest reverse micelles, these effects dominate and all water molecules have the same long time reorientational dynamics. To understand and characterize the transition in the water dynamics from two ensembles to collective reorientation, polarization and frequency selective infrared pump-probe experiments are conducted on the complete range of reverse micelle sizes from a diameter of 1.6–20 nm. The crossover between two ensemble and collective reorientation occurs near a reverse micelle diameter of 4 nm. Below this size, the small number of confined water molecules and structural changes in the reverse micelle interface leads to homogeneous long time reorientation. PMID:19586114

Ground-water quality and geochemistry, Carson Desert, western Nevada

USGS Publications Warehouse

Lico, Michael S.; Seiler, R.L.

1994-01-01

Aquifers in the Carson Desert are the primary source of drinking water, which is highly variable in chemical composition. In the shallow basin-fill aquifers, water chemistyr varies from a dilute calcium bicarbonate-dominated water beneath the irrigated areas to a saline sodium chloride- dominated water beneath unirrigated areas. Water samples from the shallow aquifers commonly have dissolved solids, chloride, magnesium, sulfate, arsenic, and manganese concentrations that exceed State of Nevada drinking-water standards. Water in the intermediante basin-fill aquifers is a dilute sodium bicarbonate type in the Fallon area and a distinctly more saline sodium chloride type in the Soda Lake-Upsal Hogback area. Dissolved solids, chloride, arsenic, fluoride, and manganese concen- trations commonly exceed drinking-water standards. The basalt aquifer contains a dilute sodium bicarbonate chloride water. Arsenic concentrations exceed standards in all sampled wells. The concen- trations of major constituents in ground water beneath the southern Carson Desert are the result of evapotranspiration and natural geochemical reactions with minerals derived mostly from igneous rocks. Water with higher concentrations of iron and manganese is near thermodynamic equilibrium with siderite and rhodochrosite and indicates that these elements may be limited by the solubility of their respective carbonate minerals. Naturally occurring radionuclides (uranium and radon-222) are present in ground water from the Carson Desert in concen- tratons higher than proposed drinking-water standards. High uranium concentrations in the shallow aquifers may be caused by evaporative concentration and the release of uranium during dissolution of iron and manganese oxides or the oxidation of sedimentary organic matter that typically has elevated uranium concentrations. Ground water in the Carson Desert does not appear to have be contaminated by synthetic organic chemicals.

Aquifer geochemistry and effects of pumping on ground-water quality at the Green Belt Parkway Well Field, Holbrook, Long Island, New York

USGS Publications Warehouse

Brown, Craig J.; Colabufo, Steven; Coates, John D.

2002-01-01

Geochemistry, microbiology, and water quality of the Magothy aquifer at a new supply well in Holbrook were studied to help identify factors that contribute to iron-related biofouling of public-supply wells. The organic carbon content of borehole sediments from the screen zone, and the dominant terminal electron-accepting processes (TEAPs), varied by depth. TEAP assays of core sediments indicated that iron reduction, sulfate reduction, and undetermined (possibly oxic) reactions and microbial activity are correlated with organic carbon (lignite) content. The quality of water from this well, therefore, reflects the wide range of aquifer microenvironments at this site.High concentrations of dissolved iron (3.6 to 6.4 micromoles per liter) in water samples from this well indicate that some water is derived from Fe(III)-reducing sediments within the aquifer, but traces of dissolved oxygen indicate inflow of shallow, oxygenated water from shallow units that overlie the local confining units. Water-quality monitoring before and during a 2-day pumping test indicates that continuous pumping from the Magothy aquifer at this site can induce downward flow of shallow, oxygenated water despite the locally confined conditions. Average concentrations of dissolved oxygen are high (5.2 milligrams per liter, or mg/L) in the overlying upper glacial aquifer and at the top of the Magothy aquifer (4.3 mg/L), and low ( < 0.1 mg/L) in the deeper, anaerobic part of the Magothy; average concentrations of phosphate are high (0.4 mg/L) in the upper glacial aquifer and lower (0.008 mg/L) at the top of the Magothy aquifer and in the deeper part of the Magothy (0.013 mg/L). Concentrations of both constituents increased during the 2 days of pumping. The δ34S of sulfate in shallow ground water from observation wells (3.8 to 6.4 per mil) was much heavier than that in the supplywell water (-0.1 per mil) and was used to help identify sources of water entering the supply well. The δ34S of sulfate in a

Ab initio and classical molecular dynamics studies of the structural and dynamical behavior of water near a hydrophobic graphene sheet.

PubMed

Rana, Malay Kumar; Chandra, Amalendu

2013-05-28

The behavior of water near a graphene sheet is investigated by means of ab initio and classical molecular dynamics simulations. The wetting of the graphene sheet by ab initio water and the relation of such behavior to the strength of classical dispersion interaction between surface atoms and water are explored. The first principles simulations reveal a layered solvation structure around the graphene sheet with a significant water density in the interfacial region implying no drying or cavitation effect. It is found that the ab initio results of water density at interfaces can be reproduced reasonably well by classical simulations with a tuned dispersion potential between the surface and water molecules. Calculations of vibrational power spectrum from ab initio simulations reveal a shift of the intramolecular stretch modes to higher frequencies for interfacial water molecules when compared with those of the second solvation later or bulk-like water due to the presence of free OH modes near the graphene sheet. Also, a weakening of the water-water hydrogen bonds in the vicinity of the graphene surface is found in our ab initio simulations as reflected in the shift of intermolecular vibrational modes to lower frequencies for interfacial water molecules. The first principles calculations also reveal that the residence and orientational dynamics of interfacial water are somewhat slower than those of the second layer or bulk-like molecules. However, the lateral diffusion and hydrogen bond relaxation of interfacial water molecules are found to occur at a somewhat faster rate than that of the bulk-like water molecules. The classical molecular dynamics simulations with tuned Lennard-Jones surface-water interaction are found to produce dynamical results that are qualitatively similar to those of ab initio molecular dynamics simulations.

Coupled Soil-Plant Water Dynamics During Drought-Rewetting Transitions

NASA Astrophysics Data System (ADS)

Volkmann, T. H.; Haberer, K.; Gessler, A.; Weiler, M.

2013-12-01

The predicted climate and land-use changes could have dramatic effects on the water balance of the soil-vegetation system, particularly under frequent drought and subsequent rewetting conditions. Yet, estimation of these effects and associated consequences for the structure and functioning of ecosystems, groundwater recharge, drinking water availability, and the water cycle is currently impeded by gaps in our understanding of the spatiotemporal dynamics of soil water in the rooted soil horizons, the dynamics and driving physiological processes of plant water acquisition, and the transpiration from plant leaves under changing environmental conditions. Combining approaches from the disciplines of plant ecophysiology and soil and isotope hydrology, this work aims to fill this gap by quantitatively characterizing the interaction between plant water use - as affected by rooting patterns and ecophysiology of different plant functional groups - and the water balance of variably complex ecosystems with emphasis on drought and rewetting phases. Results from artificial drought and subsequent rewetting in field experiments using isotopically and dye (Brilliant Blue FCF) labeled water conducted on plots of various surface cover (bare soil, grass, beech, oak, vine) established on luvisol on loess in southwestern Germany are presented. Detailed spatiotemporal insights into the coupled short-term (hours to days) dynamics of soil and plant water during the experiments is facilitated by the application of newly developed techniques for high-frequency in-situ monitoring of stable isotope signatures in both pore water and transpired water using commercial laser-based spectrometers in conjunction with plant ecophysiological, soil physical state, and dye staining observations. On the one hand, the spatiotemporal patterns of plant water uptake are assessed and related to morphological and physiological traits driving plant water uptake, functional adaptations of plants to changes of

Spatial Autocorrelation, Source Water and the Distribution of Total and Viable Microbial Abundances within a Crystalline Formation to a Depth of 800 m

PubMed Central

Beaton, E. D.; Stuart, Marilyne; Stroes-Gascoyne, Sim; King-Sharp, Karen J.; Gurban, Ioana; Festarini, Amy; Chen, Hui Q.

2017-01-01

Proposed radioactive waste repositories require long residence times within deep geological settings for which we have little knowledge of local or regional subsurface dynamics that could affect the transport of hazardous species over the period of radioactive decay. Given the role of microbial processes on element speciation and transport, knowledge and understanding of local microbial ecology within geological formations being considered as host formations can aid predictions for long term safety. In this relatively unexplored environment, sampling opportunities are few and opportunistic. We combined the data collected for geochemistry and microbial abundances from multiple sampling opportunities from within a proposed host formation and performed multivariate mixing and mass balance (M3) modeling, spatial analysis and generalized linear modeling to address whether recharge can explain how subsurface communities assemble within fracture water obtained from multiple saturated fractures accessed by boreholes drilled into the crystalline formation underlying the Chalk River Laboratories site (Deep River, ON, Canada). We found that three possible source waters, each of meteoric origin, explained 97% of the samples, these are: modern recharge, recharge from the period of the Laurentide ice sheet retreat (ca. ∼12000 years before present) and a putative saline source assigned as Champlain Sea (also ca. 12000 years before present). The distributed microbial abundances and geochemistry provide a conceptual model of two distinct regions within the subsurface associated with bicarbonate – used as a proxy for modern recharge – and manganese; these regions occur at depths relevant to a proposed repository within the formation. At the scale of sampling, the associated spatial autocorrelation means that abundances linked with geochemistry were not unambiguously discerned, although fine scale Moran’s eigenvector map (MEM) coefficients were correlated with the abundance

Water transport dynamics in trees and stands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pallardy, S.G.; Cermak, J.; Ewers, F.W.

1995-07-01

Water transport dynamics in trees and stands of conifers have certain features that are characteristic of this group and are at least rare among angiosperms. Among these features is the xylem transport system that is dependent on tracheids for long-distance water transport. Tracheid-containing xylem is relatively inefficient, a property that can reduce submaximum allowable rates of gas exchange, but tracheids also offer substantial capacity for water storage and high resistance to freezing-induced dysfunction. Thus, they are quite compatible with the typical evergreen habit and long transpiration season of conifers. At the stand level, canopy transpiration in conifers is primarily controlledmore » by stomatal conductance. In contrast, in dense canopies of angio-sperms, particularly those of tropical forests with limited air mixing, stand transpiration is limited by radiation input rather than by stomatal control. Because of their evergreen habit a greater proportion of evapotranspiration in conifer forests is associated with evaporation of water intercepted by the tree crowns. Other features of transport dynamics are characteristic of most conifers, but are not unique to this group. Among these features are typically shallow root systems that often must supply water in winter to replace transpiration needs of evergreen species, common occurrence of mycorrhizae that enhance mineral and water uptake, and drought tolerance adaptations that include elements of both dehydration avoidance (e.g., stomatal closure under water stress, shifts in allocation of dry matter to below-ground sinks) and dehydration tolerance (e.g., capacity for acclimation of photosynthetic apparatus to drought, osmotic adjustment). Transpiration rates from conifer foliage often are lower than those of deciduous angiosperms, probably because of the lower maximum capacity of tracheid-bearing xylem to transport water.« less

Dynamics of bound water molecules in fullerenol at different hydration levels

NASA Astrophysics Data System (ADS)

Wang, Yilin; Robey, Steven; Reutt-Robey, Janice

Fullerenols, polyhydroxylated fullerenes, are of great interest as promising materials in medical application because of their high water solubility and biocompatibility. Fullerenols are highly responsive to their environment, for example, they readily undergo hydration under ambient conditions. Understanding the dynamics of water molecules bound to fullerenols, and the interplay between water molecules and fullerenols is important in realizing biological function. Here, broadband dielectric spectroscopy (BDS), was performed on a fullerenol with 44 hydroxyl groups, C60(OH)44, between 300 K and 340 K. At room temperature and under ambient conditions, C60(OH)44 is hydrated, releasing bound water molecules with increasing temperature, as quantified by thermal gravimetric analysis (TGA) measurements. At room temperature, a dielectric band due to collective bulk-like dynamics of the bound water molecules is observed. The relaxation peak of the water molecules shifts to higher frequency with increasing of temperature, reflecting the dynamics of bound water. Upon loss of water molecules, either thermally induced or vacuum induced, the relaxation peak shifts to lower frequency. The stoichiometric relationship between the dielectric properties of the hydrated fullerenol and the interplay between the bound water molecules and C60(OH)44 will be discussed. This work was supported by the National Science Foundation (NSF) under Award Number 1310380.

The dynamic crossover in water does not require bulk water.

PubMed

Turton, David A; Corsaro, Carmelo; Martin, David F; Mallamace, Francesco; Wynne, Klaas

2012-06-14

Many of the anomalous properties of water may be explained by invoking a second critical point that terminates the coexistence line between the low- and high-density amorphous states in the liquid. Direct experimental evidence of this point, and the associated polyamorphic liquid-liquid transition, is elusive as it is necessary for liquid water to be cooled below its homogeneous-nucleation temperature. To avoid crystallization, water in the eutectic LiCl solution has been studied but then it is generally considered that "bulk" water cannot be present. However, recent computational and experimental studies observe cooperative hydration in which case it is possible that sufficient hydrogen-bonded water is present for the essential characteristics of water to be preserved. For femtosecond optical Kerr-effect and nuclear magnetic resonance measurements, we observe in each case a fractional Stokes-Einstein relation with evidence of the dynamic crossover appearing near 220 K and 250 K respectively. Spectra obtained in the glass state also confirm the complex nature of the hydrogen-bonding modes reported for neat room-temperature water and support predictions of anomalous diffusion due to "worm-hole" structure.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

USGS Publications Warehouse

Druschel, G.K.; Schoonen, M.A.A.; Nordstorm, D.K.; Ball, J.W.; Xu, Y.; Cohn, C.A.

2003-01-01

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad??? AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site IC analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad??? AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns. ?? The Royal Society of Chemistry and the Division of Geochemistry of the American Chemical Society 2003.

STABLE ISOTOPES AS INDICATORS OF SOIL WATER DYNAMICS IN WATERSHEDS

EPA Science Inventory

Stream water quality and quantity depend on discharge rates of water and nutrients from soils. However, soil-water storage is very dynamic and strongly influenced by plants. We analyzed stable isotopes of oxygen and hydrogen to quantify spatial and temporal changes in evaporati...

Sulfur and carbon geochemistry of the Santa Elena peridotites: Comparing oceanic and continental processes during peridotite alteration

NASA Astrophysics Data System (ADS)

Schwarzenbach, Esther M.; Gill, Benjamin C.; Gazel, Esteban; Madrigal, Pilar

2016-05-01

Ultramafic rocks exposed on the continent serve as a window into oceanic and continental processes of water-peridotite interaction, so called serpentinization. In both environments there are active carbon and sulfur cycles that contain abiogenic and biogenic processes, which are eventually imprinted in the geochemical signatures of the basement rocks and the calcite and magnesite deposits associated with fluids that issue from these systems. Here, we present the carbon and sulfur geochemistry of ultramafic rocks and carbonate deposits from the Santa Elena ophiolite in Costa Rica. The aim of this study is to leverage the geochemistry of the ultramafic sequence and associated deposits to distinguish between processes that were dominant during ocean floor alteration and those dominant during low-temperature, continental water-peridotite interaction. The peridotites are variably serpentinized with total sulfur concentrations up to 877 ppm that is typically dominated by sulfide over sulfate. With the exception of one sample the ultramafic rocks are characterized by positive δ34Ssulfide (up to + 23.1‰) and δ34Ssulfate values (up to + 35.0‰). Carbon contents in the peridotites are low and are isotopically distinct from typical oceanic serpentinites. In particular, δ13C of the inorganic carbon suggests that the carbon is not derived from seawater, but rather the product of the interaction of meteoric water with the ultramafic rocks. In contrast, the sulfur isotope data from sulfide minerals in the peridotites preserve evidence for interaction with a hydrothermal fluid. Specifically, they indicate closed system abiogenic sulfate reduction suggesting that oceanic serpentinization occurred with limited input of seawater. Overall, the geochemical signatures preserve evidence for both oceanic and continental water-rock interaction with the majority of carbon (and possibly sulfate) being incorporated during continental water-rock interaction. Furthermore, there is

Geochemistry of Enceladus and the Galilean Moons from in situ Analysis of Ejecta

NASA Astrophysics Data System (ADS)

Postberg, F.; Schmidt, J.; Hillier, J. K.; Kempf, S.; Srama, R.

2012-09-01

The contribution of Cassini's dust detector CDA in revealing subsurface liquid water on Enceladus has demonstrated how questions in planetary science can be addressed by in situ analyses of icy dust particles. As the measurements are particularly sensitive to non-ice compounds embedded in an ice matrix, concentrations of various salts and organic compounds can be identified in different dust populations. This has successfully been demonstrated at Enceladus, giving insights in the moons subsurface geochemistry. This method can be applied to any planetary body that ejects particles to distances suitable for spacecraft sensing. The Galilean moons are of particular relevance since they are believed to steadily emit grains from their surfaces either by active volcanism (Io) or stimulated by micrometeoroid bombardment (Europa, Ganymede, Callisto).

Ultrafast Hydration Dynamics and Coupled Water-Protein Fluctuations in Apomyoglobin

NASA Astrophysics Data System (ADS)

Yang, Yi; Zhang, Luyuan; Wang, Lijuan; Zhong, Dongping

2009-06-01

Protein hydration dynamics are of fundamental importance to its structure and function. Here, we characterize the global solvation dynamics and anisotropy dynamics around the apomyoglobin surface in different conformational states (native and molten globule) by measuring the Stokes shift and anisotropy decay of tryptophan with femtosecond-resolved fluorescence upconversion. With site-directed mutagenesis, we designed sixteen mutants with one tryptophan in each, and placed the probe at a desirable position ranging from buried in the protein core to fully solvent-exposed on the protein surface. In all protein sites studied, two distinct solvation relaxations (1-8 ps and 20-200 ps) were observed, reflecting the initial collective water relaxation and subsequent hydrogen-bond network restructuring, respectively, and both are strongly correlated with protein's local structures and chemical properties. The hydration dynamics of the mutants in molten globule state are faster than those observed in native state, indicating that the protein becomes more flexible and less structured when its conformation is converted from fully-folded native state to partially-folded molten globule state. Complementary, fluorescence anisotropy dynamics of all mutants in native state show an increasing trend of wobbling times (40-260 ps) when the location of the probe is changed from a loop, to a lateral helix, and then, to the compact protein core. Such an increase in wobbling times is related to the local protein structural rigidity, which relates the interaction of water with side chains. The ultrafast hydration dynamics and related side-chain motion around the protein surface unravel the coupled water-protein fluctuations on the picosecond time scales and indicate that the local protein motions are slaved by hydrating water fluctuations.

Development and application of coupled system dynamics and game theory: A dynamic water conflict resolution method.

PubMed

Zomorodian, Mehdi; Lai, Sai Hin; Homayounfar, Mehran; Ibrahim, Shaliza; Pender, Gareth

2017-01-01

Conflicts over water resources can be highly dynamic and complex due to the various factors which can affect such systems, including economic, engineering, social, hydrologic, environmental and even political, as well as the inherent uncertainty involved in many of these factors. Furthermore, the conflicting behavior, preferences and goals of stakeholders can often make such conflicts even more challenging. While many game models, both cooperative and non-cooperative, have been suggested to deal with problems over utilizing and sharing water resources, most of these are based on a static viewpoint of demand points during optimization procedures. Moreover, such models are usually developed for a single reservoir system, and so are not really suitable for application to an integrated decision support system involving more than one reservoir. This paper outlines a coupled simulation-optimization modeling method based on a combination of system dynamics (SD) and game theory (GT). The method harnesses SD to capture the dynamic behavior of the water system, utilizing feedback loops between the system components in the course of the simulation. In addition, it uses GT concepts, including pure-strategy and mixed-strategy games as well as the Nash Bargaining Solution (NBS) method, to find the optimum allocation decisions over available water in the system. To test the capability of the proposed method to resolve multi-reservoir and multi-objective conflicts, two different deterministic simulation-optimization models with increasing levels of complexity were developed for the Langat River basin in Malaysia. The later is a strategic water catchment that has a range of different stakeholders and managerial bodies, which are however willing to cooperate in order to avoid unmet demand. In our first model, all water users play a dynamic pure-strategy game. The second model then adds in dynamic behaviors to reservoirs to factor in inflow uncertainty and adjust the strategies for

Development and application of coupled system dynamics and game theory: A dynamic water conflict resolution method

PubMed Central

Lai, Sai Hin; Homayounfar, Mehran; Ibrahim, Shaliza; Pender, Gareth

2017-01-01

Conflicts over water resources can be highly dynamic and complex due to the various factors which can affect such systems, including economic, engineering, social, hydrologic, environmental and even political, as well as the inherent uncertainty involved in many of these factors. Furthermore, the conflicting behavior, preferences and goals of stakeholders can often make such conflicts even more challenging. While many game models, both cooperative and non-cooperative, have been suggested to deal with problems over utilizing and sharing water resources, most of these are based on a static viewpoint of demand points during optimization procedures. Moreover, such models are usually developed for a single reservoir system, and so are not really suitable for application to an integrated decision support system involving more than one reservoir. This paper outlines a coupled simulation-optimization modeling method based on a combination of system dynamics (SD) and game theory (GT). The method harnesses SD to capture the dynamic behavior of the water system, utilizing feedback loops between the system components in the course of the simulation. In addition, it uses GT concepts, including pure-strategy and mixed-strategy games as well as the Nash Bargaining Solution (NBS) method, to find the optimum allocation decisions over available water in the system. To test the capability of the proposed method to resolve multi-reservoir and multi-objective conflicts, two different deterministic simulation-optimization models with increasing levels of complexity were developed for the Langat River basin in Malaysia. The later is a strategic water catchment that has a range of different stakeholders and managerial bodies, which are however willing to cooperate in order to avoid unmet demand. In our first model, all water users play a dynamic pure-strategy game. The second model then adds in dynamic behaviors to reservoirs to factor in inflow uncertainty and adjust the strategies for

Geochemistry of the Amazon Estuary

USGS Publications Warehouse

Smoak, Joseph M.; Krest, James M.; Swarzenski, Peter W

2006-01-01

The Amazon River supplies more freshwater to the ocean than any other river in the world. This enormous volume of freshwater forces the estuarine mixing out of the river channel and onto the continental shelf. On the continental shelf, the estuarine mixing occurs in a very dynamic environment unlike that of a typical estuary. The tides, the wind, and the boundary current that sweeps the continental shelf have a pronounced influence on the chemical and biological processes occurring within the estuary. The dynamic environment, along with the enormous supply of water, solutes and particles makes the Amazon estuary unique. This chapter describes the unique features of the Amazon estuary and how these features influence the processes occurring within the estuary. Examined are the supply and cycling of major and minor elements, and the use of naturally occurring radionuclides to trace processes including water movement, scavenging, sediment-water interaction, and sediment accumulation rates. The biogeochemical cycling of carbon, nitrogen, and phosphorus, and the significances of the Amazon estuary in the global mass balance of these elements are examined.

Molecular Dynamics implementation of BN2D or 'Mercedes Benz' water model

NASA Astrophysics Data System (ADS)

Scukins, Arturs; Bardik, Vitaliy; Pavlov, Evgen; Nerukh, Dmitry

2015-05-01

Two-dimensional 'Mercedes Benz' (MB) or BN2D water model (Naim, 1971) is implemented in Molecular Dynamics. It is known that the MB model can capture abnormal properties of real water (high heat capacity, minima of pressure and isothermal compressibility, negative thermal expansion coefficient) (Silverstein et al., 1998). In this work formulas for calculating the thermodynamic, structural and dynamic properties in microcanonical (NVE) and isothermal-isobaric (NPT) ensembles for the model from Molecular Dynamics simulation are derived and verified against known Monte Carlo results. The convergence of the thermodynamic properties and the system's numerical stability are investigated. The results qualitatively reproduce the peculiarities of real water making the model a visually convenient tool that also requires less computational resources, thus allowing simulations of large (hydrodynamic scale) molecular systems. We provide the open source code written in C/C++ for the BN2D water model implementation using Molecular Dynamics.

Holistic irrigation water management approach based on stochastic soil water dynamics

NASA Astrophysics Data System (ADS)

Alizadeh, H.; Mousavi, S. J.

2012-04-01

Appreciating the essential gap between fundamental unsaturated zone transport processes and soil and water management due to low effectiveness of some of monitoring and modeling approaches, this study presents a mathematical programming model for irrigation management optimization based on stochastic soil water dynamics. The model is a nonlinear non-convex program with an economic objective function to address water productivity and profitability aspects in irrigation management through optimizing irrigation policy. Utilizing an optimization-simulation method, the model includes an eco-hydrological integrated simulation model consisting of an explicit stochastic module of soil moisture dynamics in the crop-root zone with shallow water table effects, a conceptual root-zone salt balance module, and the FAO crop yield module. Interdependent hydrology of soil unsaturated and saturated zones is treated in a semi-analytical approach in two steps. At first step analytical expressions are derived for the expected values of crop yield, total water requirement and soil water balance components assuming fixed level for shallow water table, while numerical Newton-Raphson procedure is employed at the second step to modify value of shallow water table level. Particle Swarm Optimization (PSO) algorithm, combined with the eco-hydrological simulation model, has been used to solve the non-convex program. Benefiting from semi-analytical framework of the simulation model, the optimization-simulation method with significantly better computational performance compared to a numerical Mote-Carlo simulation-based technique has led to an effective irrigation management tool that can contribute to bridging the gap between vadose zone theory and water management practice. In addition to precisely assessing the most influential processes at a growing season time scale, one can use the developed model in large scale systems such as irrigation districts and agricultural catchments. Accordingly

Spatial and temporal dynamics of sediment in contrasted mountainous watersheds (Mexican transvolcanic belt and French Southern Alps) combining river gauging, elemental geochemistry and fallout radionuclides

NASA Astrophysics Data System (ADS)

Evrard, O.; Navratil, O.; Gratiot, N.; Némery, J.; Duvert, C.; Ayrault, S.; Lefèvre, I.; Legout, C.; Bonté, P.; Esteves, M.

2009-12-01

In mountainous environments, an excessive fine sediment supply to the rivers typically leads to an increase in water turbidity, contaminant transport and a rapid filling of reservoirs. This situation is particularly problematic in regions where water reservoirs are used to provide drinking water to large cities (e.g. in central Mexico) or where stream water is used to run hydroelectric power plants (e.g. in the French Southern Alps). In such areas, sediment source areas first need to be delineated and sediment fluxes between hillslopes and the river system must be better understood before implementing efficient erosion control measures. In this context, the STREAMS (« Sediment Transport and Erosion Across MountainS ») project funded by the French National Research Agency (ANR) aims at understanding the spatial and temporal dynamics of sediment at the scale of mountainous watersheds (between 500 - 1000 km2) located in contrasted environments. This 3-years study is carried out simultaneously in a volcanic watershed located in the Mexican transvolcanic belt undergoing a subhumid tropical climate, as well as in a sedimentary watershed of the French Southern Alps undergoing a transitional climate with Mediterranean and continental influences. One of the main specificities of this project consists in combining traditional monitoring techniques (i.e. installation of river gauges, turbidimeters and sediment samplers in several sub-catchments) and sediment fingerprinting using elemental geochemistry (measured by Instrumental Neutron Activation Analysis - INAA - and Inductively Coupled Plasma - Mass Spectrometry - ICP-MS) and fallout radionuclides (measured by gamma spectrometry). In the French watershed, geochemical analysis allows outlining different sediment sources (e.g. the contribution of calcareous vs. marl-covered sub-watersheds). Radionuclide ratios (e.g.Be-7/Cs-137) allow identifying the dominant erosion processes occurring within the watershed. Areas mostly

The Widom line and dynamical crossover in supercritical water: Popular water models versus experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corradini, D.; Rovere, M.; Gallo, P., E-mail: gallop@fis.uniroma3.it

2015-09-21

In a previous study [Gallo et al., Nat. Commun. 5, 5806 (2014)], we have shown an important connection between thermodynamic and dynamical properties of water in the supercritical region. In particular, by analyzing the experimental viscosity and the diffusion coefficient obtained in simulations performed using the TIP4P/2005 model, we have found that the line of response function maxima in the one phase region, the Widom line, is connected to a crossover from a liquid-like to a gas-like behavior of the transport coefficients. This is in agreement with recent experiments concerning the dynamics of supercritical simple fluids. We here show howmore » different popular water models (TIP4P/2005, TIP4P, SPC/E, TIP5P, and TIP3P) perform in reproducing thermodynamic and dynamic experimental properties in the supercritical region. In particular, the comparison with experiments shows that all the analyzed models are able to qualitatively predict the dynamical crossover from a liquid-like to a gas-like behavior upon crossing the Widom line. Some of the models perform better in reproducing the pressure-temperature slope of the Widom line of supercritical water once a rigid shift of the phase diagram is applied to bring the critical points to coincide with the experimental ones.« less

On rotational dynamics of an NH4+ ion in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Tsun-Mei; Dang, Liem X.

2003-05-15

We used molecular dynamics simulations to characterize the rotational dynamics of the NH4+ ion in liquid water. The polarizable potential models were to describe the ion-water and water-water interactions. This study complements the work of Karim and Haymet (J. Chem. Phys., 93, 5961, 1990), who employed effective pir potential models. The computed rotational diffusion coefficients of the NH4+ ion in water, which were determined from the angular momentum autocorrelation function and the angular mean-square displacement, are 0.093 x 1012 rad2/s and 0.067 x 1012 rad2/s, repectively. These results are in good agreement with the 0.075 x 1012 rad2/s value determinedmore » from the nuclear magnetic resonance (NMR) spectroscopy studies of Perrin and Gipe (J. Am. Chem. Soc., 108, 1088, 1986; Science, 238, 1393, 1987).« less

POLLUTION PREVENTION OPPORTUNITY ASSESSMENT - GEOCHEMISTRY LABORATORY AT SANDIA NATIONAL LABORATORIES

EPA Science Inventory

These reports summarize pollution prevention opportunity assessments conducted jointly by EPA and DOE at the Geochemistry Laboratory and the Manufacturing and Fabrication Repair Laboratory at the Department of Energy's Sandia National Laboratories facility in Albuquerque, New Mex...

Solute rotational dynamics at the water liquid/vapor interface.

PubMed

Benjamin, Ilan

2007-11-28

The rotational dynamics of a number of diatomic molecules adsorbed at different locations at the interface between water and its own vapors are studied using classical molecular dynamics computer simulations. Both equilibrium orientational and energy correlations and nonequilibrium orientational and energy relaxation correlations are calculated. By varying the dipole moment of the molecule and its location, and by comparing the results with those in bulk water, the effects of dielectric and mechanical frictions on reorientation dynamics and on rotational energy relaxation can be studied. It is shown that for nonpolar and weekly polar solutes, the equilibrium orientational relaxation is much slower in the bulk than at the interface. As the solute becomes more polar, the rotation slows down and the surface and bulk dynamics become similar. The energy relaxation (both equilibrium and nonequilibrium) has the opposite trend with the solute dipole (larger dipoles relax faster), but here again the bulk and surface results converge as the solute dipole is increased. It is shown that these behaviors correlate with the peak value of the solvent-solute radial distribution function, which demonstrates the importance of the first hydration shell structure in determining the rotational dynamics and dependence of these dynamics on the solute dipole and location.

Leaf water dynamics of Arabidopsis thaliana monitored in-vivo using terahertz time-domain spectroscopy

NASA Astrophysics Data System (ADS)

Castro-Camus, E.; Palomar, M.; Covarrubias, A. A.

2013-10-01

The declining water availability for agriculture is becoming problematic for many countries. Therefore the study of plants under water restriction is acquiring extraordinary importance. Botanists currently follow the dehydration of plants comparing the fresh and dry weight of excised organs, or measuring their osmotic or water potentials; these are destructive methods inappropriate for in-vivo determination of plants' hydration dynamics. Water is opaque in the terahertz band, while dehydrated biological tissues are partially transparent. We used terahertz spectroscopy to study the water dynamics of Arabidopsis thaliana by comparing the dehydration kinetics of leaves from plants under well-irrigated and water deficit conditions. We also present measurements of the effect of dark-light cycles and abscisic acid on its water dynamics. The measurements we present provide a new perspective on the water dynamics of plants under different external stimuli and confirm that terahertz can be an excellent non-contact probe of in-vivo tissue hydration.

Soil Water Balance and Vegetation Dynamics in two Contrasting Water-limited Mediterranean Ecosystems on Sardinia, Italy

NASA Astrophysics Data System (ADS)

Montaldo, N.; Albertson, J. D.; Corona, R.

2011-12-01

Water limited conditions strongly impacts soil and vegetation dynamics in Mediterranean regions, which are commonly heterogeneous ecosystems, characterized by inter-annual rainfall variability, topography variability and contrasting plant functional types (PFTs) competing for water use. Mediterranean regions are characterized by two main ecosystems, grassland and woodland, which for both natural and anthropogenic causes can grow in soils with different characteristics, highly impacting water resources. Water resources and forestal planning need a deep understanding of the dynamics between PFTs, soil and atmosphere and their impacts on water and CO2 distributions of these two main ecosystems. The first step is the monitoring of land surface fluxes, soil moisture, and vegetation dynamics of the two contrasting ecosystems. Moreover, due to the large percentage of soils with low depth (< 50 cm), and due to the quick hydrologic answer to atmospheric forcing in these soils, there is also the need to understand the impact of the soil depth in the vegetation dynamics, and make measurements in these types of soils. Sardinia island is a very interesting and representative region of Mediterranean ecosystems. It is low urbanized, and is not irrigated, except some plan areas close to the main cities where main agricultural activities are concentrated. The case study sites are within the Flumendosa river basin on Sardinia. Two sites, both in the Flumendosa river and with similar height a.s.l., are investigated. The distance between the sites is around 4 km but the first is a typically grass site located on an alluvial plan valley with a soil depth more than 2m, while the second site is a patchy mixture of Mediterranean vegetation types Oaks, creepers of the wild olive trees and C3 herbaceous species and the soil thickness varies from 15-40 cm, bounded from below by a rocky layer of basalt, partially fractured. In both sites land-surface fluxes and CO2 fluxes are estimated by

Dynamic Ice-Water Interactions Form Europa's Chaos Terrains

NASA Astrophysics Data System (ADS)

Blankenship, D. D.; Schmidt, B. E.; Patterson, G. W.; Schenk, P.

2011-12-01

Unique to the surface of Europa, chaos terrain is diagnostic of the properties and dynamics of its icy shell. We present a new model that suggests large melt lenses form within the shell and that water-ice interactions above and within these lenses drive the production of chaos. This model is consistent with key observations of chaos, predicts observables for future missions, and indicates that the surface is likely still active today[1]. We apply lessons from ice-water interaction in the terrestrial cryosphere to hypothesize a dynamic lense-collapse model to for Europa's chaos terrain. Chaos terrain morphology, like that of Conamara chaos and Thera Macula, suggests a four-phase formation [1]: 1) Surface deflection occurs as ice melts over ascending thermal plumes, as regularly occurs on Earth as subglacial volcanoes activate. The same process can occur at Europa if thermal plumes cause pressure melt as they cross ice-impurity eutectics. 2) Resulting hydraulic gradients and driving forces produce a sealed, pressurized melt lense, akin to the hydraulic sealing of subglacial caldera lakes. On Europa, the water cannot escape the lense due to the horizontally continuous ice shell. 3) Extension of the brittle ice lid above the lense opens cracks, allowing for the ice to be hydrofractured by pressurized water. Fracture, brine injection and percolation within the ice and possible iceberg toppling produces ice-melange-like granular matrix material. 4) Refreezing of the melt lense and brine-filled pores and cracks within the matrix results in raised chaos. Brine soaking and injection concentrates the ice in brines and adds water volume to the shell. As this englacial water freezes, the now water-filled ice will expand, not unlike the process of forming pingos and other "expansion ice" phenomena on Earth. The refreezing can raise the surface and create the oft-observed matrix "domes" In this presentation, we describe how catastrophic ice-water interactions on Earth have

Structure and Dynamics of the Instantaneous Water/Vapor Interface Revisited by Path-Integral and Ab Initio Molecular Dynamics Simulations.

PubMed

Kessler, Jan; Elgabarty, Hossam; Spura, Thomas; Karhan, Kristof; Partovi-Azar, Pouya; Hassanali, Ali A; Kühne, Thomas D

2015-08-06

The structure and dynamics of the water/vapor interface is revisited by means of path-integral and second-generation Car-Parrinello ab initio molecular dynamics simulations in conjunction with an instantaneous surface definition [Willard, A. P.; Chandler, D. J. Phys. Chem. B 2010, 114, 1954]. In agreement with previous studies, we find that one of the OH bonds of the water molecules in the topmost layer is pointing out of the water into the vapor phase, while the orientation of the underlying layer is reversed. Therebetween, an additional water layer is detected, where the molecules are aligned parallel to the instantaneous water surface.

Ecohydrology of dry regions: storage versus pulse soil water dynamics

USGS Publications Warehouse

Lauenroth, William K.; Schlaepfer, Daniel R.; Bradford, John B.

2014-01-01

Although arid and semiarid regions are defined by low precipitation, the seasonal timing of temperature and precipitation can influence net primary production and plant functional type composition. The importance of precipitation seasonality is evident in semiarid areas of the western U.S., which comprise the Intermountain (IM) zone, a region that receives important winter precipitation and is dominated by woody plants and the Great Plains (GP), a region that receives primarily summer precipitation and is dominated by perennial grasses. Although these general relationships are well recognized, specific differences in water cycling between these regions have not been well characterized. We used a daily time step soil water simulation model and twenty sites from each region to analyze differences in soil water dynamics and ecosystem water balance. IM soil water patterns are characterized by storage of water during fall, winter, and spring resulting in relatively reliable available water during spring and early summer, particularly in deep soil layers. By contrast, GP soil water patterns are driven by pulse precipitation events during the warm season, resulting in fluctuating water availability in all soil layers. These contrasting patterns of soil water—storage versus pulse dynamics—explain important differences between the two regions. Notably, the storage dynamics of the IN sites increases water availability in deep soil layers, favoring the deeper rooted woody plants in that region, whereas the pulse dynamics of the Great Plains sites provide water primarily in surface layers, favoring the shallow-rooted grasses in that region. In addition, because water received when plants are either not active or only partially so is more vulnerable to evaporation and sublimation than water delivered during the growing season, IM ecosystems use a smaller fraction of precipitation for transpiration (47%) than GP ecosystems (49%). Recognizing the pulse-storage dichotomy in

A Dynamic Framework for Water Security

NASA Astrophysics Data System (ADS)

Srinivasan, Veena; Konar, Megan; Sivapalan, Murugesu

2017-04-01

Water security is a multi-faceted problem, going beyond mere balancing of supply and demand. Conventional attempts to quantify water security starting rely on static indices at a particular place and point in time. While these are simple and scalable, they lack predictive or explanatory power. 1) Most static indices focus on specific spatial scales and largely ignore cross-scale feedbacks between human and water systems. 2) They fail to account for the increasing spatial specialization in the modern world - some regions are cities others are agricultural breadbaskets; so water security means different things in different places. Human adaptation to environmental change necessitates a dynamic view of water security. We present a framework that defines water security as an emergent outcome of a coupled socio-hydrologic system. Over the medium term (5-25 years), water security models might hold governance, culture and infrastructure constant, but allow humans to respond to changes and thus predict how water security would evolve. But over very long time-frames (25-100 years), a society's values, norms and beliefs themselves may themselves evolve; these in turn may prompt changes in policy, governance and infrastructure. Predictions of water security in the long term involve accounting for such regime shifts in the cultural and political context of a watershed by allowing the governing equations of the models to change.

Dynamics of two-dimensional monolayer water confined in hydrophobic and charged environments.

PubMed

Kumar, Pradeep; Han, Sungho

2012-09-21

We perform molecular dynamics simulations to study the effect of charged surfaces on the intermediate and long time dynamics of water in nanoconfinements. Here, we use the transferable interaction potential with five points (TIP5P) model of a water molecule confined in both hydrophobic and charged surfaces. For a single molecular layer of water between the surfaces, we find that the temperature dependence of the lateral diffusion constant of water up to very high temperatures remains Arrhenius with a high activation energy. In case of charged surfaces, however, the dynamics of water in the intermediate time regime is drastically modified presumably due to the transient coupling of dipoles of water molecules with electric field fluctuations induced by charges on the confining surfaces. Specifically, the lateral mean square displacements display a distinct super-diffusive behavior at intermediate time scale, defined as the time scale between ballistic and diffusive regimes. This change in the intermediate time-scale dynamics in the charged confinement leads to the enhancement of long-time dynamics as reflected in increasing diffusion constant. We introduce a simple model for a possible explanation of the super-diffusive behavior and find it to be in good agreement with our simulation results. Furthermore, we find that confinement and the surface polarity enhance the low frequency vibration in confinement compared to bulk water. By introducing a new effective length scale of coupling between translational and orientational motions, we find that the length scale increases with the increasing strength of the surface polarity. Further, we calculate the correlation between the diffusion constant and the excess entropy and find a disordering effect of polar surfaces on the structure of water. Finally, we find that the empirical relation between the diffusion constant and the excess entropy holds for a monolayer of water in nanoconfinement.

Biogeochemical control points in a water-limited critical zone

NASA Astrophysics Data System (ADS)

Chorover, J.; Brooks, P. D.; Gallery, R. E.; McIntosh, J. C.; Olshansky, Y.; Rasmussen, C.

2017-12-01

The routing of water and carbon through complex terrain is postulated to control structure evolution in the sub-humid critical zone of the southwestern US. By combining measurements of land-atmosphere exchange, ecohydrologic partitioning, and subsurface biogeochemistry, we seek to quantify how a heterogeneous (in time and space) distribution of "reactants" impacts both short-term (sub-)catchment response (e.g., pore and surface water chemical dynamics) and long-term landscape evolution (e.g., soil geochemistry/morphology and regolith weathering depth) in watersheds underlain by rhyolite and schist. Instrumented pedons in convergent, planar, and divergent landscape positions show distinct depth-dependent responses to precipitation events. Wetting front propagation, dissolved carbon flux and associated biogeochemical responses (e.g., pulses of CO2 production, O2 depletion, solute release) vary with topography, revealing the influence of lateral subsidies of water and carbon. The impacts of these episodes on the evolution of porous media heterogeneity is being investigated by statistical analysis of pore water chemistry, chemical/spectroscopic studies of solid phase organo-mineral products, sensor-derived water characteristic curves, and quantification of co-located microbial community activity/composition. Our results highlight the interacting effects of critical zone structure and convergent hydrologic flows in the evolution of biogeochemical control points.

Socioeconomic dynamics of water quality in the Egyptian Nile

NASA Astrophysics Data System (ADS)

Malik, Maheen; Nisar, Zainab; Karakatsanis, Georgios

2016-04-01

The Nile River remains the most important source of freshwater for Egypt as it accounts for nearly all of the country's drinking and irrigation water. About 95% of the total population is accounted to live along the Banks of the Nile(1). Therefore, water quality deterioration in addition to general natural scarcity of water in the region(2) is the main driver for carrying out this study. What further aggravates this issue is the water conflict in the Blue Nile region. The study evaluates different water quality parameters and their concentrations in the Egyptian Nile; further assessing the temporal dynamics of water quality in the area with (a) the Environmental Kuznets Curve (EKC)(3) and (b) the Jevons Paradox (JP)(4) in order to identify water quality improvements or degradations using selected socioeconomic variables(5). For this purpose various environmental indicators including BOD, COD, DO, Phosphorus and TDS were plotted against different economic variables including Population, Gross Domestic Product (GDP), Annual Fresh Water Withdrawal and Improved Water Source. Mathematically, this was expressed by 2nd and 3rd degree polynomial regressions generating the EKC and JP respectively. The basic goal of the regression analysis is to model and highlight the dynamic trend of water quality indicators in relation to their established permissible limits, which will allow the identification of optimal future water quality policies. The results clearly indicate that the dependency of water quality indicators on socioeconomic variables differs for every indicator; while COD was above the permissible limits in all the cases despite of its decreasing trend in each case, BOD and phosphate signified increasing concentrations for the future, if they continue to follow the present trend. This could be an indication of rebound effect explained by the Jevons Paradox i.e. water quality deterioration after its improvement, either due to increase of population or intensification

Dynamic fuzzy modeling of storm water infiltration in urban fractured aquifers

USGS Publications Warehouse

Hong, Y.-S.; Rosen, Michael R.; Reeves, R.R.

2002-01-01

In an urban fractured-rock aquifer in the Mt. Eden area of Auckland, New Zealand, disposal of storm water is via "soakholes" drilled directly into the top of the fractured basalt rock. The dynamic response of the groundwater level due to the storm water infiltration shows characteristics of a strongly time-varying system. A dynamic fuzzy modeling approach, which is based on multiple local models that are weighted using fuzzy membership functions, has been developed to identify and predict groundwater level fluctuations caused by storm water infiltration. The dynamic fuzzy model is initialized by the fuzzy clustering algorithm and optimized by the gradient-descent algorithm in order to effectively derive the multiple local models-each of which is associated with a locally valid model that represents the groundwater level state as a response to different intensities of rainfall events. The results have shown that even if the number of fuzzy local models derived is small, the fuzzy modeling approach developed provides good prediction results despite the highly time-varying nature of this urban fractured-rock aquifer system. Further, it allows interpretable representations of the dynamic behavior of the groundwater system due to storm water infiltration.

Age, geochemistry and melt flux variations for the Hawaiian Ridge

NASA Astrophysics Data System (ADS)

Garcia, M. O.; Weis, D. A.; Greene, A. R.; Wessel, P.; Harrison, L.; Tree, J.

2012-12-01

The Hawaiian Ridge portion of the Hawaiian-Emperor Chain, the classic example of a mantle plume produced linear island chain, is 6000 km in length, active for 80+ Myr, and tectonically simple. Despite its importance to our understanding of mantle plumes and Cenozoic plate motion, there are large data gaps for the age and geochemistry of lavas from volcanoes along the Hawaiian Ridge (HR) portion of the Chain. Ages: Only volcanoes near the Hawaiian-Emperor bend and in the Hawaiian Islands have modern Ar-Ar ages, leaving a gap of 2000 km where existing K-Ar ages suggest synchronous volcanism over a 1000 km section. Geochemistry: There is a 2900 km gap in high precision geochemical data for the HR. The Emperor Seamounts (>45 Ma) have better regional coverage of recent isotopic data and show a correlation of Sr isotope composition with age of the underlying oceanic lithosphere (Regelous et al. 2003). The HR has an unexplained, exponential increase in magma flux over the last 30 Myr (Vidal & Bonneville 2004). Potential explanations for the increase in magma flux include: changes in melting conditions (temperature and/or pressure), change in source fertility related to rock type (pyroxenite vs. peridotite) or previous melting history, and/or changes in plate stresses resulting from reconfigurations of plate motion. Our new multi-disciplinary project will: 1) Determine 40Ar/39Ar ages, and whole-rock major, trace element, and Pb, Sr, Nd and Hf isotopic geochemistry for lavas from 20 volcanoes spanning ~2150 km of the HR (NW of the Hawaiian Islands). 2) Use the geochemical data to determine the long-term evolution of the Hawaiian mantle plume source components and to evaluate whether there have been systematic variations in mantle potential temperature, melting pressure, and/or source lithology during the creation of the HR. If so, are they responsible for the 300% variation in melt production along the Ridge? Also, we will assess when the more fertile Loa source component

Self-gravity, self-consistency, and self-organization in geodynamics and geochemistry

NASA Astrophysics Data System (ADS)

Anderson, Don L.

The results of seismology and geochemistry for mantle structure are widely believed to be discordant, the former favoring whole-mantle convection and the latter favoring layered convection with a boundary near 650 km. However, a different view arises from recognizing effects usually ignored in the construction of these models, including physical plausibility and dimensionality. Self-compression and expansion affect material properties that are important in all aspects of mantle geochemistry and dynamics, including the interpretation of tomographic images. Pressure compresses a solid and changes physical properties that depend on volume and does so in a highly nonlinear way. Intrinsic, anelastic, compositional, and crystal structure effects control seismic velocities; temperature is not the only parameter, even though tomographic images are often treated as temperature maps. Shear velocity is not a good proxy for density, temperature, and composition or for other elastic constants. Scaling concepts are important in mantle dynamics, equations of state, and wherever it is necessary to extend laboratory experiments to the parameter range of the Earth's mantle. Simple volume-scaling relations that permit extrapolation of laboratory experiments, in a thermodynamically self-consistent way, to deep mantle conditions include the quasiharmonic approximation but not the Boussinesq formalisms. Whereas slabs, plates, and the upper thermal boundary layer of the mantle have characteristic thicknesses of hundreds of kilometers and lifetimes on the order of 100 million years, volume-scaling predicts values an order of magnitude higher for deep-mantle thermal boundary layers. This implies that deep-mantle features are sluggish and ancient. Irreversible chemical stratification is consistent with these results; plausible temperature variations in the deep mantle cause density variations that are smaller than the probable density contrasts across chemical interfaces created by

Dynamics of large-diameter water pipes in hydroelectric power plants

NASA Astrophysics Data System (ADS)

Pavić, G.; Chevillotte, F.; Heraud, J.

2017-04-01

An outline is made of physical behaviour of water - filled large pipes. The fluid-wall coupling, the key factor governing the pipe dynamics, is discussed in some detail. Different circumferential pipe modes and the associated cut-on frequencies are addressed from a theoretical as well as practical point of view. Major attention is paid to the breathing mode in view of its importance regarding main dynamic phenomena, such as water hammer. Selected measurement results done at EDF are presented to demonstrate how an external, non-intrusive sensor can detect pressure pulsations of the breathing mode in a pressure pipe. Differences in the pressure measurement using intrusive and non-intrusive sensors reveal the full complexity of large-diameter pipe dynamics.

Geochemistry of thermal water from selected wells, Boise, Idaho

USGS Publications Warehouse

Mariner, R.H.; Young, H.W.; Parliman, D.J.; Evans, William C.

1989-01-01

Samples of thermal water from selected wells in the Boise area were analyzed for chemical composition; stable isotopes of hydrogen, oxygen, and dissolved carbon; radioactive carbon; and dissolved-gas concentrations. Chemically, the waters are virtually identical to those of the adjacent Idaho batholith. Isotopically, the thermal waters are more depleted in deuterium and oxygen-18 than coldwater springs in the presumed recharge area. Chemical and isotopic data indicate the presence of two separate geothermal systems. Radioactive carbon and dissolved helium concentrations are interpreted to indicate recharge during the Pleistocene. Hot water in or southeast of Boise probably recharged 20,000 to 30,000 years ago, and warm water 2.5 miles northwest of Boise probably recharged at least 15,000 years ago.

Large explosive basaltic eruptions at Katla volcano, Iceland: Fragmentation, grain size and eruption dynamics

NASA Astrophysics Data System (ADS)

Schmith, Johanne; Höskuldsson, Ármann; Holm, Paul Martin; Larsen, Guðrún

2018-04-01

Katla volcano in Iceland produces hazardous large explosive basaltic eruptions on a regular basis, but very little quantitative data for future hazard assessments exist. Here details on fragmentation mechanism and eruption dynamics are derived from a study of deposit stratigraphy with detailed granulometry and grain morphology analysis, granulometric modeling, componentry and the new quantitative regularity index model of fragmentation mechanism. We show that magma/water interaction is important in the ash generation process, but to a variable extent. By investigating the large explosive basaltic eruptions from 1755 and 1625, we document that eruptions of similar size and magma geochemistry can have very different fragmentation dynamics. Our models show that fragmentation in the 1755 eruption was a combination of magmatic degassing and magma/water-interaction with the most magma/water-interaction at the beginning of the eruption. The fragmentation of the 1625 eruption was initially also a combination of both magmatic and phreatomagmatic processes, but magma/water-interaction diminished progressively during the later stages of the eruption. However, intense magma/water interaction was reintroduced during the final stages of the eruption dominating the fine fragmentation at the end. This detailed study of fragmentation changes documents that subglacial eruptions have highly variable interaction with the melt water showing that the amount and access to melt water changes significantly during eruptions. While it is often difficult to reconstruct the progression of eruptions that have no quantitative observational record, this study shows that integrating field observations and granulometry with the new regularity index can form a coherent model of eruption evolution.

Structure and Dynamics of Urea/Water Mixtures Investigated by Vibrational Spectroscopy and Molecular Dynamics Simulation

PubMed Central

Carr, J. K.; Buchanan, L. E.; Schmidt, J. R.; Zanni, M. T.; Skinner, J. L.

2013-01-01

Urea/water is an archetypical “biological” mixture, and is especially well known for its relevance to protein thermodynamics, as urea acts as a protein denaturant at high concentration. This behavior has given rise to an extended debate concerning urea’s influence on water structure. Based on a variety of methods and of definitions of water structure, urea has been variously described as a structure-breaker, a structure-maker, or as remarkably neutral towards water. Because of its sensitivity to microscopic structure and dynamics, vibrational spectroscopy can help resolve these debates. We report experimental and theoretical spectroscopic results for the OD stretch of HOD/H2O/urea mixtures (linear IR, 2DIR, and pump-probe anisotropy decay) and for the CO stretch of urea-D4/D2O mixtures (linear IR only). Theoretical results are obtained using existing approaches for water, and a modification of a frequency map developed for acetamide. All absorption spectra are remarkably insensitive to urea concentration, consistent with the idea that urea only very weakly perturbs water structure. Both this work and experiments by Rezus and Bakker, however, show that water’s rotational dynamics are slowed down by urea. Analysis of the simulations casts doubt on the suggestion that urea immobilizes particular doubly hydrogen bonded water molecules. PMID:23841646

Effects of Dimerization of Serratia marcescens Endonuclease on Water Dynamics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chuanying; Beck, Brian W.; Krause, Kurt

2007-02-15

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. The dynamics and structure of Serratia marcescens endonuclease and its neighboring solvent are investigated by molecular dynamics (MD). Comparisons are made with structural and biochemical experiments. The dimer form is physiologic and functions more processively than the monomer. We previously found a channel formed by connected clusters of waters from the active site to the dimer interface. Here, we showmore » that dimerization clearly changes correlations in the water structure and dynamics in the active site not seen in the monomer. Our results indicate that water at the active sites of the dimer is less affected compared with bulk solvent than in the monomer where it has much slower characteristic relaxation times. Given that water is a required participant in the reaction, this gives a clear advantage to dimerization in the absence of an apparent ability to use both active sites simultaneously.« less

Seeking evidence of multidisciplinarity in environmental geochemistry and health: an analysis of arsenic in drinking water research.

PubMed

Aderibigbe, Abiodun D; Stewart, Alex G; Hursthouse, Andrew S

2018-02-01

A multidisciplinary approach to research affords the opportunity of objectivity, creation of new knowledge and potentially a more generally acceptable solution to problems that informed the research in the first place. It increasingly features in national programmes supporting basic and applied research, but for over 40 years, has been the arena for many research teams in environmental geochemistry and health. This study explores the nature of multidisciplinary research in the earth and health sciences using a sample selected from co-authored articles reporting research on arsenic (As) in drinking water from 1979 to 2013. A total of 889 relevant articles were sourced using the online version of the science citation index-expanded (SCI-expanded). The articles were classified according to author affiliation and later by author discipline/research interests using the Revised Field of Science and Technology Frascati manual DSTI/EAS/STP/NESTI (2006) 19/FINAL and a decision algorithm. Few articles were published on the topic until 2000. More articles were published across all affiliations in the last 10 years of the review period (2004-2013) than in the first 10 years (1979-1988). Only 84 (~9%) articles fell within the "earth and health" only and "earth, health and other" categories when classification was undertaken by author affiliation alone. This suggests that level of collaboration between earth and health scientists in arsenic in drinking water research may be very low. By refining the classification further using author discipline/research interests, only 28 of the 84 articles appear to be co-authored by earth and health scientists alongside professionals in other fields. More than half of these 28 articles involved descriptive non-experimental, observational study designs, limited in direct causal hypotheses and mechanistic investigation. If collaborative research is to lead to the increased multidisciplinary research, early interaction should be encouraged

A decision support tool for sustainable planning of urban water systems: presenting the Dynamic Urban Water Simulation Model.

PubMed

Willuweit, Lars; O'Sullivan, John J

2013-12-15

Population growth, urbanisation and climate change represent significant pressures on urban water resources, requiring water managers to consider a wider array of management options that account for economic, social and environmental factors. The Dynamic Urban Water Simulation Model (DUWSiM) developed in this study links urban water balance concepts with the land use dynamics model MOLAND and the climate model LARS-WG, providing a platform for long term planning of urban water supply and water demand by analysing the effects of urbanisation scenarios and climatic changes on the urban water cycle. Based on potential urbanisation scenarios and their effects on a city's water cycle, DUWSiM provides the functionality for assessing the feasibility of centralised and decentralised water supply and water demand management options based on forecasted water demand, stormwater and wastewater generation, whole life cost and energy and potential for water recycling. DUWSiM has been tested using data from Dublin, the capital of Ireland, and it has been shown that the model is able to satisfactorily predict water demand and stormwater runoff. Copyright © 2013 Elsevier Ltd. All rights reserved.

Water table dynamics and biogeochemical cycling in a shallow, variably-saturated floodplain

DOE PAGES

Yabusaki, Steven B.; Wilkins, Michael J.; Fang, Yilin; ...

2017-02-20

Three-dimensional variably saturated flow and multicomponent biogeochemical reactive transport modeling, based on published and newly generated data, is used to better understand the interplay of hydrology, geochemistry, and biology controlling the cycling of carbon, nitrogen, oxygen, iron, sulfur, and uranium in a shallow floodplain. In this system, aerobic respiration generally maintains anoxic groundwater below an oxic vadose zone until seasonal snowmelt-driven water table peaking transports dissolved oxygen (DO) and nitrate from the vadose zone into the alluvial aquifer. The response to this perturbation is localized due to distinct physico-biogeochemical environments and relatively long time scales for transport through the floodplainmore » aquifer and vadose zone. Naturally reduced zones (NRZs) containing sediments higher in organic matter, iron sulfides, and non-crystalline U(IV) rapidly consume DO and nitrate to maintain anoxic conditions, yielding Fe(II) from FeS oxidative dissolution, nitrite from denitrification, and U(VI) from nitrite-promoted U(IV) oxidation. Redox cycling is a key factor for sustaining the observed aquifer behaviors despite continuous oxygen influx and the annual hydrologically induced oxidation event. Furthermore, depth-dependent activity of fermenters, aerobes, nitrate reducers, sulfate reducers, and chemolithoautotrophs (e.g., oxidizing Fe(II), S compounds, and ammonium) is linked to the presence of DO, which has higher concentrations near the water table.« less

Geochemistry of formation waters from the Wolfcamp and “Cline” shales: Insights into brine origin, reservoir connectivity, and fluid flow in the Permian Basin, USA

USGS Publications Warehouse

Engle, Mark A.; Reyes, Francisco R.; Varonka, Matthew S.; Orem, William H.; Lin, Ma; Ianno, Adam J.; Westphal, Tiffani M.; Xu, Pei; Carroll, Kenneth C.

2016-01-01

Despite being one of the most important oil producing provinces in the United States, information on basinal hydrogeology and fluid flow in the Permian Basin of Texas and New Mexico is lacking. The source and geochemistry of brines from the basin were investigated (Ordovician- to Guadalupian-age reservoirs) by combining previously published data from conventional reservoirs with geochemical results for 39 new produced water samples, with a focus on those from shales. Salinity of the Ca–Cl-type brines in the basin generally increases with depth reaching a maximum in Devonian (median = 154 g/L) reservoirs, followed by decreases in salinity in the Silurian (median = 77 g/L) and Ordovician (median = 70 g/L) reservoirs. Isotopic data for B, O, H, and Sr and ion chemistry indicate three major types of water. Lower salinity fluids (<70 g/L) of meteoric origin in the middle and upper Permian hydrocarbon reservoirs (1.2–2.5 km depth; Guadalupian and Leonardian age) likely represent meteoric waters that infiltrated through and dissolved halite and anhydrite in the overlying evaporite layer. Saline (>100 g/L), isotopically heavy (O and H) water in Leonardian [Permian] to Pennsylvanian reservoirs (2–3.2 km depth) is evaporated, Late Permian seawater. Water from the Permian Wolfcamp and Pennsylvanian “Cline” shales, which are isotopically similar but lower in salinity and enriched in alkalis, appear to have developed their composition due to post-illitization diffusion into the shales. Samples from the “Cline” shale are further enriched with NH4, Br, I and isotopically light B, sourced from the breakdown of marine kerogen in the unit. Lower salinity waters (<100 g/L) in Devonian and deeper reservoirs (>3 km depth), which plot near the modern local meteoric water line, are distinct from the water in overlying reservoirs. We propose that these deep meteoric waters are part of a newly identified hydrogeologic unit: the Deep Basin Meteoric Aquifer System

The hydro- and multi-isotope geochemistry of iron-rich ground waters emerging at the southern Baltic Sea coast line

NASA Astrophysics Data System (ADS)

Lipka, Marko; Wu, Zijun; Escher, Peter; Struck, Ulrich; Dellwig, Olaf; Schafmeister, Maria; Böttcher*, Michael E.

2013-04-01

Iron-rich groundwater springs emerging at the shore zone of the southern Baltic Sea (BS; Site Meschendorf) were examined on a seasonal base for a period of about two years. Besides major, minor, and trace elements, stable isotopes of water (H-2, O-18), dissolved inorganic carbon (DIC; C-13), and sulfate (S-34) were analyzed. The stream bed sediment was extracted for the geochemistry of the newly formed precipitates and further characterized via SEM-EDAX. Subsequently, the hydrogeochemical results were subjected to a thermodynamic analysis via the PHREEQC speciation model. The springs emerge from small pits (about 60 cm diameter; up to 15cm depth). Surrounding sediments are sandy with gravels found at depth and corresponding high permeabilities. The positions of different springs on the shore zone were stable during the investigation period while the shape of the pits and the stream beds may vary due to wind- and wave-driven forces. Selected measurements of spring yield discharges close to 10 L/min. The H-2 and O-18 contents of the spring waters indicate the ground water to originate from relatively young mixed meteoric waters. The hydrochemistry of the springs was similar and showed some variability in between which indicates that the genetic processes for the ground water before reaching the surface may slightly differ. The springs are characterized by dissolved Ca, Mg, Na, DIC and sulfate, mainly reflecting the interaction with soils and bedrocks in the recharge area that is dominated by marly till. The oxygen-free ground water is rich in Fe, P, and DIC. Iron and dissolved sulfate originate from the oxidation of pyrite, as further confirmed by the 34-S signature of sulfate. The carbon isotope signature of DIC indicates a mixture of biogenic CO2 from the soil zone with some water-rock interaction with carbonate minerals. The streams flow towards the BS and, in contact with the atmosphere, outgas carbon dioxide and takes up oxygen. Upon CO2-degassing, C-12 is

Dynamic Assessment of Water Quality Based on a Variable Fuzzy Pattern Recognition Model

PubMed Central

Xu, Shiguo; Wang, Tianxiang; Hu, Suduan

2015-01-01

Water quality assessment is an important foundation of water resource protection and is affected by many indicators. The dynamic and fuzzy changes of water quality lead to problems for proper assessment. This paper explores a method which is in accordance with the water quality changes. The proposed method is based on the variable fuzzy pattern recognition (VFPR) model and combines the analytic hierarchy process (AHP) model with the entropy weight (EW) method. The proposed method was applied to dynamically assess the water quality of Biliuhe Reservoir (Dailan, China). The results show that the water quality level is between levels 2 and 3 and worse in August or September, caused by the increasing water temperature and rainfall. Weights and methods are compared and random errors of the values of indicators are analyzed. It is concluded that the proposed method has advantages of dynamism, fuzzification and stability by considering the interval influence of multiple indicators and using the average level characteristic values of four models as results. PMID:25689998

Dynamic assessment of water quality based on a variable fuzzy pattern recognition model.

PubMed

Xu, Shiguo; Wang, Tianxiang; Hu, Suduan

2015-02-16

Water quality assessment is an important foundation of water resource protection and is affected by many indicators. The dynamic and fuzzy changes of water quality lead to problems for proper assessment. This paper explores a method which is in accordance with the water quality changes. The proposed method is based on the variable fuzzy pattern recognition (VFPR) model and combines the analytic hierarchy process (AHP) model with the entropy weight (EW) method. The proposed method was applied to dynamically assess the water quality of Biliuhe Reservoir (Dailan, China). The results show that the water quality level is between levels 2 and 3 and worse in August or September, caused by the increasing water temperature and rainfall. Weights and methods are compared and random errors of the values of indicators are analyzed. It is concluded that the proposed method has advantages of dynamism, fuzzification and stability by considering the interval influence of multiple indicators and using the average level characteristic values of four models as results.

Future directions in geobiology and low-temperature geochemistry

USGS Publications Warehouse

Freeman, Katherine H.; Goldhaber, M.B.

2011-01-01

Humanity is confronted with an enormous challenge, as succinctly stated by the late Steven Schneider (2001; quoted by Jantzen 2004*): “Humans are forcing the Earth’s environmental systems to change at a rate that is more advanced than their knowledge of the consequences.” Geobiologists and low-temperature geochemists characterize material from the lithosphere, hydrosphere, atmosphere, and biosphere to understand processes operating within and between these components of the Earth system from the atomic to the planetary scale. For this reason, the interwoven disciplines of geobiology and low-temperature geochemistry are central to understanding and ultimately predicting the behavior of these life-sustaining systems. We present here comments and recommendations from the participants of a workshop entitled “Future Directions in Geobiology and Low-Temperature Geochemistry,” hosted by the Carnegie Institution of Washington, Geophysical Laboratory, Washington, DC, on 27–28 August 2010. The goal of the workshop was to suggest ways to leverage the vast intellectual and analytical capabilities of our diverse scientific community to characterize the Earth’s past, present, and future geochemical habitat as we enter the second decade of what E. O. Wilson dubbed “the century of the environment.”

Dynamics of Surface Reorganization of Poly(methyl methacrylate) in Contact with Water

NASA Astrophysics Data System (ADS)

Horinouchi, Ayanobu; Atarashi, Hironori; Fujii, Yoshihisa; Tanaka, Keiji

2013-03-01

New tools for tailor-made diagnostics, such as DNA arrays and tips for micro-total-analysis systems, are generally made from polymers. In these applications, the polymer surface is in contact with a water phase. However, despite the importance of detailed knowledge of the fundamental interactions of polymer interfaces with liquids, such studies are very limited. As an initial benchmark for designing and constructing specialized biomedical surfaces containing polymer, aggregation states and dynamics of chains at the water interface should be systematically examined. We here apply time-resolved contact angle measurement to study the dynamics of the surface reorganization of poly(methyl methacrylate) (PMMA) in contact with water. By doing the measurements at various temperatures, it is possible to discuss the surface dynamics of PMMA based on the apparent activation energy. Also, sum-frequency generation spectroscopy revealed that the surface reorganization involves the conformational changes in the main chain part as well as the side chains. Hence, the dynamics observed here may reflect the segmental motion at the outermost region of the PMMA film, in which water plays as a plasticizer.

Total water storage dynamics derived from tree-ring records and terrestrial gravity observations

NASA Astrophysics Data System (ADS)

Creutzfeldt, Benjamin; Heinrich, Ingo; Merz, Bruno

2015-10-01

For both societal and ecological reasons, it is important to understand past and future subsurface water dynamics but estimating subsurface water storage is notoriously difficult. In this pilot study, we suggest the reconstruction of subsurface water dynamics by a multi-disciplinary approach combining hydrology, dendrochronology and geodesy. In a first step, nine complete years of high-precision gravimeter observations are used to estimate water storage changes in the subsurface at the Geodetic Observatory Wettzell in the Bavarian Forest, Germany. The record is extended to 63 years by calibrating a hydrological model against the 9 years of gravimeter observations. The relationship between tree-ring growth and water storage changes is evaluated as well as that between tree-ring growth and supplementary hydro-meteorological data. Results suggest that tree-ring growth is influenced primarily by subsurface water storage. Other variables related to the overall moisture status (e.g., Standardized Precipitation Index, Palmer Drought Severity Index, streamflow) are also strongly correlated with tree-ring width. While these indices are all indicators of water stored in the landscape, water storage changes of the subsurface estimated by depth-integral measurements give us the unique opportunity to directly reconstruct subsurface water storage dynamics from records of tree-ring width. Such long reconstructions will improve our knowledge of past water storage variations and our ability to predict future developments. Finally, knowing the relationship between subsurface storage dynamics and tree-ring growth improves the understanding of the different signal components contained in tree-ring chronologies.

Water Plan 2030: A Dynamic Education Model for Teaching Water Management Issues

NASA Astrophysics Data System (ADS)

Rupprecht, C.; Washburne, J.; Lansey, K.; Williams, A.

2006-12-01

Dynamic educational tools to assist teachers and students in recognizing the impacts of water management decisions in a realistic context are not readily available. Water policy issues are often complex and difficult for students trying to make meaningful connections between system components. To fill this need, we have developed a systems modeling-based educational decision support system (DSS) with supplementary materials. This model, called Water Plan 2030, represents a general semi-arid watershed; it allows users to examine water management alternatives by changing input values for various water uses and basin conditions and immediately receive graphical outputs to compare decisions. The main goal of our DSS model is to foster students' abilities to make knowledgeable decisions with regard to water resources issues. There are two reasons we have developed this model for traditional classroom settings. First, the DSS model provides teachers with a mechanism for educating students about inter-related hydrologic concepts, complex systems and facilitates discussion of water resources issues. Second, Water Plan 2030 encourages student discovery of cause/effect relationships in a dynamic, hands-on environment and develops the ability to realize the implications of water management alternatives. The DSS model has been utilized in an undergraduate, non-major science class for 5 course hours, each of the past 4 semesters. Accompanying the PC-based model are supplementary materials to improve the effectiveness of implementation by emphasizing important concepts and guiding learners through the model components. These materials include in-class tutorials, introductory questions, role-playing activities and homework extensions that have been revised after each user session, based on student and instructor feedback. Most recently, we have developed individual lessons that teach specific model functions and concepts. These modules provide teachers the flexibility to adapt

Quantum effects in the dynamics of deeply supercooled water

DOE PAGES

Agapov, Alexander L.; Kolesnikov, Alexander I.; Novikov, Vladimir N.; ...

2015-02-26

In spite of its simple chemical structure, water remains one of the most puzzling liquids with many anomalies at low temperatures. Combining neutron scattering and dielectric relaxation spectroscopy, we show that quantum fluctuations are not negligible in deeply supercooled water. Our dielectric measurements reveal the anomalously weak temperature dependence of structural relaxation in vapor-deposited water close to the glass transition temperature T g~136K. We demonstrate that this anomalous behavior can be explained well by quantum effects. In conclusion, these results have significant implications for our understanding of water dynamics.

Effect of water table dynamics on land surface hydrologic memory

NASA Astrophysics Data System (ADS)

Lo, Min-Hui; Famiglietti, James S.

2010-11-01

The representation of groundwater dynamics in land surface models has received considerable attention in recent years. Most studies have found that soil moisture increases after adding a groundwater component because of the additional supply of water to the root zone. However, the effect of groundwater on land surface hydrologic memory (persistence) has not been explored thoroughly. In this study we investigate the effect of water table dynamics on National Center for Atmospheric Research Community Land Model hydrologic simulations in terms of land surface hydrologic memory. Unlike soil water or evapotranspiration, results show that land surface hydrologic memory does not always increase after adding a groundwater component. In regions where the water table level is intermediate, land surface hydrologic memory can even decrease, which occurs when soil moisture and capillary rise from groundwater are not in phase with each other. Further, we explore the hypothesis that in addition to atmospheric forcing, groundwater variations may also play an important role in affecting land surface hydrologic memory. Analyses show that feedbacks of groundwater on land surface hydrologic memory can be positive, negative, or neutral, depending on water table dynamics. In regions where the water table is shallow, the damping process of soil moisture variations by groundwater is not significant, and soil moisture variations are mostly controlled by random noise from atmospheric forcing. In contrast, in regions where the water table is very deep, capillary fluxes from groundwater are small, having limited potential to affect soil moisture variations. Therefore, a positive feedback of groundwater to land surface hydrologic memory is observed in a transition zone between deep and shallow water tables, where capillary fluxes act as a buffer by reducing high-frequency soil moisture variations resulting in longer land surface hydrologic memory.

Soil-water dynamics and unsaturated storage during snowmelt following wildfire

USGS Publications Warehouse

Ebel, Brian A.; Hinckley, E.S.; Martin, Deborah

2012-01-01

Many forested watersheds with a substantial fraction of precipitation delivered as snow have the potential for landscape disturbance by wildfire. Little is known about the immediate effects of wildfire on snowmelt and near-surface hydrologic responses, including soil-water storage. Montane systems at the rain-snow transition have soil-water dynamics that are further complicated during the snowmelt period by strong aspect controls on snowmelt and soil thawing. Here we present data from field measurements of snow hydrology and subsurface hydrologic and temperature responses during the first winter and spring after the September 2010 Fourmile Canyon Fire in Colorado, USA. Our observations of soil-water content and soil temperature show sharp contrasts in hydrologic and thermal conditions between north- and south-facing slopes. South-facing burned soils were ∼1–2 °C warmer on average than north-facing burned soils and ∼1.5 °C warmer than south-facing unburned soils, which affected soil thawing during the snowmelt period. Soil-water dynamics also differed by aspect: in response to soil thawing, soil-water content increased approximately one month earlier on south-facing burned slopes than on north-facing burned slopes. While aspect and wildfire affect soil-water dynamics during snowmelt, soil-water storage at the end of the snowmelt period reached the value at field capacity for each plot, suggesting that post-snowmelt unsaturated storage was not substantially influenced by aspect in wildfire-affected areas. Our data and analysis indicate that the amount of snowmelt-driven groundwater recharge may be larger in wildfire-impacted areas, especially on south-facing slopes, because of earlier soil thaw and longer durations of soil-water contents above field capacity in those areas.

Surface nanobubble nucleation dynamics during water-ethanol exchange

NASA Astrophysics Data System (ADS)

Chan, Chon U.; Ohl, Claus-Dieter

2015-11-01

Water-ethanol exchange has been a promising nucleation method for surface attached nanobubbles since their discovery. In this process, water and ethanol displace each other sequentially on a substrate. As the gas solubility is 36 times higher in ethanol than water, it was suggested that the exchange process leads to transient supersaturation and is responsible for the nanobubble nucleation. In this work, we visualize the nucleation dynamics by controllably mixing water and ethanol. It depicts the temporal evolution of the conventional exchange in a single field of view, detailing the conditions for surface nanobubble nucleation and the flow field that influences their spatial organization. This technique can also pattern surface nanobubbles with variable size distribution.

Power-law Growth and Punctuated Equilibrium Dynamics in Water Resources Systems

NASA Astrophysics Data System (ADS)

Parolari, A.; Katul, G. G.; Porporato, A. M.

2015-12-01

The global rise in population-driven water scarcity and recent appreciation of strong dynamic coupling between human and natural systems has called for new approaches to predict the future sustainability of regional and global water resources systems. The dynamics of coupled human-water systems are driven by a complex set of social, environmental, and technological factors. Present projections of water resources systems range from a finite carrying capacity regulated by accessible freshwater, or `peak renewable water,' to punctuated evolution with new supplied and improved efficiency gained from technological and social innovation. However, these projections have yet to be quantified from observations or in a comprehensive theoretical framework. Using data on global water withdrawals and storage capacity of regional water supply systems, non-trivial dynamics are identified in water resources systems development over time, including power-law growth and punctuated equilibria. Two models are introduced to explain this behavior: (1) a delay differential equation and (2) a power-law with log-periodic oscillations, both of which rely on past conditions (or system memory) to describe the present rate of growth in the system. In addition, extension of the first model demonstrates how system delays and punctuated equilibria can emerge from coupling between human population growth and associated resource demands. Lastly, anecdotal evidence is used to demonstrate the likelihood of power-law growth in global water use from the agricultural revolution 3000 BC to the present. In a practical sense, the presence of these patterns in models with delayed oscillations suggests that current decision-making related to water resources development results from the historical accumulation of resource use decisions, technological and social changes, and their consequences.

Hydro-dynamic damping theory in flowing water

NASA Astrophysics Data System (ADS)

Monette, C.; Nennemann, B.; Seeley, C.; Coutu, A.; Marmont, H.

2014-03-01

Fluid-structure interaction (FSI) has a major impact on the dynamic response of the structural components of hydroelectric turbines. On mid-head to high-head Francis runners, the rotor-stator interaction (RSI) phenomenon always has to be considered carefully during the design phase to avoid operational issues later on. The RSI dynamic response amplitudes are driven by three main factors: (1) pressure forcing amplitudes, (2) excitation frequencies in relation to natural frequencies and (3) damping. The prediction of the two first factors has been largely documented in the literature. However, the prediction of fluid damping has received less attention in spite of being critical when the runner is close to resonance. Experimental damping measurements in flowing water on hydrofoils were presented previously. Those results showed that the hydro-dynamic damping increased linearly with the flow. This paper presents development and validation of a mathematical model, based on momentum exchange, to predict damping due to fluid structure interaction in flowing water. The model is implemented as an analytical procedure for simple structures, such as cantilever beams, but is also implemented in more general ways using three different approaches for more complex structures such as runner blades: a finite element procedure, a CFD modal work based approach and a CFD 1DOF approach. The mathematical model and all three implementation approaches are shown to agree well with experimental results.

Role of oxygen functional groups for structure and dynamics of interfacial water on low rank coal surface: a molecular dynamics simulation

NASA Astrophysics Data System (ADS)

You, Xiaofang; Wei, Hengbin; Zhu, Xianchang; Lyu, Xianjun; Li, Lin

2018-07-01

Molecular dynamics simulations were employed to study the effects of oxygen functional groups for structure and dynamics properties of interfacial water molecules on the subbituminous coal surface. Because of complex composition and structure, the graphite surface modified by hydroxyl, carboxyl and carbonyl groups was used to represent the surface model of subbituminous coal according to XPS results, and the composing proportion for hydroxyl, carbonyl and carboxyl is 25:3:5. The hydration energy with -386.28 kJ/mol means that the adsorption process between water and coal surface is spontaneous. Density profiles for oxygen atoms and hydrogen atoms indicate that the coal surface properties affect the structural and dynamic characteristics of the interfacial water molecules. The interfacial water exhibits much more ordering than bulk water. The results of radial distribution functions, mean square displacement and local self-diffusion coefficient for water molecule related to three oxygen moieties confirmed that the water molecules prefer to absorb with carboxylic groups, and adsorption of water molecules at the hydroxyl and carbonyl is similar.

Predicting Displaceable Water Sites Using Mixed-Solvent Molecular Dynamics.

PubMed

Graham, Sarah E; Smith, Richard D; Carlson, Heather A

2018-02-26

Water molecules are an important factor in protein-ligand binding. Upon binding of a ligand with a protein's surface, waters can either be displaced by the ligand or may be conserved and possibly bridge interactions between the protein and ligand. Depending on the specific interactions made by the ligand, displacing waters can yield a gain in binding affinity. The extent to which binding affinity may increase is difficult to predict, as the favorable displacement of a water molecule is dependent on the site-specific interactions made by the water and the potential ligand. Several methods have been developed to predict the location of water sites on a protein's surface, but the majority of methods are not able to take into account both protein dynamics and the interactions made by specific functional groups. Mixed-solvent molecular dynamics (MixMD) is a cosolvent simulation technique that explicitly accounts for the interaction of both water and small molecule probes with a protein's surface, allowing for their direct competition. This method has previously been shown to identify both active and allosteric sites on a protein's surface. Using a test set of eight systems, we have developed a method using MixMD to identify conserved and displaceable water sites. Conserved sites can be determined by an occupancy-based metric to identify sites which are consistently occupied by water even in the presence of probe molecules. Conversely, displaceable water sites can be found by considering the sites which preferentially bind probe molecules. Furthermore, the inclusion of six probe types allows the MixMD method to predict which functional groups are capable of displacing which water sites. The MixMD method consistently identifies sites which are likely to be nondisplaceable and predicts the favorable displacement of water sites that are known to be displaced upon ligand binding.

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

NASA Technical Reports Server (NTRS)

Benjamin, Ilan; Pohorille, Andrew

1993-01-01

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

Molecular Dynamics Studies of Structure and Functions of Water-Membrane Interfaces

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Wilson, Michael A.; DeVincenzi, Donald L. (Technical Monitor)

2001-01-01

A large number of essential cellular processes occur at the interfaces between water and membranes. The selectivity and dynamics of these processes are largely determined by the structural and electrical properties of the water-membrane interface. We investigate these properties by the molecular dynamics method. Over the time scales of the simulations, the membrane undergoes fluctuations described by the capillary wave model. These fluctuations produce occasional thinning defects in the membrane which provide effective pathways for passive transport of ions and small molecules across the membrane. Ions moving through the membrane markedly disrupt its structure and allow for significant water penetration into the membrane interior. Selectivity of transport, with respect to ionic charge, is determined by the interfacial electrostatic potential. Many small molecules. of potential significance in catalysis, bioenergetics and pharmacology, are shown to bind to the interface. The energetics and dynamics of this process will be discussed.

Microbial ecology of two hot springs of Sikkim: Predominate population and geochemistry.

PubMed

Najar, Ishfaq Nabi; Sherpa, Mingma Thundu; Das, Sayak; Das, Saurav; Thakur, Nagendra

2018-10-01

Northeastern regions of India are known for their floral and faunal biodiversity. Especially the state of Sikkim lies in the eastern Himalayan ecological hotspot region. The state harbors many sulfur rich hot springs which have therapeutic and spiritual values. However, these hot springs are yet to be explored for their microbial ecology. The development of neo generation techniques such as metagenomics has provided an opportunity for inclusive study of microbial community of different environment. The present study describes the microbial diversity in two hot springs of Sikkim that is Polok and Borong with the assist of culture dependent and culture independent approaches. The culture independent techniques used in this study were next generation sequencing (NGS) and Phospholipid Fatty Acid Analysis (PLFA). Having relatively distinct geochemistry both the hot springs are thermophilic environments with the temperature range of 50-77 °C and pH range of 5-8. Metagenomic data revealed the dominance of bacteria over archaea. The most abundant phyla were Proteobacteria and Bacteroidetes although other phyla were also present such as Acidobacteria, Nitrospirae, Firmicutes, Proteobacteria, Parcubacteria and Spirochaetes. The PLFA studies have shown the abundance of Gram Positive bacteria followed by Gram negative bacteria. The culture dependent technique was correlative with PLFA studies. Most abundant bacteria as isolated and identified were Gram-positive genus Geobacillus and Anoxybacillus. The genus Geobacillus has been reported for the first time in North-Eastern states of India. The Geobacillus species obtained from the concerned hot springs were Geobacillus toebii, Geobacillus lituanicus, Geobacillus Kaustophillus and the Anoxybacillus species includes Anoxybacillus gonensis and Anoxybacillus Caldiproteolyticus. The distribution of major genera and their statistical correlation analyses with the geochemistry of the springs predicted that the temperature, p

Structure, dynamics and stability of water/scCO2/mineral interfaces from ab initio molecular dynamics simulations.

PubMed

Lee, Mal-Soon; Peter McGrail, B; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2015-10-12

The boundary layer at solid-liquid interfaces is a unique reaction environment that poses significant scientific challenges to characterize and understand by experimentation alone. Using ab initio molecular dynamics (AIMD) methods, we report on the structure and dynamics of boundary layer formation, cation mobilization and carbonation under geologic carbon sequestration scenarios (T = 323 K and P = 90 bar) on a prototypical anorthite (001) surface. At low coverage, water film formation is enthalpically favored, but entropically hindered. Simulated adsorption isotherms show that a water monolayer will form even at the low water concentrations of water-saturated scCO2. Carbonation reactions readily occur at electron-rich terminal Oxygen sites adjacent to cation vacancies that readily form in the presence of a water monolayer. These results point to a carbonation mechanism that does not require prior carbonic acid formation in the bulk liquid. This work also highlights the modern capabilities of theoretical methods to address structure and reactivity at interfaces of high chemical complexity.

Cavitation in confined water: ultra-fast bubble dynamics

NASA Astrophysics Data System (ADS)

Vincent, Olivier; Marmottant, Philippe

2012-02-01

In the hydraulic vessels of trees, water can be found at negative pressure. This metastable state, corresponding to mechanical tension, is achieved by evaporation through a porous medium. It can be relaxed by cavitation, i.e. the sudden nucleation of vapor bubbles. Harmful for the tree due to the subsequent emboli of sap vessels, cavitation is on the contrary used by ferns to eject spores very swiftly. We will focus here on the dynamics of the cavitation bubble, which is of primary importance to explain the previously cited natural phenomena. We use the recently developed method of artificial tress, using transparent hydrogels as the porous medium. Our experiments, on water confined in micrometric hydrogel cavities, show an extremely fast dynamics: bubbles are nucleated at the microsecond timescale. For cavities larger than 100 microns, the bubble ``rings'' with damped oscillations at MHz frequencies, whereas for smaller cavities the oscillations become overdamped. This rich dynamics can be accounted for by a model we developed, leading to a modified Rayleigh-Plesset equation. Interestingly, this model predicts the impossibility to nucleate bubbles above a critical confinement that depends on liquid negative pressure and corresponds to approximately 100 nm for 20 MPa tensions.

Impacts of changes in groundwater recharge on the isotopic composition and geochemistry of seasonally ice-covered lakes: insights for sustainable management

NASA Astrophysics Data System (ADS)

Arnoux, Marie; Barbecot, Florent; Gibert-Brunet, Elisabeth; Gibson, John; Noret, Aurélie

2017-11-01

Lakes are under increasing pressure due to widespread anthropogenic impacts related to rapid development and population growth. Accordingly, many lakes are currently undergoing a systematic decline in water quality. Recent studies have highlighted that global warming and the subsequent changes in water use may further exacerbate eutrophication in lakes. Lake evolution depends strongly on hydrologic balance, and therefore on groundwater connectivity. Groundwater also influences the sensitivity of lacustrine ecosystems to climate and environmental changes, and governs their resilience. Improved characterization of groundwater exchange with lakes is needed today for lake preservation, lake restoration, and sustainable management of lake water quality into the future. In this context, the aim of the present paper is to determine if the future evolution of the climate, the population, and the recharge could modify the geochemistry of lakes (mainly isotopic signature and quality via phosphorous load) and if the isotopic monitoring of lakes could be an efficient tool to highlight the variability of the water budget and quality. Small groundwater-connected lakes were chosen to simulate changes in water balance and water quality expected under future climate change scenarios, namely representative concentration pathways (RCPs) 4.5 and 8.5. Contemporary baseline conditions, including isotope mass balance and geochemical characteristics, were determined through an intensive field-based research program prior to the simulations. Results highlight that future lake geochemistry and isotopic composition trends will depend on four main parameters: location (and therefore climate conditions), lake catchment size (which impacts the intensity of the flux change), lake volume (which impacts the range of variation), and lake G index (i.e., the percentage of groundwater that makes up total lake inflows), the latter being the dominant control on water balance conditions, as revealed by

Effect of water on structure and dynamics of [BMIM][PF6] ionic liquid: An all-atom molecular dynamics simulation investigation.

PubMed

Sharma, Anirban; Ghorai, Pradip Kr

2016-03-21

Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure IL but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.

Very Tiny Rocks: Site-Specific, Size-Dependent Reaction Kinetics at Nanoparticle-Water Interfaces

NASA Astrophysics Data System (ADS)

Rustad, J. R.

2008-12-01

One of the most fundamental challenges in geochemistry is to be able to understand the rates and mechanisms of elementary reactions that describe chemical processes occurring at mineral-water interfaces. One of the reasons for the primitive conceptual state of reaction kinetics in solid earth geochemistry is that it is very difficult to identify defensible elementary reactions where theoretical predictions can be made and the results can tested experimentally at the same length and time scale of the prediction. For example, the most fundamental predictor of complexation kinetics in aqueous solution is the characteristic water exchange rate, which are well known for the aquo ions and vary by 20 orders of magnitude even for simple trivalent ions. In contrast, for interfacial reactions, it was not even known whether water exchange rates were faster or slower than equivalent metal sites in solution, prohibiting any quantitive understanding of mineral reaction kinetics at the molecular level. Recent advances in synthesis and characterization of materials at nanometer length scales has been able to bridge the gap in scale, and nanometer-sized minerals have given us our first quantitative understanding of elementary reaction rates for fundamental processes involving water and hydroxide exchange reactions. I describe the results of molecular dynamics calculation and experimental measurement of the rates of water, hydroxide, and proton exchange reactions on nanoparticle surfaces. The calculations already show that transition state theory is completely inadequate to understand the rates of even the simplest elementary reactions. Furthermore, the mechanistic implications of rate parameters such as activation volume and activation enthalpy may be different in moving from aquo ions to interfaces. Is a molecular understanding of geochemical processes really needed? One might have asked a biologist at the turn of the century whether studying the structure of proteins would ever

Dynamics of the Urban Water-Energy Nexuses of Mumbai and London

NASA Astrophysics Data System (ADS)

De Stercke, S.; Mijic, A.; Buytaert, W.; Chaturvedi, V.

2016-12-01

Both in developing as well as industrialized countries, cities are seeing their populations increase as more people concentrate in urban settlements. This burdens existing water and energy systems, which are also increasingly stressed on the supply side due to availability, and policy goals. In addition to the water and energy embedded in the electricity, fuels and water delivered to the city, the linkages in the urban environment itself are important and in magnitude they significantly exceed those upstream in the case of industrialized countries. However, little research has been published on urban water-energy linkages in developing countries. For cities in general, there is also a dearth of studies on the dynamics of these linkages with urban growth and socioeconomic development, and hence of the mutual influence of the urban water and energy systems. System dynamics modeling was used to understand and simulate these dynamics, building on modeling techniques from the water, energy, and urban systems literature. For each of the two characteristically different cities of Mumbai and London a model was constructed and calibrated with data from various public sources and personal interviews. The differences between the two cases are discussed by means of the models. Transition pathways to sustainable cities with respect to water use, energy use and greenhouse gas emissions are illustrated for each city. Furthermore, uncertainties and model sensitivity, and their implications, are presented. Finally, applicability of either or a hybrid of these models to other cities is investigated.

Vibration-rotation-tunneling dynamics in small water clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pugliano, Nick

The goal of this work is to characterize the intermolecular vibrations of small water clusters. Using tunable far infrared laser absorption spectroscopy, large amplitude vibration-rotation-tunneling (VRT) dynamics in vibrationally excited states of the water dimer and the water trimer are investigated. This study begins with the measurement of 12 VRT subbands, consisting of approximately 230 transitions, which are assigned to an 82.6 cm -1 intermolecular vibration of the water dimer-d 4. Each of the VRT subbands originate from K a''=0 and terminate in either K a'=0 or 1. These data provide a complete characterization of the tunneling dynamics in themore » vibrationally excited state as well as definitive symmetry labels for all VRT energy levels. Furthermore, an accurate value for the A' rotational constant is found to agree well with its corresponding ground state value. All other excited state rotational constants are fitted, and discussed in terms of the corresponding ground state constants. In this vibration, the quantum tunneling motions are determined to exhibit large dependencies with both the K a' quantum number and the vibrational coordinate, as is evidenced by the measured tunneling splittings. The generalized internal-axis-method treatment which has been developed to model the tunneling dynamics, is considered for the qualitative description of each tunneling pathway, however, the variation of tunneling splittings with vibrational excitation indicate that the high barrier approximation does not appear to be applicable for this vibrational coordinate. The data are consistent with a motion possessing a' symmetry, and the vibration is assigned as the v 12 acceptor bending coordinate. This assignment is in agreement with the vibrational symmetry, the resultsof high level ab initio calculations, and preliminary data assigned to the analogous vibration in the D 2O-DOH isotopomer.« less

Water table dynamics in undisturbed, drained and restored blanket peat

NASA Astrophysics Data System (ADS)

Holden, J.; Wallage, Z. E.; Lane, S. N.; McDonald, A. T.

2011-05-01

SummaryPeatland water table depth is an important control on runoff production, plant growth and carbon cycling. Many peatlands have been drained but are now subject to activities that might lead to their restoration including the damming of artificial drains. This paper investigates water table dynamics on intact, drained and restored peatland slopes in a blanket peat in northern England using transects of automated water table recorders. Long-term (18 month), seasonal and short-term (storm event) records are explored. The restored site had drains blocked 6 years prior to monitoring commencing. The spatially-weighted mean water table depths over an 18 month period were -5.8 cm, -8.9 cm and -11.5 cm at the intact, restored and drained sites respectively. Most components of water table behaviour at the restored site, including depth exceedance probability curves, seasonality of water table variability, and water table responses to individual rainfall events were intermediate between that of the drained and intact sites. Responses also depended on location with respect to the drains. The results show that restoration of drained blanket peat is difficult and the water table dynamics may not function in the same way as those in undisturbed blanket peat even many years after management intervention. Further measurement of hydrological processes and water table responses to peatland restoration are required to inform land managers of the hydrological success of those projects.

Phosphate rock formation and marine phosphorus geochemistry: the deep time perspective.

PubMed

Filippelli, Gabriel M

2011-08-01

The role that phosphorite formation, the ultimate source rock for fertilizer phosphate reserves, plays in the marine phosphorus (P) cycle has long been debated. A shift has occurred from early models that evoked strikingly different oceanic P cycling during times of widespread phosphorite deposition to current thinking that phosphorite deposits may be lucky survivors of a series of inter-related tectonic, geochemical, sedimentological, and oceanic conditions. This paradigm shift has been facilitated by an awareness of the widespread nature of phosphogenesis-the formation of authigenic P-bearing minerals in marine sediments that contributes to phosphorite formation. This process occurs not just in continental margin sediments, but in deep sea oozes as well, and helps to clarify the driving forces behind phosphorite formation and links to marine P geochemistry. Two processes come into play to make phosphorite deposits: chemical dynamism and physical dynamism. Chemical dynamism involves the diagenetic release and subsequent concentration of P-bearing minerals particularly in horizons, controlled by a number of sedimentological and biogeochemical factors. Physical dynamism involves the reworking and sedimentary capping of P-rich sediments, which can either concentrate the relatively heavy and insoluble disseminated P-bearing minerals or provide an episodic change in sedimentology to concentrate chemically mobilized P. Both processes can result from along-margin current dynamics and/or sea level variations. Interestingly, net P accumulation rates are highest (i.e., the P removal pump is most efficient) when phosphorites are not forming. Both physical and chemical pathways involve processes not dominant in deep sea environments and in fact not often coincide in space and time even on continental margins, contributing to the rarity of high-quality phosphorite deposits and the limitation of phosphate rock reserves. This limitation is becoming critical, as the human demand

Synthesis and review: African environmental processes and water-cycle dynamics.

PubMed

Ichoku, Charles; Adegoke, Jimmy

2016-12-01

Africa's vast landmass harbors a variety of physical processes that affect the environment and the water cycle. This focus issue on 'African Environmental Processes and Water-Cycle Dynamics' contains eight articles that address these phenomena from different but complementary perspectives. Fires used for agricultural and related purposes play a major role in land-cover change, surface albedo modifications, and smoke emission; all of which affect the environment and the water cycle in different ways. However, emissions of aerosols and trace gases are not restricted to fires, but also emanate from other natural and human activities. The African water cycle undergoes significant perturbations that are attributable to several factors, including the aforesaid environmental processes. These changes in the water cycle have produced severe drought and flooding events in recent decades that affect societal wellbeing across sub-Saharan Africa. The combined effects of the environmental processes and water-cycle dynamics affect and are affected by climate variability and can be propagated beyond the continent. Future studies should utilize the wealth of observations and modeling tools that are constantly improving to clearly elucidate the interrelationships between all of these phenomena for the benefit of society.

Differential effects of fine root morphology on water dynamics in the root-soil interface

NASA Astrophysics Data System (ADS)

DeCarlo, K. F.; Bilheux, H.; Warren, J.

2017-12-01

Soil water uptake form plants, particularly in the rhizosphere, is a poorly understood question in the plant and soil sciences. Our study analyzed the role of belowground plant morphology on soil structural and water dynamics of 5 different plant species (juniper, grape, maize, poplar, maple), grown in sandy soils. Of these, the poplar system was extended to capture drying dynamics. Neutron radiography was used to characterize in-situ dynamics of the soil-water-plant system. A joint map of root morphology and soil moisture was created for the plant systems using digital image processing, where soil pixels were connected to associated root structures via minimum distance transforms. Results show interspecies emergent behavior - a sigmoidal relationship was observed between root diameter and bulk/rhizosphere soil water content difference. Extending this as a proxy for extent of rhizosphere development with root age, we observed a logistic growth pattern for the rhizosphere: minimal development in the early stages is superceded by rapid onset of rhizosphere formation, which then stabilizes/decays with the likely root suberization. Dynamics analysis of water content differences between the root/rhizosphere, and rhizosphere/bulk soil interface highlight the persistently higher water content in the root at all water content and root size ranges. At the rhizosphere/bulk soil interface, we observe a shift in soil water dynamics by root size: in super fine roots, we observe that water content is primarily lower in the rhizosphere under wetter conditions, which then gradually increases to a relatively higher water content under drier conditions. This shifts to a persistently higher rhizosphere water content relative to bulk soil in both wet/dry conditions with increased root size, suggesting that, by size, the finest root structures may contribute the most to total soil water uptake in plants.

Nano-confined water in the interlayers of hydrocalumite: Reorientational dynamics probed by neutron spectroscopy and molecular dynamics computer simulations

NASA Astrophysics Data System (ADS)

Kalinichev, A. G.; Faraone, A.; Udovic, T.; Kolesnikov, A. I.; de Souza, N. R.; Reinholdt, M. X.; Kirkpatrick, R.

2008-12-01

Layered double hydroxides (LDHs, anionic clays) represent excellent model systems for detailed molecular- level studies of the structure, dynamics, and energetics of nano-confined water in mineral interlayers and nano-pores, because LDH interlayers can have a well-defined structures and contain H2O molecules and a wide variety of anions in structurally well-defined positions and coordinations. [Ca2Al(OH)6]Cl·2H2O, also known as hydrocalumite or Friedel's salt, has a well- ordered Ca,Al distribution in the hydroxide layer and a very high degree of H2O,Cl ordering in the interlayer. It is also one of the only LDH phase for which a single crystal structure refinement is available. Thus, it is currently the best model compound for understanding the structure and dynamical behavior of interlayer and surface species in other, less-ordered, LDHs. We investigated the structural and dynamic behavior of water in the interlayers of hydrocalumite using inelastic (INS) and quasielastic (QENS) neutron scattering and molecular dynamics computer simulations. The comperehensive neutron scattering studies were performed for one fully hydrated and one dehydrated sample of hydrocalumite using several complementary instruments (HFBS, DCS and FANS at NCNR; HRMECS and QENS at IPNS) at temperatures above and below the previously discovered order-disorder interlayer phase transition. Together the experimental and molecular modeling results capture the important details of the dynamics of nano-confined water and the effects of the orientational ordering of H2O molecules above and below the phase transition. They provide otherwise unobtainable experimental information about the transformation of H2O librational and diffusional modes across the order-disorder phase transition and significantly add to our current understanding of the structure and dynamics of water in LDH phases based on the earlier NMR, IR, X-ray, and calorimetric measurements. The approach can now be extended to probe the

Quantitative description of human skin water dynamics by a disposition-decomposition analysis (DDA) of trans-epidermal water loss and epidermal capacitance.

PubMed

Rodrigues, Luis Monteiro; Pinto, Pedro Contreiras; Pereira, Luis Marcelo

2003-02-01

In vivo water assessment would greatly benefit from a dynamical approach since the evaluation of common related variables such as trans-epidermal water loss or "capacitance" measurements is always limited to instantaneous data. Mathematical modelling is still an attractive alternative already attempted with bi-exponential empirical models. A classical two-compartment interpretation of such models raises a number of questions about the underlying fundamentals, which can hardly be experimentally confirmed. However, in a system analysis sense, skin water dynamics may be approached as an ensemble of many factors, impossible to discretize, but conceptually grouped in terms of feasible properties of the system. The present paper explores the applicability of this strategy to the in vivo water dynamics assessment. From the plastic occlusion stress test (POST) skin water balance is assessed by modelling trans-epidermal water loss (TEWL) and "capacitance" data obtained at skin's surface. With system analysis (disposition-decomposition analysis) the distribution function, H(t), modelled as a sum of exponential terms, covers only the distribution characteristics of water molecules traversing the skin. This may correspond macroscopically to the experimental data accessed by "corneometry". Separately, the hyperbolic elimination function Q(TEWL) helps to characterise the dynamic aspects of water influx through the skin. In the observable range there seems to be a linear relationship between the net amount of water lost at the surface by evaporation, and the capability of the system to replenish that loss. This may be a specific characteristic of the system related to what may be described as the skin's "intrinsic hydration capacity" (IHC) a new functional parameter only identified by this strategy. These new quantitative tools are expected to find different applicabilities (from the in vivo skin characterisation to efficacy testing) contributing to disclose the dynamical nature

Potential and limitations of satellite laser altimetry for monitoring water surface dynamics: ICESat for US lakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shu, Liu; Qigang, Jiang; Zhang, Xuesong

Elevation measurements from the Ice, Cloud and Land Elevation Satellite (ICESat) have been applied to monitor dynamics of lakes and other surface water bodies. Despite such potential, the true utility of ICESat--more generally, satellite laser altimetry--for tracking surface water dynamics over time has not been adequately assessed, especially in the continental or global contexts. Here, we analyzed ICESat elevation data for the conterminous United States and examined the potential and limitations of satellite laser altimetry in measuring water-level dynamics. Owing to a lack of spatially-explicit ground-based water-level data, we first resorted to high-fidelity land elevation data acquired by airborne lidarmore » to quantify ICESat’s ranging accuracy. We then performed trend and frequency analyses to evaluate how reliably ICESat could capture water-level dynamics over a range of temporal scales, as compared to in-situ gauge measurements. Our analyses showed that ICESat had a vertical ranging error of 0.16 m at the footprint level—a limit on the detectable range of water-level dynamics. The sparsity of data over time was identified as a major factor limiting the use of ICESat for water dynamics studies. Of all the US lakes, only 361 had quality ICESat measurements for more than two flight passes. Even for those lakes with sufficient temporal coverage, ICESat failed to capture the true interannual water-level dynamics in 68% of the cases. Our frequency analysis suggested that even with a repeat cycle of two months, ICESat could capture only 60% of the variations in water-level dynamics for at most 34 % of the US lakes. To capture 60% of the water-level variation for most of the US lakes, a weekly repeat cycle (e.g., less than 5 days) is needed – a requirement difficult to meet in current designs of spaceborne laser altimetry. Overall, our results highlight that current or near-future satellite laser missions, though with high ranging accuracies, are unlikely

Mapping hydration dynamics and coupled water-protein fluctuations around a protein surface

NASA Astrophysics Data System (ADS)

Zhang, Luyuan; Wang, Lijuan; Kao, Ya-Ting; Qiu, Weihong; Yang, Yi; Okobiah, Oghaghare; Zhong, Dongping

2009-03-01

Elucidation of the molecular mechanism of water-protein interactions is critical to understanding many fundamental aspects of protein science, such as protein folding and misfolding and enzyme catalysis. We recently carried out a global mapping of protein-surface hydration dynamics around a globular α-helical protein apomyoglobin. The intrinsic optical probe tryptophan was employed to scan the protein surface one at a time by site-specific mutagenesis. With femtosecond resolution, we mapped out the dynamics of water-protein interactions with more than 20 mutants and for two states, native and molten globular. A robust bimodal distribution of time scales was observed, representing two types of water motions: local relaxation and protein-coupled fluctuations. The time scales show a strong correlation with the local protein structural rigidity and chemical identity. We also resolved two distinct contributions to the overall Stokes-shifts from the two time scales. These results are significant to understanding the role of hydration water on protein structural stability, dynamics and function.

Nonlinear fluid dynamics of nanoscale hydration water layer

NASA Astrophysics Data System (ADS)

Jhe, Wonho; Kim, Bongsu; Kim, Qhwan; An, Sangmin

In nature, the hydration water layer (HWL) ubiquitously exists in ambient conditions or aqueous solutions, where water molecules are tightly bound to ions or hydrophilic surfaces. It plays an important role in various mechanisms such as biological processes, abiotic materials, colloidal interaction, and friction. The HWL, for example, can be easily formed between biomaterials since most biomaterials are covered by hydrophilic molecules such as lipid bilayers, and this HWL is expected to be significant to biological and physiological functions. Here (1) we present the general stress tensor of the hydration water layer. The hydration stress tensor provided the platform form for holistic understanding of the dynamic behaviors of the confined HWL including tapping and shear dynamics which are until now individually studied. And, (2) through fast shear velocity ( 1mm/s) experiments, the elastic turbulence caused by elastic property of the HWL is indirectly observed. Our results may contribute to a deeper study of systems where the HWL plays an important role such as biomolecules, colloidal particles, and the MEMS. This work was supported by the National Research Foundation of Korea(NRF) Grant funded by the Korea government(MSIP) (2016R1A3B1908660).

Dynamic Modeling of Process Technologies for Closed-Loop Water Recovery Systems

NASA Technical Reports Server (NTRS)

Allada, Rama Kumar; Lange, Kevin E.; Anderson, Molly S.

2012-01-01

Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents dynamic simulations of chemical process for primary processor technologies including: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system, the Wiped-Film Rotating Disk (WFRD), and post-distillation water polishing processes such as the Volatiles Removal Assembly (VRA). These dynamic models were developed using the Aspen Custom Modeler (Registered TradeMark) and Aspen Plus(Registered TradeMark) process simulation tools. The results expand upon previous work for water recovery technology models and emphasize dynamic process modeling and results. The paper discusses system design, modeling details, and model results for each technology and presents some comparisons between the model results and available test data. Following these initial comparisons, some general conclusions and forward work are discussed.

Energy deposition dynamics of femtosecond pulses in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minardi, Stefano, E-mail: stefano@stefanominardi.eu; Pertsch, Thomas; Milián, Carles

2014-12-01

We exploit inverse Raman scattering and solvated electron absorption to perform a quantitative characterization of the energy loss and ionization dynamics in water with tightly focused near-infrared femtosecond pulses. A comparison between experimental data and numerical simulations suggests that the ionization energy of water is 8 eV, rather than the commonly used value of 6.5 eV. We also introduce an equation for the Raman gain valid for ultra-short pulses that validates our experimental procedure.

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

USGS Publications Warehouse

Nordstrom, D. Kirk; McCleskey, R. Blaine; Ball, J.W.

2009-01-01

Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH ??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values 350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

Interplay between microorganisms and geochemistry in geological carbon storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Altman, Susan J.; Kirk, Matthew Fletcher; Santillan, Eugenio-Felipe U.

Researchers at the Center for Frontiers of Subsurface Energy Security (CFSES) have conducted laboratory and modeling studies to better understand the interplay between microorganisms and geochemistry for geological carbon storage (GCS). We provide evidence of microorganisms adapting to high pressure CO 2 conditions and identify factors that may influence survival of cells to CO 2 stress. Factors that influenced the ability of cells to survive exposure to high-pressure CO 2 in our experiments include mineralogy, the permeability of cell walls and/or membranes, intracellular buffering capacity, and whether cells live planktonically or within biofilm. Column experiments show that, following exposure tomore » acidic water, biomass can remain intact in porous media and continue to alter hydraulic conductivity. Our research also shows that geochemical changes triggered by CO 2 injection can alter energy available to populations of subsurface anaerobes and that microbial feedbacks on this effect can influence carbon storage. Our research documents the impact of CO 2 on microorganisms and in turn, how subsurface microorganisms can influence GCS. Furthermore, we conclude that microbial presence and activities can have important implications for carbon storage and that microorganisms should not be overlooked in further GCS research.« less

Interplay between microorganisms and geochemistry in geological carbon storage

DOE PAGES

Altman, Susan J.; Kirk, Matthew Fletcher; Santillan, Eugenio-Felipe U.; ...

2016-02-28

Researchers at the Center for Frontiers of Subsurface Energy Security (CFSES) have conducted laboratory and modeling studies to better understand the interplay between microorganisms and geochemistry for geological carbon storage (GCS). We provide evidence of microorganisms adapting to high pressure CO 2 conditions and identify factors that may influence survival of cells to CO 2 stress. Factors that influenced the ability of cells to survive exposure to high-pressure CO 2 in our experiments include mineralogy, the permeability of cell walls and/or membranes, intracellular buffering capacity, and whether cells live planktonically or within biofilm. Column experiments show that, following exposure tomore » acidic water, biomass can remain intact in porous media and continue to alter hydraulic conductivity. Our research also shows that geochemical changes triggered by CO 2 injection can alter energy available to populations of subsurface anaerobes and that microbial feedbacks on this effect can influence carbon storage. Our research documents the impact of CO 2 on microorganisms and in turn, how subsurface microorganisms can influence GCS. Furthermore, we conclude that microbial presence and activities can have important implications for carbon storage and that microorganisms should not be overlooked in further GCS research.« less

Effects of spatial variability of soil hydraulic properties on water dynamics

NASA Astrophysics Data System (ADS)

Gumiere, Silvio Jose; Caron, Jean; Périard, Yann; Lafond, Jonathan

2013-04-01

Soil hydraulic properties may present spatial variability and dependence at the scale of watersheds or fields even in man-made single soil structures, such as cranberry fields. The saturated hydraulic conductivity (Ksat) and soil moisture curves were measured at two depths for three cranberry fields (about 2 ha) at three different sites near Québec city, Canada. Two of the three studied fields indicate strong spatial dependence for Ksat values and soil moisture curves both in horizontal and vertical directions. In the summer of 2012, the three fields were equipped with 55 tensiometers installed at a depth of 0.10 m in a regular grid. About 20 mm of irrigation water were applied uniformly by aspersion to the fields, raising soil water content to near saturation condition. Soil water tension was measured once every hour during seven days. Geostatistical techniques such as co-kriging and cross-correlograms estimations were used to investigate the spatial dependence between variables. The results show that soil tension varied faster in high Ksat zones than in low Ksatones in the cranberry fields. These results indicate that soil water dynamic is strongly affected by the variability of saturated soil hydraulic conductivity, even in a supposed homogenous anthropogenic soil. This information may have a strong impact in irrigation management and subsurface drainage efficiency as well as other water conservation issues. Future work will involve 3D numerical modeling of the field water dynamics with HYDRUS software. The anticipated outcome will provide valuable information for the understanding of the effect of spatial variability of soil hydraulic properties on soil water dynamics and its relationship with crop production and water conservation.

Soil Water Balance and Vegetation Dynamics in two Water-limited Mediterranean Ecosystem on Sardinia under past and future climate change

NASA Astrophysics Data System (ADS)

Corona, R.; Montaldo, N.; Albertson, J. D.

2016-12-01

Water limited conditions strongly impacts soil and vegetation dynamics in Mediterranean regions, which are commonly heterogeneous ecosystems, characterized by inter-annual rainfall variability, topography variability and contrasting plant functional types (PFTs) competing for water use. Historical human influences (e.g., deforestation, urbanization) further altered these ecosystems. Sardinia island is a representative region of Mediterranean ecosystems. It is low urbanized except some plan areas close to the main cities where main agricultural activities are concentrated. Two contrasting case study sites are within the Flumendosa river basin (1700 km2). The first site is a typical grassland on an alluvial plan valley (soil depth > 2m) while the second is a patchy mixture of Mediterranean vegetation species (mainly wild olive trees and C3 herbaceous) that grow in a soil bounded from below by a rocky layer of basalt, partially fractured (soil depth 15 - 40 cm). In both sites land-surface fluxes and CO2 fluxes are estimated by the eddy correlation technique while soil moisture was continuously estimated with water content reflectometers, and periodically leaf area index (LAI) was estimated. The following objectives are addressed:1) pointing out the dynamics of land surface fluxes, soil moisture, CO2 and vegetation cover for two contrasting water-limited ecosystems; 2) assess the impact of the soil depth and type on the CO2 and water balance dynamics; 3) evaluate the impact of past and future climate change scenarios on the two contrasting ecosystems. For reaching the objectives an ecohydrologic model that couples a vegetation dynamic model (VDM), and a 3-component (bare soil, grass and woody vegetation) land surface model (LSM) has been used. Historical meteorological data are available from 1922 and hydro-meteorological scenarios are then generated using a weather generator. The VDM-LSM model predict soil water balance and vegetation dynamics for the generated

First principles molecular dynamics of metal/water interfaces under bias potential

NASA Astrophysics Data System (ADS)

Pedroza, Luana; Brandimarte, Pedro; Rocha, Alexandre; Fernandez-Serra, Marivi

2014-03-01

Understanding the interaction of the water-metal system at an atomic level is extremely important in electrocatalysts for fuel cells, photocatalysis among other systems. The question of the interface energetics involves a detailed study of the nature of the interactions between water-water and water-substrate. A first principles description of all components of the system is the most appropriate methodology in order to advance understanding of electrochemically processes. In this work we describe, using first principles molecular dynamics simulations, the dynamics of a combined surface(Au and Pd)/water system both in the presence and absence of an external bias potential applied to the electrodes, as one would come across in electrochemistry. This is accomplished using a combination of density functional theory (DFT) and non-equilibrium Green's functions methods (NEGF), thus accounting for the fact that one is dealing with an out-of-equilibrium open system, with and without van der Waals interactions. DOE Early Career Award No. DE-SC0003871.

Geochemistry of spring water, southeastern Uinta Basin, Utah and Colorado

USGS Publications Warehouse

Kimball, Briant A.

1981-01-01

The chemical quality of water in the southeastern Uinta Basin, Utah and Colorado, is important to the future development of the abundant oil-shale resources of the area. This report examines the observed changes in chemistry as water circulates in both shallow and deep ground-water systems. Mass-balance and mass- transfer calculations are used to define reactions that simulate the observed water chemistry in the mixed sandstone, siltstone, and carbonate lithology of the Green River Formation of Tertiary age.The mass-transfer calculations determine a reaction path particular to this system. The early dominance of calcite dissolution produces a calcium carbonate water. After calcite saturation, deeper circulation and further rock-water interaction cause the reprecipitation of calcite, the dissolution of dolomite and plagioclase, and the oxidation of pyrite; all combining to produce a calcium magnesium sodium bicarbonate sulfate water. The calculations suggest that silica concentrations are controlled by a kaolinite-Ca-montmorillonite phase boundary. Close agreement of mineral-saturation indices calculated by both an aqueous-equilibrium model and the mass-transfer model support the selection of reactions from the mass-transfer calculations.

Petrology and Geochemistry of Mercury

NASA Astrophysics Data System (ADS)

Weider, Shoshana Z.

2018-04-01

Although having knowledge of a terrestrial planet's chemistry is fundamental to understanding the origin and composition of its rocks, until recently, the geochemistry of Mercury—the Solar System's innermost planet—was largely unconstrained. Without the availability of geological specimens from Mercury, studying the planet's surface and bulk composition relies on remote sensing techniques. Moreover, Mercury's proximity to the Sun makes it difficult to study with Earth/space-based telescopes, or with planetary probes. Indeed, to date, only NASA's Mariner 10 and MESSENGER missions have been sent to Mercury. The former made three "flyby" encounters of Mercury between 1974 and 1975, but did not carry any instrument to make geochemical or mineralogical measurements of the surface. Until the MESSENGER flyby and orbital campaigns (2008–2015), therefore, knowledge of Mercury's chemical composition was severely limited and consisted of only a few facts. For example, it has long been known that Mercury has the highest uncompressed density of all the terrestrial planets (and thus a disproportionately large iron core). In addition, Earth-based spectral reflectance observations indicated a dark surface, largely devoid of iron within silicate minerals. To improve understanding of Mercury's geochemistry, the MESSENGER payload included a suite of geochemical sensing instruments: namely the X-Ray Spectrometer, Gamma-Ray Spectrometer, and Neutron Spectrometer. Indeed, the datasets obtained from these instruments (as well as from other complementary instruments) during MESSENGER's 3.5-year orbital mission allow a much more complete picture of Mercury's geochemistry to be drawn, and quantitative abundance estimates for several major rock-forming elements in Mercury's crust are now available. Overall, the MESSENGER data reveal a surface that is rich in Mg, but poor in Al and Ca, compared with typical terrestrial and lunar crustal materials. Mercury's surface also contains high

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf])

NASA Astrophysics Data System (ADS)

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J.; Cisneros, G. Andrés

2018-01-01

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]).

PubMed

Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés

2018-01-14

We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17 O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO 4 ]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf] - anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

Sedimentary Geochemistry of Martian Samples from the Pathfinder Mission

NASA Technical Reports Server (NTRS)

McLennan, Scott M.

2001-01-01

The purpose of this research project was to evaluate the APXS data collected on soils and rocks at the Pathfinder site in terms of sedimentary geochemistry. Below are described the major findings of this research: (1) An influential model to explain the chemical variation among Pathfinder soils and rocks is a two component mixing model where rocks of fairly uniform composition mix with soil of uniform composition; (2) The very strong positive correlation between MgO and SO, points to a control by a MgSO4 mineral however, spectroscopic data continue to suggest that Fe-sulfates, notably schwertmannite and jarosite, may be important components; (3) In an attempt to better understand the causes of complexities in mixing relationships, the possible influence of sedimentary transport has been evaluated; (4) Another aspect of this research has been to examine the possibility of sedimentary silica being a significant phase on Mars; and (5) On Earth, the geochemistry of sedimentary rocks has been used to constrain the chemical composition of the continental crust and an important part of this research was to evaluate this approach for Mars.

Coupling between amino acid and water dynamics by broadband dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Saiz, Luciana; Cerveny, Silvina

2014-05-01

The dynamics of proline aqueous solution was investigated for water concentrations from 40 to 60 wt% by dielectric spectroscopy (106 - 109 Hz) in the temperature range from 230 to 300 K, where the solutions remain amorphous. We found two relaxation processes, related with the reorientation of proline and water as previously observed in a higher frequency range at room temperature [1]. We found that both dynamics are strongly coupled, as previously observed in hydrated proteins powders, in spite of the fact that a single amino acid is a molecule much simpler than a protein.

Using land-cover change as dynamic variables in surface-water and water-quality models

USGS Publications Warehouse

Karstensen, Krista A.; Warner, Kelly L.; Kuhn, Anne

2010-01-01

Land-cover data are typically used in hydrologic modeling to establish or describe land surface dynamics. This project is designed to demonstrate the use of land-cover change data in surface-water and water-quality models by incorporating land-cover as a variable condition. The project incorporates three different scenarios that vary hydrologically and geographically: 1) Agriculture in the Plains, 2) Loon habitat in New England, and 3) Forestry in the Ozarks.

Water transport in human aquaporin-4: molecular dynamics (MD) simulations.

PubMed

Cui, Yubao; Bastien, David A

2011-09-09

Aquaporin-4 (AQP4) is the predominant water channel in the central nervous system, where it has been reported to be involved in many pathophysiological roles including water transport. In this paper, the AQP4 tetramer was modeled from its PDB structure file, embedded in a palmitoyl-oleoyl-phosphatidyl-choline (POPC) lipid bilayer, solvated in water, then minimized and equilibrated by means of molecular dynamics simulations. Analysis of the equilibrated structure showed that the central pore along the fourfold axis of the tetramers is formed with hydrophobic amino acid residues. In particular, Phe-195, Leu-191 and Leu-75, form the narrowest part of the pore. Therefore water molecules are not expected to transport through the central pore, which was confirmed by MD simulations. Each monomer of the AQP4 tetramers forms a channel whose walls consist mostly of hydrophilic residues. There are eight water molecules in single file observed in each of the four channels, transporting through the selectivity filter containing Arg-216, His-201, Phe-77, Ala-210, and the two conserved Asn-Pro-Ala (NPA) motifs containing Asn-213 and Asn-97. By using Brownian dynamics fluctuation-dissipation-theorem (BD-FDT), the overall free-energy profile was obtained for water transporting through AQP4 for the first time, which gives a complete map of the entire channel of water permeation. Copyright © 2011. Published by Elsevier Inc.

Dynamics of water in sulfonated poly(phenylene) membranes

NASA Astrophysics Data System (ADS)

Osti, Naresh; Etampawala, Thusitha; Shrestha, Umesh; Perahia, Dvora; Cornelius, Christopher

2011-03-01

The dynamics of water in networks formed by highly rigid ionic polymers, sulfonated poly(phenylene) as observed by quasi elastic neutron scattering (QENS) is presented. These rigid ionic polymers have potential as effective ion exchange membranes with impact on a large number of applications from water purification to clean energy, where its rigidity distinguishes it from other ionic polymers. Its transport characteristics are affected by its rigidness as well as by direct interactions with the solvent. Our QENS studies as a function of sulfonation levels, temperature and solvent content have shown that on the time scale of the measurement, the polymers are rigid. While macroscopically all samples swell, and transport water, the water molecules appear locally rather confined. Water however remind non-frozen to subzero temperatures. The results will be discussed in view of theoretical models including continues diffusion and hopping of solvent molecules.

Dynamics of water in strawberry and red onion as studied by dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Jansson, H.; Huldt, C.; Bergman, R.; Swenson, J.

2005-01-01

We have investigated the microscopic dynamics of strawberry and red onion by means of broadband dielectric spectroscopy. In contrast to most of the previous experiments on carbohydrate-rich biological materials, which have mainly considered the more global dynamics of the “biological matrix,” we are here focusing on the microscopic dynamics of mainly the associated water. The results for both strawberry and red onion show that the imaginary part of the permittivity contains one conductivity term and a clear dielectric loss peak, which was found to be similar to the strongest relaxation process of water in carbohydrate solutions. The temperature dependence of the relaxation process was analyzed for different water content. The relaxation process slows down, and its temperature dependence becomes more non-Arrhenius, with decreasing water content. The reason for this is most likely that, on average, the water molecules interact more strongly with carbohydrates and other biological materials at low water content, and the dynamical properties of this biological matrix changes substantially with increasing temperature (from an almost rigid matrix where the water is basically unable to perform long-range diffusion due to confinement effects, to a dynamic matrix with no static confinement effects), which also changes (i.e., reduces) the activation energy of the relaxation process with increasing temperature (i.e., causes a non-Arrhenius temperature dependence). This further changes the conductivity from mainly polarization effects at low temperatures, due to hindered ionic motions, to long-range diffusivity at T>250K . Thus, around this temperature ions in the carbohydrate solution no longer get stuck in confined cavities, since the motion of the biological matrix “opens up” the cavities and the ions are then able to perform long-range migration.

A review of the structure and dynamics of nanoconfined water and ionic liquids via molecular dynamics simulation.

PubMed

Foroutan, Masumeh; Fatemi, S Mahmood; Esmaeilian, Farshad

2017-02-01

During the past decade, the research on fluids in nanoconfined geometries has received considerable attention as a consequence of their wide applications in different fields. Several nanoconfined systems such as water and ionic liquids, together with an equally impressive array of nanoconfining media such as carbon nanotube, graphene and graphene oxide have received increasingly growing interest in the past years. Water is the first system that has been reviewed in this article, due to its important role in transport phenomena in environmental sciences. Water is often considered as a highly nanoconfined system, due to its reduction to a few layers of water molecules between the extended surface of large macromolecules. The second system discussed here is ionic liquids, which have been widely studied in the modern green chemistry movement. Considering the great importance of ionic liquids in industry, and also their oil/water counterpart, nanoconfined ionic liquid system has become an important area of research with many fascinating applications. Furthermore, the method of molecular dynamics simulation is one of the major tools in the theoretical study of water and ionic liquids in nanoconfinement, which increasingly has been joined with experimental procedures. In this way, the choice of water and ionic liquids in nanoconfinement is justified by applying molecular dynamics simulation approaches in this review article.

Geochemistry of molybdenum in some stream sediments and waters

NASA Astrophysics Data System (ADS)

Kaback, Dawn S.; Runnells, Donald D.

1980-03-01

Elevated concentrations of Mo are present in both the waters and sediments of Tenmile Creek, downstream from the large Mo deposit at Climax. Colorado. Concentrations of Mo reach a maximum of 10mg/1 in the water and 384μ/g in the (-) 80 mesh fraction of the sediment. The Mo anomaly extends for more than 80 km downstream from Climax, and results from the mining and milling at Climax. Background Mo concentrations in the nearby mountainous area are < 10μg/l (water) and < 5μg/g (sediment). Immediately below three small unmined Mo-rich orebodies elsewhere in Colorado < 3μg/l Mo are present in the waters and 20-30μg/g Mo in the fine fraction of the sediments. The Mo in the sediment of Tenmile Creek is chiefly adsorbed on coatings of amorphous Fe oxyhydroxide. and is similar to its form below two small, unmined Mo deposits. Mining has not changed the character of the chemical processes responsible for Mo dispersion from the Climax site. A modified version of the WATEQF computer program ( PLUMMERet al., 1976) predicts that Tenmile Creek is undersaturated with respect to ferrimolybdite. molybdenite, powellite, and ilsemannite. The Mo in the stream water occurs as the molybdate ion which can be adsorbed on amorphous Fe oxyhydroxides. These predictions are supported by the absence of Mo minerals in the sediment of Tenmile Creek.

Structure of water clusters on graphene: A classical molecular dynamics approach

NASA Astrophysics Data System (ADS)

Maekawa, Yuki; Sasaoka, Kenji; Yamamoto, Takahiro

2018-03-01

The microscopic structure of surface water adsorbed on graphene is elucidated theoretically by classical molecular dynamics simulation. At a low temperature (100 K), the main polygon consisting of hydrogen bonds in single-layered water on graphene is tetragonal, whereas the dominant polygons in double-layered water are tetragonal, pentagonal, and hexagonal. On the other hand, at room temperature, the tetragonal, pentagonal, and hexagonal water clusters are the main structures in both single- and double-layered water.

Water age and stream solute dynamics at the Hubbard Brook Experimental Forest (US)

NASA Astrophysics Data System (ADS)

Botter, Gianluca; Benettin, Paolo; McGuire, Kevin; Rinaldo, Andrea

2016-04-01

The contribution discusses experimental and modeling results from a headwater catchment at the Hubbard Brook Experimental Forest (New Hampshire, USA) to explore the link between stream solute dynamics and water age. A theoretical framework based on water age dynamics, which represents a general basis for characterizing solute transport at the catchment scale, is used to model both conservative and weathering-derived solutes. Based on the available information about the hydrology of the site, an integrated transport model was developed and used to estimate the relevant hydrochemical fluxes. The model was designed to reproduce the deuterium content of streamflow and allowed for the estimate of catchment water storage and dynamic travel time distributions (TTDs). Within this framework, dissolved silicon and sodium concentration in streamflow were simulated by implementing first-order chemical kinetics based explicitly on dynamic TTD, thus upscaling local geochemical processes to catchment scale. Our results highlight the key role of water stored within the subsoil glacial material in both the short-term and long-term solute circulation at Hubbard Brook. The analysis of the results provided by the calibrated model allowed a robust estimate of the emerging concentration-discharge relationship, streamflow age distributions (including the fraction of event water) and storage size, and their evolution in time due to hydrologic variability.

Incorporating water table dynamics in climate modeling: 1. Water table observations and equilibrium water table simulations

NASA Astrophysics Data System (ADS)

Fan, Ying; Miguez-Macho, Gonzalo; Weaver, Christopher P.; Walko, Robert; Robock, Alan

2007-05-01

Soil moisture is a key participant in land-atmosphere interactions and an important determinant of terrestrial climate. In regions where the water table is shallow, soil moisture is coupled to the water table. This paper is the first of a two-part study to quantify this coupling and explore its implications in the context of climate modeling. We examine the observed water table depth in the lower 48 states of the United States in search of salient spatial and temporal features that are relevant to climate dynamics. As a means to interpolate and synthesize the scattered observations, we use a simple two-dimensional groundwater flow model to construct an equilibrium water table as a result of long-term climatic and geologic forcing. Model simulations suggest that the water table depth exhibits spatial organization at watershed, regional, and continental scales, which may have implications for the spatial organization of soil moisture at similar scales. The observations suggest that water table depth varies at diurnal, event, seasonal, and interannual scales, which may have implications for soil moisture memory at these scales.

Hydrogen Isotope Geochemistry of Mariana Trough Lavas

NASA Astrophysics Data System (ADS)

Oleary, J.; Kitchen, N.; Eiler, J.

2002-12-01

Basaltic lavas from the Marianas trough vary in water content from values similar to mid-ocean ridge basalts (MORBs) to ten times those values. These variations plausibly reflect addition of subducted water to the mantle wedge, but must also reflect variations in extent of melting and crystallization-differentiation. We report hydrogen isotope data for 18 samples of lavas from the Mariana trough; these measurements, when combined with other geochemical data, constrain the relative proportions of subducted vs. 'primitive' water in their mantle sources. Previous measurements of the hydrogen isotope composition of Mariana trough lavas [1] found a correlation between dD and measured water content, consistent with two-component mixing between water in the ambient MORB source and water from the subducted slab, but include only four samples, only two of which have known major and minor element geochemistry. Our purpose is to confirm this result and expand it to include a more representative sampling. Our measurements made use of a recently developed technique for on-line stepped heating, water reduction and hydrogen isotope mass spectrometry [2]. This method is appropriate for relatively small samples of basaltic glass (ca. 100 μg to 1 mg) and up to 10 analyses can be performed per day. Its principle advantages for our purposes are that it can be applied to even small or glass-poor samples and it is fast enough to permit replication of all data and analysis of relatively large numbers of standards. Hydrogen isotope compositions of Mariana trough lavas vary between -74 per mil and -34 per mil (SMOW); this compares with a range of -46 to -32 per mil for related lavas in [1] and is similar to the previously observed range for back-arc-basin basalts generally (-70 to -32 per mil). Two-thirds of our sample suite span a small range in dD (-40+/-4 ). We suggest this average is the most representative value for back arc basin basalts measured to-date. Our data are inconsistent

Dynamic equilibrium strategy for drought emergency temporary water transfer and allocation management

NASA Astrophysics Data System (ADS)

Xu, Jiuping; Ma, Ning; Lv, Chengwei

2016-08-01

Efficient water transfer and allocation are critical for disaster mitigation in drought emergencies. This is especially important when the different interests of the multiple decision makers and the fluctuating water resource supply and demand simultaneously cause space and time conflicts. To achieve more effective and efficient water transfers and allocations, this paper proposes a novel optimization method with an integrated bi-level structure and a dynamic strategy, in which the bi-level structure works to deal with space dimension conflicts in drought emergencies, and the dynamic strategy is used to deal with time dimension conflicts. Combining these two optimization methods, however, makes calculation complex, so an integrated interactive fuzzy program and a PSO-POA are combined to develop a hybrid-heuristic algorithm. The successful application of the proposed model in a real world case region demonstrates its practicality and efficiency. Dynamic cooperation between multiple reservoirs under the coordination of a global regulator reflects the model's efficiency and effectiveness in drought emergency water transfer and allocation, especially in a fluctuating environment. On this basis, some corresponding management recommendations are proposed to improve practical operations.

A system dynamics model of human-water interaction in anthropogenic droughts

NASA Astrophysics Data System (ADS)

Blair, Peter; Buytaert, Wouter

2016-04-01

Modelling is set to be a key part of socio-hydrology's quest to understand the dynamics and long-term consequences of human-water interactions. As a subject in its infancy, still learning the questions to ask, conceptual models are of particular use in trying to understand the general nature of human-water systems. The conceptual model of Di Baldassarre et al. (2013), which investigates human-flood interactions, has been widely discussed, prompting great steps forward in understanding and coverage of socio-hydrology. The development of further conceptual models could generate further discussion and understanding. Flooding is one archetypal example of a system of human-water interaction; another is the case of water stress and drought. There has been a call to recognise and understand anthropogenic drought (Aghakouchak et al. 2015), and so this study investigates the nature of the socio-hydrological dynamics involved in these situations. Here we present a system dynamics model to simulate human-water interactions in the context of water-stressed areas, where drought is induced via a combination of lower than usual water availability and relatively high water use. It is designed based on an analysis of several case-studies where recent droughts have occurred, or where the prospect of drought looms. The locations investigated are Spain, Southeast Brazil, Northeast China and California. The numerical system dynamics model is based on causal loop, and stocks and flows diagrams, which are in turn developed from the qualitative analysis of the different cases studied. The study uses a comparative approach, which has the advantage of eliciting general system characteristics from the similarities between cases, while using the differences to determine the important factors which lead to different system behaviours. References: Aghakouchak, A., Feldman, D., Hoerling, M., Huxman, T., Lund, J., 2015. Recognize anthropogenic drought. Nature, 524, pp.409-411. Di Baldassarre, G

Effect of water phase transition on dynamic ruptures with thermal pressurization: Numerical simulations with changes in physical properties of water

NASA Astrophysics Data System (ADS)

Urata, Yumi; Kuge, Keiko; Kase, Yuko

2015-02-01

Phase transitions of pore water have never been considered in dynamic rupture simulations with thermal pressurization (TP), although they may control TP. From numerical simulations of dynamic rupture propagation including TP, in the absence of any water phase transition process, we predict that frictional heating and TP are likely to change liquid pore water into supercritical water for a strike-slip fault under depth-dependent stress. This phase transition causes changes of a few orders of magnitude in viscosity, compressibility, and thermal expansion among physical properties of water, thus affecting the diffusion of pore pressure. Accordingly, we perform numerical simulations of dynamic ruptures with TP, considering physical properties that vary with the pressure and temperature of pore water on a fault. To observe the effects of the phase transition, we assume uniform initial stress and no fault-normal variations in fluid density and viscosity. The results suggest that the varying physical properties decrease the total slip in cases with high stress at depth and small shear zone thickness. When fault-normal variations in fluid density and viscosity are included in the diffusion equation, they activate TP much earlier than the phase transition. As a consequence, the total slip becomes greater than that in the case with constant physical properties, eradicating the phase transition effect. Varying physical properties do not affect the rupture velocity, irrespective of the fault-normal variations. Thus, the phase transition of pore water has little effect on dynamic ruptures. Fault-normal variations in fluid density and viscosity may play a more significant role.

Integrated approach to monitor water dynamics with drones

NASA Astrophysics Data System (ADS)

Raymaekers, Dries; De Keukelaere, Liesbeth; Knaeps, Els; Strackx, Gert; Decrop, Boudewijn; Bollen, Mark

2017-04-01

Remote sensing has been used for more than 20 years to estimate water quality in the open ocean and study the evolution of vegetation on land. More recently big improvements have been made to extend these practices to coastal and inland waters, opening new monitoring opportunities, eg. monitoring the impact of dredging activities on the aquatic environment. While satellite sensors can provide complete coverage and historical information of the study area, they are limited in their temporal revisit time and spatial resolution. Therefore, deployment of drones can create an added value and in combination with satellite information increase insights in the dynamics and actors of coastal and aquatic systems. Drones have the advantages of monitoring at high spatial detail (cm scale), with high frequency and are flexible. One of the important water quality parameters is the suspended sediment concentration. However, retrieving sediment concentrations from unmanned systems is a challenging task. The sediment dynamics in the port of Breskens, the Netherlands, were investigated by combining information retrieved from different data sources: satellite, drone and in-situ data were collected, analysed and inserted in sediment models. As such, historical (satellite), near-real time (drone) and predictive (sediment models) information, integrated in a spatial data infrastructure, allow to perform data analysis and can support decision makers.

Influence of vegetation dynamic modeling on the allocation of green and blue waters

NASA Astrophysics Data System (ADS)

Ruiz-Pérez, Guiomar; Francés, Félix

2015-04-01

The long history of the Mediterranean region is dominated by the interactions and co-evolution between man and its natural environment. It is important to consider that the Mediterranean region is recurrently or permanently confronted with the scarcity of the water. The issue of climate change is (and will be) aggravating this situation. This raises the question of a loss of services that ecosystems provide to human and also the amount of available water to be used by vegetation. The question of the water cycle, therefore, should be considered in an integrated manner by taking into account both blue water (water in liquid form used for the human needs or which flows into the oceans) and green water (water having the vapor for resulting from evaporation and transpiration processes). In spite of this, traditionally, very few hydrological models have incorporated the vegetation dynamic as a state variable. In fact, most of them are able to represent fairly well the observed discharge, but usually including the vegetation as a static parameter. However, in the last decade, the number of hydrological models which explicitly take into account the vegetation development as a state variable has increased substantially. In this work, we want to analyze if it is really necessary to use a dynamic vegetation model to quantify adequately the distribution of water into blue and green water. The study site is located in the Public Forest Monte de la Hunde y Palomeras (Spain). The vegetation in the study area is dominated by Aleppo pine of high tree density with scant presence of other species. Two different daily models were applied (with static and dynamic vegetation representation respectively) in three different scenarios: dry year (2005), normal year (2008) and wet year (2010). The static vegetation model simulates the evapotranspiration considering the vegetation as a stationary parameter. Contrarily, the dynamic vegetation model connects the hydrological model with a

Microbial dynamics in acetate-enriched ballast water at different temperatures.

PubMed

Stehouwer, Peter Paul; van Slooten, Cees; Peperzak, Louis

2013-10-01

The spread of invasive species through ships' ballast water is considered as a major ecological threat to the world's oceans. For that reason, the International Maritime Organization (IMO) has set performance standards for ballast water discharge. Ballast water treatment systems have been developed that employ either UV-radiation or 'active substances' to reduce the concentration of living cells to below the IMOs standards. One such active substance is a chemical mixture known as Peraclean(®) Ocean. The residual of Peraclean(®) Ocean is acetate that might be present at high concentrations in discharged ballast water. In cold coastal waters the breakdown of acetate might be slow, causing a buildup of acetate concentrations in the water if regularly discharged by ships. To study the potential environmental impact, microbial dynamics and acetate degradation were measured in discharge water from a Peraclean(®) Ocean treatment system in illuminated microcosms. In addition, microbial dynamics and acetate degradation were studied at -1, 4, 10, 15 and 25°C in dark microcosms that simulated enclosed ballast water tanks. Acetate breakdown indeed occurred faster at higher temperatures. At 25°C the highest bacteria growth, fastest nutrient and oxygen consumption and highest DOC reduction occurred. On the other hand, at -1°C bacterial growth was strongly delayed, only starting to increase after 12 days. Furthermore, at 25°C the acetate pool was not depleted, probably due to nutrient and oxygen limitation. This means that not all acetate will be broken down in ballast water tanks, even during long voyages in warm waters. In addition, at low temperatures acetate breakdown in ballast water tanks and in discharged water will be extremely slow. Therefore, regular discharge of acetate enriched ballast water in harbors and bays may cause eutrophication and changes in the microbial community, especially in colder regions. Copyright © 2013 Elsevier Inc. All rights reserved.

Water and sediment temperature dynamics in shallow tidal environments: The role of the heat flux at the sediment-water interface

NASA Astrophysics Data System (ADS)

Pivato, M.; Carniello, L.; Gardner, J.; Silvestri, S.; Marani, M.

2018-03-01

In the present study, we investigate the energy flux at the sediment-water interface and the relevance of the heat exchanged between water and sediment for the water temperature dynamics in shallow coastal environments. Water and sediment temperature data collected in the Venice lagoon show that, in shallow, temperate lagoons, temperature is uniform within the water column, and enabled us to estimate the net heat flux at the sediment-water interface. We modeled this flux as the sum of a conductive component and of the solar radiation reaching the bottom, finding the latter being negligible. We developed a "point" model to describe the temperature dynamics of the sediment-water continuum driven by vertical energy transfer. We applied the model considering conditions characterized by negligible advection, obtaining satisfactory results. We found that the heat exchange between water and sediment is crucial for describing sediment temperature but plays a minor role on the water temperature.

Interstitial Water Geochemistry and Low Temperature Alteration in Volcaniclastic Sediments from the Amami Sankaku Basin at IODP Site U1438 (Expedition 351)

NASA Astrophysics Data System (ADS)

Loudin, L. C.; Yogodzinski, G. M.; Sena, C.; van der Land, C.; Zhang, Z.; Marsaglia, K. M.; Meffre, S.

2014-12-01

Interstitial water (IW) geochemistry provides insight into the diagenetic transformation of sediment to rock by component dissolution/alteration and precipitation of new mineral phases as pore-filling cements, as well as providing insight into ion exchange reactions with secondary minerals. At Site U1438, 67 IW samples were collected within a ~950 m section of volcaniclastic sediments. These were analyzed for pH as well as major and trace elements. The corresponding host sediments were mineralogically characterized by XRD and petrographic observations. Three alteration zones are inferred: 1) the upper alteration zone (~0-300 mbsf) characterized by maximum IW concentrations of Si (790.1 μM), Sr (138.5 μM) and Mn (279.5 μM), consistent with volcanic glass and siliceous microfossil dissolution, enhanced reduction of Mn oxides, and carbonate recrystallization. Maximum concentrations in Li and B coupled with the lowest pH (6.7) imply that Li and B are released into the IW due to silicate dissolution and clay desorption. 2) At intermediate depths (~300 to ~550 mbsf) Mg, K, Sr, Si, Mn, Li, and B are at concentration minima, possibly due to growth of authigenic minerals. B and Li minimum concentrations occur at high pH (~9) suggesting that these elements are preferentially removed from high pH waters during the precipitation of clay mineral and zeolite cements in primary and secondary (dissolution) pores. The mineralogy of these phases is confirmed by XRD data, and their pore-filling nature is seen in thin sections of the coarser lithologies. 3) The deep alteration zone (>~550m) is characterized by an increase in B, Li, Sr and Ca. At ~650 mbsf, Ca becomes the dominant cation in solution consistent with either mineral interaction with the IW, or diffusive input from underlying igneous basement (~1400 mbsf).

Vibration-rotation-tunneling dynamics in small water clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pugliano, N.

The goal of this work is to characterize the intermolecular vibrations of small water clusters. Using tunable far infrared laser absorption spectroscopy, large amplitude vibration-rotation-tunneling (VRT) dynamics in vibrationally excited states of the water dimer and the water trimer are investigated. This study begins with the measurement of 12 VRT subbands, consisting of approximately 230 transitions, which are assigned to an 82.6 cm[sup [minus]1] intermolecular vibration of the water dimer-d[sub 4]. Each of the VRT subbands originate from K[sub a][double prime]=0 and terminate in either K[sub a][prime]=0 or 1. These data provide a complete characterization of the tunneling dynamics inmore » the vibrationally excited state as well as definitive symmetry labels for all VRT energy levels. Furthermore, an accurate value for the A[prime] rotational constant is found to agree well with its corresponding ground state value. All other excited state rotational constants are fitted, and discussed in terms of the corresponding ground state constants. In this vibration, the quantum tunneling motions are determined to exhibit large dependencies with both the K[sub a][prime] quantum number and the vibrational coordinate, as is evidenced by the measured tunneling splittings. The generalized internal-axis-method treatment which has been developed to model the tunneling dynamics, is considered for the qualitative description of each tunneling pathway, however, the variation of tunneling splittings with vibrational excitation indicate that the high barrier approximation does not appear to be applicable for this vibrational coordinate. The data are consistent with a motion possessing a[prime] symmetry, and the vibration is assigned as the [nu][sub 12] acceptor bending coordinate. This assignment is in agreement with the vibrational symmetry, the resultsof high level ab initio calculations, and preliminary data assigned to the analogous vibration in the D[sub 2]O-DOH isotopomer.« less

Rare Earth Element Geochemistry for Produced Waters, WY

DOE Data Explorer

Quillinan, Scott; Nye, Charles; McLing, Travis; Neupane, Hari

2016-06-30

These data represent major, minor, trace, isotopes, and rare earth element concentrations in geologic formations and water associated with oil and gas production. *Note - Link below contains updated version of spreadsheet (6/14/2017)

Butane dihedral angle dynamics in water is dominated by internal friction

PubMed Central

Daldrop, Jan O.; Kappler, Julian; Brünig, Florian N.; Netz, Roland R.

2018-01-01

The dihedral dynamics of butane in water is known to be rather insensitive to the water viscosity; possible explanations for this involve inertial effects or Kramers’ turnover, the finite memory time of friction, and the presence of so-called internal friction. To disentangle these factors, we introduce a method to directly extract the friction memory function from unconstrained simulations in the presence of an arbitrary free-energy landscape. By analysis of the dihedral friction in butane for varying water viscosity, we demonstrate the existence of an internal friction contribution that does not scale linearly with water viscosity. At normal water viscosity, the internal friction turns out to be eight times larger than the solvent friction and thus completely dominates the effective friction. By comparison with simulations of a constrained butane molecule that has the dihedral as the only degree of freedom, we show that internal friction comes from the six additional degrees of freedom in unconstrained butane that are orthogonal to the dihedral angle reaction coordinate. While the insensitivity of butane’s dihedral dynamics to water viscosity is solely due to the presence of internal friction, inertial effects nevertheless crucially influence the resultant transition rates. In contrast, non-Markovian effects due to the finite memory time are present but do not significantly influence the dihedral barrier-crossing rate of butane. These results not only settle the character of dihedral dynamics in small solvated molecular systems such as butane, they also have important implications for the folding of polymers and proteins. PMID:29712838

Butane dihedral angle dynamics in water is dominated by internal friction.

PubMed

Daldrop, Jan O; Kappler, Julian; Brünig, Florian N; Netz, Roland R

2018-05-15

The dihedral dynamics of butane in water is known to be rather insensitive to the water viscosity; possible explanations for this involve inertial effects or Kramers' turnover, the finite memory time of friction, and the presence of so-called internal friction. To disentangle these factors, we introduce a method to directly extract the friction memory function from unconstrained simulations in the presence of an arbitrary free-energy landscape. By analysis of the dihedral friction in butane for varying water viscosity, we demonstrate the existence of an internal friction contribution that does not scale linearly with water viscosity. At normal water viscosity, the internal friction turns out to be eight times larger than the solvent friction and thus completely dominates the effective friction. By comparison with simulations of a constrained butane molecule that has the dihedral as the only degree of freedom, we show that internal friction comes from the six additional degrees of freedom in unconstrained butane that are orthogonal to the dihedral angle reaction coordinate. While the insensitivity of butane's dihedral dynamics to water viscosity is solely due to the presence of internal friction, inertial effects nevertheless crucially influence the resultant transition rates. In contrast, non-Markovian effects due to the finite memory time are present but do not significantly influence the dihedral barrier-crossing rate of butane. These results not only settle the character of dihedral dynamics in small solvated molecular systems such as butane, they also have important implications for the folding of polymers and proteins. Copyright © 2018 the Author(s). Published by PNAS.

On the dynamics of water molecules at the protein solute interfaces.

PubMed

Bernini, A; Spiga, O; Ciutti, A; Chiellini, S; Menciassi, N; Venditti, V; Niccolai, N

2004-10-01

Proteins, with the large variety of chemical groups they present at their molecular surface, are a class of molecules which can be very informative on most of the possible solute-solvent interactions. Hen egg white lysozyme has been used as a probe to investigate the complex solvent dynamics occurring at the protein surface, by analysing the results obtained from Nuclear Magnetic Resonance, X-ray diffractometry and Molecular Dynamics simulations. A consistent overall picture for the dynamics of water molecules close to the protein is obtained, suggesting that a rapid exchange occurs, in a picosecond timescale, among all the possible hydration surface sites both in solution and the solid state, excluding the possibility that solvent molecules can form liquid-crystal-like supramolecular adducts, which have been proposed as a molecular basis of 'memory of water'.

Beaver Mediated Water Table Dynamics in Mountain Peatlands

NASA Astrophysics Data System (ADS)

Karran, D. J.; Westbrook, C.; Bedard-Haughn, A.

2016-12-01

Water table dynamics play an important role in the ecological and biogeochemical processes that regulate carbon and water storage in peatlands. Beaver are common in these habitats and the dams they build have been shown to raise water tables in other environments. However, the impact of beaver dams in peatlands, where water tables rest close to the surface, has yet to be determined. We monitored a network of 50 shallow wells in a Canadian Rocky Mountain peatland for 6 years. During this period, a beaver colony was maintaining a number of beaver ponds for four years until a flood event removed the colony from the area and breached some of the dams. Two more years of data were collected after the flood event to assess whether the dams enhanced groundwater storage. Beaver dams raised water tables just as they do in other environments. Furthermore, water tables within 100 meters of beaver dams were more stable than those further away and water table stability overall was greater before the flood event. Our results suggest the presence/absence of beaver in peatlands has implications for groundwater water storage and overall system function.

Dynamical properties of water-methanol solutions

NASA Astrophysics Data System (ADS)

Mallamace, Francesco; Corsaro, Carmelo; Mallamace, Domenico; Vasi, Cirino; Vasi, Sebastiano; Stanley, H. Eugene

2016-02-01

We study the relaxation times tα in the water-methanol system. We examine new data and data from the literature in the large temperature range 163 < T < 335 K obtained using different experimental techniques and focus on how tα affects the hydrogen bond structure of the system and the hydrophobicity of the alcohol methyl group. We examine the relaxation times at a fixed temperature as a function of the water molar fraction XW and observe two opposite behaviors in their curvature when the system moves from high to low T regimes. This behavior differs from that of an ideal solution in that it has excess values located at different molar fractions (XW = 0.5 for high T and 0.75 in the deep supercooled regime). We analyze the data and find that above a crossover temperature T ˜ 223 K, hydrophobicity plays a significant role and below it the water tetrahedral network dominates. This temperature is coincident with the fragile-to-strong dynamical crossover observed in confined water and supports the liquid-liquid phase transition hypothesis. At the same time, the reported data suggest that this crossover temperature (identified as the Widom line temperature) also depends on the alcohol concentration.

Effect of Glycerol Water Binary Mixtures on the Structure and Dynamics of Protein Solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ghattyvenkatakrishna, Pavan K; Carri, Gustavo A.

We have performed 20ns of fully atomistic molecular dynamics simulations of Hen Egg-White Lysozyme in 0, 10, 20, 30 and 100% by weight of glycerol in water to better understand the microscopic physics behind the bioprotection offered by glycerol to naturally occuring biological systems. The sovlent exposure of protein surface residues changes when glycerol is introduced. The dynamic behavior of the protein, as quantified by the Incoherent Intermediate Scattering Function, shows a non-monotonic dependence on glycerol content. The fluctuations of the protein residues with respect to each other were found to be similar in all water containing solvents; but differentmore » from the pure glycerol case. The increase in the number of protein glycerol hydrogen bonds in glycerol water binary mixtures explains the slowing down of protein dynamics as the glycerol content increases. We also explored the dynamic behavior of the hydration layer. We show that the short-length scale dynamics of this layer are insenstive to glycerol concentration. However, the long-length scale behavior shows a significant dependence on glycerol content. We also provide insights into the behavior of bound and mobile water molecules.« less

The Caspian Sea water dynamics based on satellite imagery and altimetry

NASA Astrophysics Data System (ADS)

Kostianoy, Andrey G.; Lebedev, Sergey

The Caspian Sea water dynamics is poorly known due to a lack of special hydrographic measurements. The known schemes of general circulation of the sea proposed by N.M. Knipovich in 1914-1915 and 1921, A.I. Mikhalevskiy (1931), G.N. Zaitsev (1935) and V.N. Zenin (1942) represent the basin-scale cyclonic gyres in the Middle and Southern Caspian, and no clear scheme for the shallow Northern Caspian. Later numerical models could move forward from these simple schemes of circulation to the more detailed seasonal or climatic schemes of currents, but different approaches and models give different results which significantly differ from each other (Trukhchev et al., 1995; Ibrayev et al., 2003, 2010; Popov, 2004, 2009; Knysh et al., 2008). Satellite monitoring of the Caspian Sea, we perform since 2000, is a useful tool for investigation of water dynamics in the Caspian Sea. To determine mesoscale water structure and dynamics, we used different kind of physical (SST and ice), chemical (suspended matter and water turbidity) and biological (chlorophyll concentration and algal bloom) tracers on satellite imagery. Satellite altimetry (sea level anomalies in combination with the mean dynamic level derived from numerical modeling) provides fields of currents in the whole Caspian Sea on a regular basis (every 10 days). Seasonal fields of currents derived from satellite altimetry also differ from those obtained in numerical models. Finally, we show the results of the first drifter experiment performed in the Caspian Sea in 2006-2008 in the framework of the MACE Project. Special attention is paid to the seasonal upwelling along the eastern coast of the sea, coastal currents, and a giant intrusion of warm water from the Southern to the Middle Caspian Sea.

Geochemistry of Standard Mine Waters, Gunnison County, Colorado, July 2009

USGS Publications Warehouse

Verplanck, Philip L.; Manning, Andrew H.; Graves, Jeffrey T.; McCleskey, R. Blaine; Todorov, Todor I.; Lamothe, Paul J.

2009-01-01

In many hard-rock-mining districts water flowing from abandoned mine adits is a primary source of metals to receiving streams. Understanding the generation of adit discharge is an important step in developing remediation plans. In 2006, the U.S. Environmental Protection Agency listed the Standard Mine in the Elk Creek drainage basin near Crested Butte, Colorado as a superfund site because drainage from the Standard Mine enters Elk Creek, contributing dissolved and suspended loads of zinc, cadmium, copper, and other metals to the stream. Elk Creek flows into Coal Creek, which is a source of drinking water for the town of Crested Butte. In 2006 and 2007, the U.S. Geological Survey undertook a hydrogeologic investigation of the Standard Mine and vicinity and identified areas of the underground workings for additional work. Mine drainage, underground-water samples, and selected spring water samples were collected in July 2009 for analysis of inorganic solutes as part of a follow-up study. Water analyses are reported for mine-effluent samples from Levels 1 and 5 of the Standard Mine, underground samples from Levels 2 and 3 of the Standard Mine, two spring samples, and an Elk Creek sample. Reported analyses include field measurements (pH, specific conductance, water temperature, dissolved oxygen, and redox potential), major constituents and trace elements, and oxygen and hydrogen isotopic determinations. Overall, water samples collected in 2009 at the same sites as were collected in 2006 have similar chemical compositions. Similar to 2006, water in Level 3 did not flow out the portal but was observed to flow into open workings to lower parts of the mine. Many dissolved constituent concentrations, including calcium, magnesium, sulfate, manganese, zinc, and cadmium, in Level 3 waters substantially are lower than in Level 1 effluent. Concentrations of these dissolved constituents in water samples collected from Level 2 approach or exceed concentrations of Level 1 effluent

Water Dynamics in Egg White Peptide, Asp-His-Thr-Lys-Glu, Powder Monitored by Dynamic Vapor Sorption and LF-NMR.

PubMed

Yang, Shuailing; Liu, Xuye; Jin, Yan; Li, Xingfang; Chen, Feng; Zhang, Mingdi; Lin, Songyi

2016-03-16

Water absorbed into the bulk amorphous structure of peptides can have profound effects on their properties. Here, we elucidated water dynamics in Asp-His-Thr-Lys-Glu (DHTKE), an antioxidant peptide derived from egg white ovalbumin, using water dynamic vapor sorption (DVS) and low-field nuclear magnetic resonance (LF-NMR). The DVS results indicated that parallel exponential kinetics model fitted well to the data of sorption kinetics behavior of DHTKE. Four different proton fractions with different mobilities were identified based on the degree of interaction between peptide and water. The water could significantly change the proton distribution and structure of the sample. The different phases of moisture absorption were reflected in the T2 parameters. In addition, the combined water content was dominant in the hygroscopicity of DHTKE. This study provides an effective real-time monitoring method for water mobility and distribution in synthetic peptides, and this method may have applications in promoting peptide quality assurance.

Monitoring water phase dynamics in winter clouds

NASA Astrophysics Data System (ADS)

Campos, Edwin F.; Ware, Randolph; Joe, Paul; Hudak, David

2014-10-01

This work presents observations of water phase dynamics that demonstrate the theoretical Wegener-Bergeron-Findeisen concepts in mixed-phase winter storms. The work analyzes vertical profiles of air vapor pressure, and equilibrium vapor pressure over liquid water and ice. Based only on the magnitude ranking of these vapor pressures, we identified conditions where liquid droplets and ice particles grow or deplete simultaneously, as well as the conditions where droplets evaporate and ice particles grow by vapor diffusion. The method is applied to ground-based remote-sensing observations during two snowstorms, using two distinct microwave profiling radiometers operating in different climatic regions (North American Central High Plains and Great Lakes). The results are compared with independent microwave radiometer retrievals of vertically integrated liquid water, cloud-base estimates from a co-located ceilometer, reflectivity factor and Doppler velocity observations by nearby vertically pointing radars, and radiometer estimates of liquid water layers aloft. This work thus makes a positive contribution toward monitoring and nowcasting the evolution of supercooled droplets in winter clouds.

Monitoring water phase dynamics in winter clouds

DOE PAGES

Campos, Edwin F.; Ware, Randolph; Joe, Paul; ...

2014-10-01

This work presents observations of water phase dynamics that demonstrate the theoretical Wegener–Bergeron–Findeisen concepts in mixed-phase winter storms. The work analyzes vertical profiles of air vapor pressure, and equilibrium vapor pressure over liquid water and ice. Based only on the magnitude ranking of these vapor pressures, we identified conditions where liquid droplets and ice particles grow or deplete simultaneously, as well as the conditions where droplets evaporate and ice particles grow by vapor diffusion. The method is applied to ground-based remote-sensing observations during two snowstorms, using two distinct microwave profiling radiometers operating in different climatic regions (North American Central Highmore » Plains and Great Lakes). The results are compared with independent microwave radiometer retrievals of vertically integrated liquid water, cloud-base estimates from a co-located ceilometer, reflectivity factor and Doppler velocity observations by nearby vertically pointing radars, and radiometer estimates of liquid water layers aloft. This work thus makes a positive contribution toward monitoring and now casting the evolution of supercooled droplets in winter clouds.« less

Tree water dynamics in a drying and warming world: Future tree water dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grossiord, Charlotte; Sevanto, Sanna; Borrego, Isaac

Disentangling the relative impacts of precipitation reduction and vapour pressure deficit (VPD) on plant water dynamics and determining whether acclimation may influence these patterns in the future is an important challenge. Here, we report sap flux density (FD), stomatal conductance (Gs), hydraulic conductivity (KL) and xylem anatomy in piñon pine (Pinus edulis) and juniper (Juniperus monosperma) trees subjected to five years of precipitation reduction, atmospheric warming (elevated VPD) and their combined effects. No acclimation occurred under precipitation reduction: lower Gs and FD were found for both species compared to ambient conditions. Warming reduced the sensibility of stomata to VPD formore » both species but resulted in the maintenance of Gs and FD to ambient levels only for piñon. For juniper, reduced soil moisture under warming negated benefits of stomatal adjustments and resulted in reduced FD, Gs and KL. Although reduced stomatal sensitivity to VPD also occurred under combined stresses, reductions in Gs, FD and KL took place to similar levels as under single stresses for both species. Our results show that stomatal conductance adjustments to high VPD could minimize but not entirely prevent additive effects of warming and drying on water use and carbon acquisition of trees in semi-arid regions.« less

2D-HB-Network at the air-water interface: A structural and dynamical characterization by means of ab initio and classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Pezzotti, Simone; Serva, Alessandra; Gaigeot, Marie-Pierre

2018-05-01

Following our previous work where the existence of a special 2-Dimensional H-Bond (2D-HB)-Network was revealed at the air-water interface [S. Pezzotti et al., J. Phys. Chem. Lett. 8, 3133 (2017)], we provide here a full structural and dynamical characterization of this specific arrangement by means of both Density Functional Theory based and Force Field based molecular dynamics simulations. We show in particular that water at the interface with air reconstructs to maximize H-Bonds formed between interfacial molecules, which leads to the formation of an extended and non-interrupted 2-Dimensional H-Bond structure involving on average ˜90% of water molecules at the interface. We also show that the existence of such an extended structure, composed of H-Bonds all oriented parallel to the surface, constrains the reorientional dynamics of water that is hence slower at the interface than in the bulk. The structure and dynamics of the 2D-HB-Network provide new elements to possibly rationalize several specific properties of the air-water interface, such as water surface tension, anisotropic reorientation of interfacial water under an external field, and proton hopping.

Coupling all-atom molecular dynamics simulations of ions in water with Brownian dynamics.

PubMed

Erban, Radek

2016-02-01

Molecular dynamics (MD) simulations of ions (K + , Na + , Ca 2+ and Cl - ) in aqueous solutions are investigated. Water is described using the SPC/E model. A stochastic coarse-grained description for ion behaviour is presented and parametrized using MD simulations. It is given as a system of coupled stochastic and ordinary differential equations, describing the ion position, velocity and acceleration. The stochastic coarse-grained model provides an intermediate description between all-atom MD simulations and Brownian dynamics (BD) models. It is used to develop a multiscale method which uses all-atom MD simulations in parts of the computational domain and (less detailed) BD simulations in the remainder of the domain.

Effect of water on structure and dynamics of [BMIM][PF{sub 6}] ionic liquid: An all-atom molecular dynamics simulation investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Anirban; Ghorai, Pradip Kr., E-mail: pradip@iiserkol.ac.in

2016-03-21

Composition dependent structural and dynamical properties of aqueous hydrophobic 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF{sub 6}]) ionic liquid (IL) have been investigated by using all-atom molecular dynamics simulation. We observe that addition of water does not increase significant number of dissociated ions in the solution over the pure state. As a consequence, self-diffusion coefficient of the cation and anion is comparable to each other at all water concentration similar to that is observed for the pure state. Voronoi polyhedra analysis exhibits strong dependence on the local environment of IL concentration. Void and neck distributions in Voronoi tessellation are approximately Gaussian for pure ILmore » but upon subsequent addition of water, we observe deviation from the Gaussian behaviour with an asymmetric broadening with long tail of exponential decay at large void radius, particularly at higher water concentrations. The increase in void space and neck size at higher water concentration facilitates ionic motion, thus, decreasing dynamical heterogeneity and IL reorientation time and increases self-diffusion coefficient significantly.« less

Geohydrology, water quality, and nitrogen geochemistry in the saturated and unsaturated zones beneath various land uses, Riverside and San Bernardino counties, California, 1991-93

USGS Publications Warehouse

Rees, Terry F.; Bright, Daniel J.; Fay, Ronald G.; Christensen, Allen H.; Anders, Robert; Baharie, Brian S.; Land, Michael T.

1995-01-01

The U.S. Geological Survey, in cooperation with the Eastern Municipal Water District, the Metropolitan Water District of Southern California, and the Orange County Water District, has completed a detailed study of the Hemet groundwater basin. The quantity of ground water stored in the basin in August 1992 is estimated to be 327,000 acre-feet. Dissolved-solids concentration ranged from 380 to 700 mg/L (milligrams per liter), except in small areas where the concentration exceeded 1,000 mg/L. Nitrate concentrations exceeded the U.S. Environmental Protection Agency Maximum Contaminant Level (MCL) of 10 mg/L nitrate (as nitrogen) in the southeastern part of the basin, in the Domenigoni Valley area, and beneath a dairy in the Diamond Valley area. Seven sites representing selected land uses-- residential, turf grass irrigated with reclaimed water, citrus grove, irrigated farm, poultry farm, and dairy (two sites)--were selected for detailed study of nitrogen geochemistry in the unsaturated zone. For all land uses, nitrate was the dominant nitrogen species in the unsaturated zone.Although nitrate was seasonally present in the shallow unsaturated zone beneath the residential site, it was absent at moderate depths, suggesting negligible migration of nitrate from the surface at this time. Microbial denitrification probably is occurring in the shallow unsaturated zone. High nitrate concentrations in the deep unsaturated zone (greater than 100 ft) suggest either significantly higher nitrate loading at some time in the past, or lateral movement of nitrate at depth. Nitrate also is seasonally present in the shallow unsaturated zone beneath the reclaimed-water site, and (in contrast with the residential site), nitrate is perennially present in the deeper unsaturated zone. Microbial denitrification in the unsaturated zone and in the capillary fringe above the water table decreases the concentrations of nitrate in pore water to below the MCL before reaching the water table

A laboratory investigation of mixing dynamics between biofuels and surface waters

NASA Astrophysics Data System (ADS)

Wang, Xiaoxiang; Cotel, Aline

2017-11-01

Recently, production and usage of ethanol-blend fuels or biofuels have increased dramatically along with increasing risk of spilling into surface waters. Lack of understanding of the environmental impacts and absence of standard clean-up procedures make it crucial to study the mixing behavior between biofuels and water. Biofuels are represented by a solution of ethanol and glycol. A Plexiglas tank in conjunction with a wave generator is used to simulate the mixing of surface waters and biofuels under different natural conditions. In our previous experiments, two distinct mixing regimes were observed. One regime was driven by turbulence and the other by interfacial instabilities. However, under more realistic situations, without wind driven waves, only the first mixing regime was found. After one minute of rapid turbulent mixing, biofuels and water were fully mixed and no interface was formed. During the mixing process, chemical reactions happened simultaneously and influenced mixing dynamics. Current experiments are investigating the effect of waves on the mixing dynamics. Support from NSF CBET 1335878.

Obtaining higher-accuracy estimates of water-rich rocks and water-poor sand dunes on Mars in active neutron experiments

NASA Astrophysics Data System (ADS)

Gabriel, T. S. J.; Hardgrove, C.; Litvak, M. L.; Nowicki, S.; Mitrofanov, I. G.; Boynton, W. V.; Fedosov, F.; Golovin, D.; Jun, I.; Mischna, M.; Tate, C. G.; Moersch, J.; Harshman, K.; Kozyrev, A.; Malakhov, A. V.; Mokrousov, M.; Nikiforov, S.; Sanin, A. B.; Vostrukhin, A.; Thompson, L. M.

2017-12-01

The Dynamic Albedo of Neutrons (DAN) experiment on the Mars Science Laboratory Curiosity Rover delivers high-energy (14.1 MeV) pulses of neutrons into the surface when operating in "active" mode. Neutrons are moderated in the subsurface and return to two detectors to provide a time-of-flight profile in 64 time-bins in epithermal and thermal energy ranges. Results are compared to simulations of the experiment in the Monte Carlo N-Particle Transport Code where several aspects are modeled including the DAN detectors, neutron source, rover components, and underlying rock. Models can be improved by increasing the fidelity of the rock geochemistry as informed by instruments including the Alpha Particle X-Ray Spectrometer (APXS). Furthermore, increasing the fidelity of the rock morphology in models is enabled by the suite of imaging instruments on the rover.To rapidly interpret DAN data a set of pre-simulated generic rock density and bulk geochemistry models are compared to several DAN active observations. While, to first order, this methodology provides an indication of significant geochemical changes in the subsurface, higher-fidelity models should be used to provide accurate constraints on water content, depth of geologic layers, or abundance of neutron absorbers. For example, in high-silicon, low-iron rocks observed along the rover's traverse, generic models can differ by several wt%H2O from models that use APXS measurements of nearby drill samples. Accurate measurements of high-silicon targets are necessary in outlining the extent of aqueous alteration and hydrothermal activity in Gale Crater. Additionally, we find that for DAN active experiments over sand dunes best-fit models can differ by greater than 0.5 wt%HO when the upper layer density is reduced by 0.6 g/cm3 to account for the low-bulk density of sand. In areas where the rock geochemistry differs little from generic models the difference in results is expectedly less disparate. We report refined wt%HO values

STAND, A DYNAMIC MODEL FOR SEDIMENT TRANSPORT AND WATER QUALITY. (R825758)

EPA Science Inventory

We introduce a new model–STAND (Sediment-Transport-Associated Nutrient Dynamics)–for simulating stream flow, sediment transport, and the interactions of sediment with other attributes of water quality. In contrast to other models, STAND employs a fully dynamic ba...

Geochemistry of the Birch Creek Drainage Basin, Idaho

USGS Publications Warehouse

Swanson, Shawn A.; Rosentreter, Jeffrey J.; Bartholomay, Roy C.; Knobel, LeRoy L.

2003-01-01

The U.S. Survey and Idaho State University, in cooperation with the U.S. Department of Energy, are conducting studies to describe the chemical character of ground water that moves as underflow from drainage basins into the eastern Snake River Plain aquifer (ESRPA) system at and near the Idaho National Engineering and Environmental Laboratory (INEEL) and the effects of these recharge waters on the geochemistry of the ESRPA system. Each of these recharge waters has a hydrochemical character related to geochemical processes, especially water-rock interactions, that occur during migration to the ESRPA. Results of these studies will benefit ongoing and planned geochemical modeling of the ESRPA at the INEEL by providing model input on the hydrochemical character of water from each drainage basin. During 2000, water samples were collected from five wells and one surface-water site in the Birch Creek drainage basin and analyzed for selected inorganic constituents, nutrients, dissolved organic carbon, tritium, measurements of gross alpha and beta radioactivity, and stable isotopes. Four duplicate samples also were collected for quality assurance. Results, which include analyses of samples previously collected from four other sites, in the basin, show that most water from the Birch Creek drainage basin has a calcium-magnesium bicarbonate character. The Birch Creek Valley can be divided roughly into three hydrologic areas. In the northern part, ground water is forced to the surface by a basalt barrier and the sampling sites were either surface water or shallow wells. Water chemistry in this area was characterized by simple evaporation models, simple calcite-carbon dioxide models, or complex models involving carbonate and silicate minerals. The central part of the valley is filled by sedimentary material and the sampling sites were wells that are deeper than those in the northern part. Water chemistry in this area was characterized by simple calcite-dolomite-carbon dioxide

Weakly bound water structure, bond valence saturation and water dynamics at the goethite (100) surface/aqueous interface: ab initio dynamical simulations.

PubMed

Chen, Ying; Bylaska, Eric J; Weare, John H

2017-03-31

Many important geochemical and biogeochemical reactions occur in the mineral/formation water interface of the highly abundant mineral, goethite [α-Fe(OOH)]. Ab initio molecular dynamics (AIMD) simulations of the goethite α-FeOOH (100) surface and the structure, water bond formation and dynamics of water molecules in the mineral/aqueous interface are presented. Several exchange correlation functionals were employed (PBE96, PBE96 + Grimme, and PBE0) in the simulations of a (3 × 2) goethite surface with 65 absorbed water molecules in a 3D-periodic supercell (a = 30 Å, FeOOH slab ~12 Å thick, solvation layer ~18 Å thick). The lowest energy goethite (100) surface termination model was determined to have an exposed surface Fe 3+ that was loosely capped by a water molecule and a shared hydroxide with a neighboring surface Fe 3+ . The water molecules capping surface Fe 3+ ions were found to be loosely bound at all DFT levels with and without Grimme corrections, indicative that each surface Fe 3+ was coordinated with only five neighbors. These long bonds were supported by bond valence theory calculations, which showed that the bond valence of the surface Fe 3+ was saturated and surface has a neutral charge. The polarization of the water layer adjacent to the surface was found to be small and affected only the nearest water. Analysis by density difference plots and localized Boys orbitals identified three types of water molecules: those loosely bound to the surface Fe 3+ , those hydrogen bonded to the surface hydroxyl, and bulk water with tetrahedral coordination. Boys orbital analysis showed that the spin down lone pair orbital of the weakly absorbed water interact more strongly with the spin up Fe 3+ ion. These weakly bound surface water molecules were found to rapidly exchange with the second water layer (~0.025 exchanges/ps) using a dissociative mechanism. Water molecules adjacent to the surface were found to only weakly interact with the surface and as a

Molecular Dynamics Simulations of Carbon Nanotubes in Water

NASA Technical Reports Server (NTRS)

Walther, J. H.; Jaffe, R.; Halicioglu, T.; Koumoutsakos, P.

2000-01-01

We study the hydrophobic/hydrophilic behavior of carbon nanotubes using molecular dynamics simulations. The energetics of the carbon-water interface are mainly dispersive but in the present study augmented with a carbon quadrupole term acting on the charge sites of the water. The simulations indicate that this contribution is negligible in terms of modifying the structural properties of water at the interface. Simulations of two carbon nanotubes in water display a wetting and drying of the interface between the nanotubes depending on their initial spacing. Thus, initial tube spacings of 7 and 8 A resulted in a drying of the interface whereas spacing of > 9 A remain wet during the course of the simulation. Finally, we present a novel particle-particle-particle-mesh algorithm for long range potentials which allows for general (curvilinear) meshes and "black-box" fast solvers by adopting an influence matrix technique.

Hydrocarbon Reservoir Identification in Volcanic Zone by using Magnetotelluric and Geochemistry Information

NASA Astrophysics Data System (ADS)

Firda, S. I.; Permadi, A. N.; Supriyanto; Suwardi, B. N.

2018-03-01

The resistivity of Magnetotelluric (MT) data show the resistivity mapping in the volcanic reservoir zone and the geochemistry information for confirm the reservoir and source rock formation. In this research, we used 132 data points divided with two line at exploration area. We used several steps to make the resistivity mapping. There are time series correction, crosspower correction, then inversion of Magnetotelluric (MT) data. Line-2 and line-3 show anomaly geological condition with Gabon fault. The geology structure from the resistivity mapping show the fault and the geological formation with the geological rock data mapping distribution. The geochemistry information show the maturity of source rock formation. According to core sample analysis information, we get the visual porosity for reservoir rock formation in several geological structure. Based on that, we make the geological modelling where the potential reservoir and the source rock around our interest area.

Dynamics of water in the amphiphilic pore of amyloid β fibrils

NASA Astrophysics Data System (ADS)

GhattyVenkataKrishna, Pavan K.; Mostofian, Barmak

2013-09-01

Alzheimers disease related amyloid peptide, Aβ, forms a fibrillar structure through aggregation. The aggregate is stabilized by a salt bridge that is responsible for the formation of an amphiphilic pore that can accommodate water molecules. None of the reported structures of Aβ, however, contain water. We present results from molecular dynamics simulations on dimeric Aβ fibrils solvated in water. Water penetrates and fills the amphiphilic pore increasing its volume. We observe a thick wire of water that is translationally and rotationally stiff in comparison to bulk water and may be essential for the stabilization of the amyloid Aβ protein.

Rapid freezing of water under dynamic compression

NASA Astrophysics Data System (ADS)

Myint, Philip C.; Belof, Jonathan L.

2018-06-01

Understanding the behavior of materials at extreme pressures is a central issue in fields like aerodynamics, astronomy, and geology, as well as for advancing technological grand challenges such as inertial confinement fusion. Dynamic compression experiments to probe high-pressure states often encounter rapid phase transitions that may cause the materials to behave in unexpected ways, and understanding the kinetics of these phase transitions remains an area of great interest. In this review, we examine experimental and theoretical/computational efforts to study the freezing kinetics of water to a high-pressure solid phase known as ice VII. We first present a detailed analysis of dynamic compression experiments in which water has been observed to freeze on sub-microsecond time scales to ice VII. This is followed by a discussion of the limitations of currently available molecular and continuum simulation methods in modeling these experiments. We then describe how our phase transition kinetics models, which are based on classical nucleation theory, provide a more physics-based framework that overcomes some of these limitations. Finally, we give suggestions on future experimental and modeling work on the liquid–ice VII transition, including an outline of the development of a predictive multiscale model in which molecular and continuum simulations are intimately coupled.

Rapid freezing of water under dynamic compression.

PubMed

Myint, Philip C; Belof, Jonathan L

2018-06-13

Understanding the behavior of materials at extreme pressures is a central issue in fields like aerodynamics, astronomy, and geology, as well as for advancing technological grand challenges such as inertial confinement fusion. Dynamic compression experiments to probe high-pressure states often encounter rapid phase transitions that may cause the materials to behave in unexpected ways, and understanding the kinetics of these phase transitions remains an area of great interest. In this review, we examine experimental and theoretical/computational efforts to study the freezing kinetics of water to a high-pressure solid phase known as ice VII. We first present a detailed analysis of dynamic compression experiments in which water has been observed to freeze on sub-microsecond time scales to ice VII. This is followed by a discussion of the limitations of currently available molecular and continuum simulation methods in modeling these experiments. We then describe how our phase transition kinetics models, which are based on classical nucleation theory, provide a more physics-based framework that overcomes some of these limitations. Finally, we give suggestions on future experimental and modeling work on the liquid-ice VII transition, including an outline of the development of a predictive multiscale model in which molecular and continuum simulations are intimately coupled.

Water dynamics and retrogradation of ultrahigh pressurized wheat starch.

PubMed

Doona, Christopher J; Feeherry, Florence E; Baik, Moo-Yeol

2006-09-06

The water dynamics and retrogradation kinetics behavior of gelatinized wheat starch by either ultrahigh pressure (UHP) processing or heat are investigated. Wheat starch completely gelatinized in the condition of 90, 000 psi at 25 degrees C for 30 min (pressurized gel) or 100 degrees C for 30 min (heated gel). The physical properties of the wheat starches were characterized in terms of proton relaxation times (T2 times) measured using time-domain nuclear magnetic resonance spectroscopy and evaluated using commercially available continuous distribution modeling software. Different T2 distributions in both micro- and millisecond ranges between pressurized and heated wheat starch gels suggest distinctively different water dynamics between pressurized and heated wheat starch gels. Smaller water self-diffusion coefficients were observed for pressurized wheat starch gels and are indicative of more restricted translational proton mobility than is observed with heated wheat starch gels. The physical characteristics associated with changes taking place during retrogradation were evaluated using melting curves obtained with differential scanning calorimetry. Less retrogradation was observed in pressurized wheat starch, and it may be related to a smaller quantity of freezable water in pressurized wheat starch. Starches comprise a major constituent of many foods proposed for commercial potential using UHP, and the present results furnish insight into the effect of UHP on starch gelatinization and the mechanism of retrogradation during storage.

Geochemistry of Israeli oil shales: a review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shirav, M.; Ginzburg, D.

1983-01-01

The oil shales of Israel are widely distributed throughout the country and have current reserves of about 3500 million tons located in the following deposits: Zin, Oron, Ef'e, Hartuv, and Nabi-Musa. The geochemistry and chemical analysis of these shales are discussed, along with the calorific value, oil yield, and trace elements. The main components influencing the quality of the oil shales are organic matter, carbonate, clay minerals, and apatite. Compositional variations within the organic matter are responsible for changes in the relative calorific value and retorted oil yield while fluidized bed combustion is affected by the inorganic components. (JMT)

Dynamic water accounting in heavily committed river basins

NASA Astrophysics Data System (ADS)

Tilmant, Amaury; Marques, Guilherme

2014-05-01

Many river basins throughout the world are increasingly under pressure as water demands keep rising due to population growth, industrialization, urbanization and rising living standards. In the past, the typical answer to meet those demands focused on the supply-side and involved the construction of hydraulic infrastructures to capture more water from surface water bodies and from aquifers. As river basins were being more and more developed, downstream water users and ecosystems have become increasingly dependant on the management actions taken by upstream users. The increased interconnectedness between water users, aquatic ecosystems and the built environment is further compounded by climate change and its impact on the water cycle. Those pressures mean that it has become increasingly important to measure and account for changes in water fluxes and their corresponding economic value as they progress throughout the river system. Such basin water accounting should provide policy makers with important information regarding the relative contribution of each water user, infrastructure and management decision to the overall economic value of the river basin. This paper presents a dynamic water accounting approach whereby the entire river basin is considered as a value chain with multiple services including production and storage. Water users and reservoirs operators are considered as economic agents who can exchange water with their hydraulic neighbors at a price corresponding to the marginal value of water. Effective water accounting is made possible by keeping track of all water fluxes and their corresponding transactions using the results of a hydro-economic model. The proposed approach is illustrated with the Eastern Nile River basin in Africa.

Time-dependent water dynamics in hydrated uranyl fluoride

DOE PAGES

Miskowiec, Andrew J.; Anderson, Brian B.; Herwig, Kenneth W.; ...

2015-09-15

In this study, uranyl fluoride is a three-layer, hexagonal structure with significant stacking disorder in the c-direction. It supports a range of unsolved ‘thermodynamic’ hydrates with 0–2.5 water molecules per uranium atom, and perhaps more. However, the relationship between water, hydrate crystal structures, and thermodynamic results, collectively representing the chemical pathway through these hydrate structures, has not been sufficiently elucidated. We used high-resolution quasielastic neutron scattering to study the dynamics of water in partially hydrated uranyl fluoride powder over the course of 4 weeks under closed conditions. The spectra are composed of two quasielastic components: one is associated with translationalmore » diffusive motion of water that is approximately five to six times slower than bulk water, and the other is a slow (on the order of 2–300 ps), spatially bounded water motion. The translational component represents water diffusing between the weakly bonded layers in the crystal, while the bounded component may represent water trapped in subnanometre ‘pockets’ formed by the space between uranium-centred polymerisation units. Complementary neutron diffraction measurements do not show any significant structural changes, suggesting that a chemical conversion of the material does not occur in the thermodynamically isolated system on this timescale.« less

Bacterial Diversity and Biogeochemistry of Two Marine Shallow-Water Hydrothermal Systems off Dominica (Lesser Antilles).

PubMed

Pop Ristova, Petra; Pichler, Thomas; Friedrich, Michael W; Bühring, Solveig I

2017-01-01

Shallow-water hydrothermal systems represent extreme environments with unique biogeochemistry and high biological productivity, at which autotrophic microorganisms use both light and chemical energy for the production of biomass. Microbial communities of these ecosystems are metabolically diverse and possess the capacity to transform a large range of chemical compounds. Yet, little is known about their diversity or factors shaping their structure or how they compare to coastal sediments not impacted by hydrothermalism. To this end, we have used automated ribosomal intergenic spacer analysis (ARISA) and high-throughput Illumina sequencing combined with porewater geochemical analysis to investigate microbial communities along geochemical gradients in two shallow-water hydrothermal systems off the island of Dominica (Lesser Antilles). At both sites, venting of hydrothermal fluids substantially altered the porewater geochemistry by enriching it with silica, iron and dissolved inorganic carbon, resulting in island-like habitats with distinct biogeochemistry. The magnitude of fluid flow and difference in sediment grain size, which impedes mixing of the fluids with seawater, were correlated with the observed differences in the porewater geochemistry between the two sites. Concomitantly, individual sites harbored microbial communities with a significantly different community structure. These differences could be statistically linked to variations in the porewater geochemistry and the hydrothermal fluids. The two shallow-water hydrothermal systems of Dominica harbored bacterial communities with high taxonomical and metabolic diversity, predominated by heterotrophic microorganisms associated with the Gammaproteobacterial genera Pseudomonas and Pseudoalteromonas , indicating the importance of heterotrophic processes. Overall, this study shows that shallow-water hydrothermal systems contribute substantially to the biogeochemical heterogeneity and bacterial diversity of coastal

Bacterial Diversity and Biogeochemistry of Two Marine Shallow-Water Hydrothermal Systems off Dominica (Lesser Antilles)

PubMed Central

Pop Ristova, Petra; Pichler, Thomas; Friedrich, Michael W.; Bühring, Solveig I.

2017-01-01

Shallow-water hydrothermal systems represent extreme environments with unique biogeochemistry and high biological productivity, at which autotrophic microorganisms use both light and chemical energy for the production of biomass. Microbial communities of these ecosystems are metabolically diverse and possess the capacity to transform a large range of chemical compounds. Yet, little is known about their diversity or factors shaping their structure or how they compare to coastal sediments not impacted by hydrothermalism. To this end, we have used automated ribosomal intergenic spacer analysis (ARISA) and high-throughput Illumina sequencing combined with porewater geochemical analysis to investigate microbial communities along geochemical gradients in two shallow-water hydrothermal systems off the island of Dominica (Lesser Antilles). At both sites, venting of hydrothermal fluids substantially altered the porewater geochemistry by enriching it with silica, iron and dissolved inorganic carbon, resulting in island-like habitats with distinct biogeochemistry. The magnitude of fluid flow and difference in sediment grain size, which impedes mixing of the fluids with seawater, were correlated with the observed differences in the porewater geochemistry between the two sites. Concomitantly, individual sites harbored microbial communities with a significantly different community structure. These differences could be statistically linked to variations in the porewater geochemistry and the hydrothermal fluids. The two shallow-water hydrothermal systems of Dominica harbored bacterial communities with high taxonomical and metabolic diversity, predominated by heterotrophic microorganisms associated with the Gammaproteobacterial genera Pseudomonas and Pseudoalteromonas, indicating the importance of heterotrophic processes. Overall, this study shows that shallow-water hydrothermal systems contribute substantially to the biogeochemical heterogeneity and bacterial diversity of coastal

Interior ice/mineral/water interface dynamics (Invited)

NASA Astrophysics Data System (ADS)

Rempel, A. W.

2009-12-01

The search for life begins with the search for liquid water. In our solar system, persistent water reservoirs are invariably found together with ice. On Earth, organisms have evolved to thrive at sub-zero temperatures in ice-bound habitats that have numerous analogues throughout our solar system and beyond. To assess the potential for life requires a thorough investigation of the dynamic interactions within these deposits. Well-established thermodynamic principles govern the stable coexistence of premelted liquid at the interface between ice and other minerals. Foreign constituents are efficiently rejected from the ice crystal lattice and are concentrated in residual liquid regions instead. This gains added importance with the recognition that the most fundamental requirements for survival include a food source and the removal of waste. This talk reviews the astrobiological implications of the availability, behavior, and properties of liquid water in association with the interiors of icy bodies and ice-mineral interfacial regions.

Photonic water dynamically responsive to external stimuli

PubMed Central

Sano, Koki; Kim, Youn Soo; Ishida, Yasuhiro; Ebina, Yasuo; Sasaki, Takayoshi; Hikima, Takaaki; Aida, Takuzo

2016-01-01

Fluids that contain ordered nanostructures with periodic distances in the visible-wavelength range, anomalously exhibit structural colours that can be rapidly modulated by external stimuli. Indeed, some fish can dynamically change colour by modulating the periodic distance of crystalline guanine sheets cofacially oriented in their fluid cytoplasm. Here we report that a dilute aqueous colloidal dispersion of negatively charged titanate nanosheets exhibits structural colours. In this ‘photonic water', the nanosheets spontaneously adopt a cofacial geometry with an ultralong periodic distance of up to 675 nm due to a strong electrostatic repulsion. Consequently, the photonic water can even reflect near-infrared light up to 1,750 nm. The structural colour becomes more vivid in a magnetic flux that induces monodomain structural ordering of the colloidal dispersion. The reflective colour of the photonic water can be modulated over the entire visible region in response to appropriate physical or chemical stimuli. PMID:27572806

Dynamic Modeling of Process Technologies for Closed-Loop Water Recovery Systems

NASA Technical Reports Server (NTRS)

Allada, Rama Kumar; Lange, Kevin; Anderson, Molly

2011-01-01

Detailed chemical process simulations are a useful tool in designing and optimizing complex systems and architectures for human life support. Dynamic and steady-state models of these systems help contrast the interactions of various operating parameters and hardware designs, which become extremely useful in trade-study analyses. NASA s Exploration Life Support technology development project recently made use of such models to compliment a series of tests on different waste water distillation systems. This paper presents dynamic simulations of chemical process for primary processor technologies including: the Cascade Distillation System (CDS), the Vapor Compression Distillation (VCD) system, the Wiped-Film Rotating Disk (WFRD), and post-distillation water polishing processes such as the Volatiles Removal Assembly (VRA) that were developed using the Aspen Custom Modeler and Aspen Plus process simulation tools. The results expand upon previous work for water recovery technology models and emphasize dynamic process modeling and results. The paper discusses system design, modeling details, and model results for each technology and presents some comparisons between the model results and available test data. Following these initial comparisons, some general conclusions and forward work are discussed.

Hydration level dependence of the microscopic dynamics of water adsorbed in ultramicroporous carbon

DOE PAGES

Mamontov, Eugene; Yue, Yanfeng; Bahadur, Jitendra; ...

2016-10-20

Even when not functionalized intentionally, most carbon materials are not hydrophobic and readily adsorb water molecules from atmospheric water vapor. We have equilibrated an ultramicroporous carbon at several levels of relative humidity, thereby attaining various hydration levels. The water molecules were adsorbed on the pore walls (but did not fill completely the pore volume) and thus could be better described as hydration, or surface, rather than confined, water. We used quasielastic neutron scattering to perform a detailed investigation of the dependence of microscopic dynamics of these adsorbed water species on the hydration level and temperature. The behavior of hydration watermore » in ultramicroporous carbon clearly demonstrates the same universal traits that characterize surface (hydration) water in other materials that are surface-hydrated. In addition, unless special treatment is intentionally applied to ultramicroporous carbon, the species filling its pores in various applications, ranging from hydrogen molecules to electrolytes, likely find themselves in contact with non-freezing water molecules characterized by rich microscopic dynamics.« less

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

PubMed

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NASA Astrophysics Data System (ADS)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

The dynamics of water in hydrated white bread investigated using quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Sjöström, J.; Kargl, F.; Fernandez-Alonso, F.; Swenson, J.

2007-10-01

The dynamics of water in fresh and in rehydrated white bread is studied using quasielastic neutron scattering (QENS). A diffusion constant for water in fresh bread, without temperature gradients and with the use of a non-destructive technique, is presented here for the first time. The self-diffusion constant for fresh bread is estimated to be Ds = 3.8 × 10-10 m2 s-1 and the result agrees well with previous findings for similar systems. It is also suggested that water exhibits a faster dynamics than previously reported in the literature using equilibration of a hydration-level gradient monitored by vibrational spectroscopy. The temperature dependence of the dynamics of low hydration bread is also investigated for T = 280-350 K. The average relaxation time at constant momentum transfer (Q) shows an Arrhenius behavior in the temperature range investigated.

The northern tidal dynamic of Aceh waters: A 3D numerical model

NASA Astrophysics Data System (ADS)

Irham, M.; Miswar, E.; Ilhamsyah, Y.; Setiawan, I.

2018-05-01

The northern tidal dynamic of Aceh waters studied by employing three-dimensional (3D) numerical hydrodynamic model. The purpose of this study is to understand the phenomena and the characteristic of the northern tidal dynamic of Aceh waters. The research used the explicit-splitting scheme numerical model of Navier-Stokes formulation. The result displays that the vertical rotation of flow movement (vertical eddy) at a depth of 15 to 25 meter eastern part of the study area. Hence, the result also informs that the current circulation identically to the upwelling in the western region of Aceh during the wet season and vice versa. However, during the transitional season, the flow circulation depends on how the tidal dynamic occurs in the area.

Vanadium Geochemistry of Oil Sands Fluid Petroleum Coke.

PubMed

Nesbitt, Jake A; Lindsay, Matthew B J

2017-03-07

Vanadium has previously been linked to elevated toxicity of leachates derived from oil sands petroleum coke. However, geochemical controls on V mobility within coke deposits remain poorly constrained. Detailed examinations of porewater and solid-phase V geochemistry were therefore performed on oil sands fluid petroleum coke deposits in Alberta, Canada. Sample collection focused on both active and reclaimed deposits, which contained more than 3 × 10 7 m 3 of fluid petroleum coke. Dissolved V concentrations were highest (up to 3.0 mg L -1 ) immediately below the water table but decreased rapidly with increasing depth. This trend corresponded to a transition from mildly acidic (pH 6-7) and oxic conditions to mildly alkaline (pH 7-8.5) and anoxic conditions. Scanning electron microscopy (SEM), electron microprobe analysis (EMPA), and micro-X-ray fluorescence (μXRF) mapping revealed coke particles exhibited an internal structure characterized by successive concentric layers. The outer margins of these layers were characterized by elevated V, Fe, Si, and Al concentrations, indicating the presence of inorganic phases. Micro-X-ray absorption near-edge structure (μXANES) spectroscopy revealed that V speciation was dominated by V(IV) porphyrins except at outer margins of layers, where octahedrally coordinated V(III) was a major component. Minor to trace V(V) was also detected within fluid petroleum coke particles.

Dynamic nuclear polarization enhanced nuclear magnetic resonance and electron spin resonance studies of hydration and local water dynamics in micelle and vesicle assemblies.

PubMed

McCarney, Evan R; Armstrong, Brandon D; Kausik, Ravinath; Han, Songi

2008-09-16

We present a unique analysis tool for the selective detection of local water inside soft molecular assemblies (hydrophobic cores, vesicular bilayers, and micellar structures) suspended in bulk water. Through the use of dynamic nuclear polarization (DNP), the (1)H NMR signal of water is amplified, as it interacts with stable radicals that possess approximately 658 times higher spin polarization. We utilized stable nitroxide radicals covalently attached along the hydrophobic tail of stearic acid molecules that incorporate themselves into surfactant-based micelle or vesicle structures. Here, we present a study of local water content and fluid viscosity inside oleate micelles and vesicles and Triton X-100 micelles to serve as model systems for soft molecular assemblies. This approach is unique because the amplification of the NMR signal is performed in bulk solution and under ambient conditions with site-specific spin labels that only detect the water that is directly interacting with the localized spin labels. Continuous wave (cw) electron spin resonance (ESR) analysis provides rotational dynamics of the spin-labeled molecular chain segments and local polarity parameters that can be related to hydration properties, whereas we show that DNP-enhanced (1)H NMR analysis of fluid samples directly provides translational water dynamics and permeability of the local environment probed by the spin label. Our technique therefore has the potential to become a powerful analysis tool, complementary to cw ESR, to study hydration characteristics of surfactant assemblies, lipid bilayers, or protein aggregates, where water dynamics is a key parameter of their structure and function. In this study, we find that there is significant penetration of water inside the oleate micelles with a higher average local water viscosity (approximately 1.8 cP) than in bulk water, and Triton X-100 micelles and oleate vesicle bilayers mostly exclude water while allowing for considerable surfactant chain

The Isotope Geochemistry of Abyssal Peridotites and Related Rocks

DTIC Science & Technology

1993-06-01

object of several cruises, including a combined geophysics and petrology cruise (R/V Robert Conrad 27-09: Dick, et al., 1991) and an ocean drilling ...al. (1991) Proceed- ings of the Ocean Drilling Program, Scientific Results Vol. 118. Snow, J., Hart, S.R. and Dick, H.J.B. (1991) "Os isotopic...the geology, petrology , and geochemistry of mantle rocks, as well as their physical and acoustic properties. The first indications that the oceanic

Spectrum of Slow and Super-Slow (Picosecond to Nanosecond) Water Dynamics around Organic and Biological Solutes.

PubMed

Ramakrishnan, Gopakumar; González-Jiménez, Mario; Lapthorn, Adrian J; Wynne, Klaas

2017-07-06

Water dynamics in the solvation shell of solutes plays a very important role in the interaction of biomolecules and in chemical reaction dynamics. However, a selective spectroscopic study of the solvation shell is difficult because of the interference of the solute dynamics. Here we report on the observation of heavily slowed down water dynamics in the solvation shell of different solutes by measuring the low-frequency spectrum of solvation water, free from the contribution of the solute. A slowdown factor of ∼50 is observed even for relatively low concentrations of the solute. We go on to show that the effect can be generalized to different solutes including proteins.

POSTFUNDOPLICATION DYSPHAGIA CAUSES SIMILAR WATER INGESTION DYNAMICS AS ACHALASIA.

PubMed

Dantas, Roberto Oliveira; Santos, Carla Manfredi; Cassiani, Rachel Aguiar; Alves, Leda Maria Tavares; Nascimento, Weslania Viviane

2016-01-01

- After surgical treatment of gastroesophageal reflux disease dysphagia is a symptom in the majority of patients, with decrease in intensity over time. However, some patients may have persistent dysphagia. - The objective of this investigation was to evaluate the dynamics of water ingestion in patients with postfundoplication dysphagia compared with patients with dysphagia caused by achalasia, idiopathic or consequent to Chagas' disease, and controls. - Thirty-three patients with postfundoplication dysphagia, assessed more than one year after surgery, together with 50 patients with Chagas' disease, 27 patients with idiopathic achalasia and 88 controls were all evaluated by the water swallow test. They drunk, in triplicate, 50 mL of water without breaks while being precisely timed and the number of swallows counted. Also measured was: (a) inter-swallows interval - the time to complete the task, divided by the number of swallows during the task; (b) swallowing flow - volume drunk divided by the time taken; (c) volume of each swallow - volume drunk divided by the number of swallows. - Patients with postfundoplication dysphagia, Chagas' disease and idiopathic achalasia took longer to ingest all the volume, had an increased number of swallows, an increase in interval between swallows, a decrease in swallowing flow and a decrease in water volume of each swallow compared with the controls. There was no difference between the three groups of patients. There was no correlation between postfundoplication time and the results. - It was concluded that patients with postfundoplication dysphagia have similar water ingestion dynamics as patients with achalasia.

Measurement and inference of profile soil-water dynamics at different hillslope positions in a semiarid agricultural watershed

NASA Astrophysics Data System (ADS)

Green, Timothy R.; Erskine, Robert H.

2011-12-01

Dynamics of profile soil water vary with terrain, soil, and plant characteristics. The objectives addressed here are to quantify dynamic soil water content over a range of slope positions, infer soil profile water fluxes, and identify locations most likely influenced by multidimensional flow. The instrumented 56 ha watershed lies mostly within a dryland (rainfed) wheat field in semiarid eastern Colorado. Dielectric capacitance sensors were used to infer hourly soil water content for approximately 8 years (minus missing data) at 18 hillslope positions and four or more depths. Based on previous research and a new algorithm, sensor measurements (resonant frequency) were rescaled to estimate soil permittivity, then corrected for temperature effects on bulk electrical conductivity before inferring soil water content. Using a mass-conservation method, we analyzed multitemporal changes in soil water content at each sensor to infer the dynamics of water flux at different depths and landscape positions. At summit positions vertical processes appear to control profile soil water dynamics. At downslope positions infrequent overland flow and unsaturated subsurface lateral flow appear to influence soil water dynamics. Crop water use accounts for much of the variability in soil water between transects that are either cropped or fallow in alternating years, while soil hydraulic properties and near-surface hydrology affect soil water variability across landscape positions within each management zone. The observed spatiotemporal patterns exhibit the joint effects of short-term hydrology and long-term soil development. Quantitative methods of analyzing soil water patterns in space and time improve our understanding of dominant soil hydrological processes and provide alternative measures of model performance.

Coral skeletal geochemistry as a monitor of inshore water quality.

PubMed

Saha, Narottam; Webb, Gregory E; Zhao, Jian-Xin

2016-10-01

Coral reefs maintain extraordinary biodiversity and provide protection from tsunamis and storm surge, but inshore coral reef health is degrading in many regions due to deteriorating water quality. Deconvolving natural and anthropogenic changes to water quality is hampered by the lack of long term, dated water quality data but such records are required for forward modelling of reef health to aid their management. Reef corals provide an excellent archive of high resolution geochemical (trace element) proxies that can span hundreds of years and potentially provide records used through the Holocene. Hence, geochemical proxies in corals hold great promise for understanding changes in ancient water quality that can inform broader oceanographic and climatic changes in a given region. This article reviews and highlights the use of coral-based trace metal archives, including metal transported from rivers to the ocean, incorporation of trace metals into coral skeletons and the current 'state of the art' in utilizing coral trace metal proxies as tools for monitoring various types of local and regional source-specific pollution (river discharge, land use changes, dredging and dumping, mining, oil spills, antifouling paints, atmospheric sources, sewage). The three most commonly used coral trace element proxies (i.e., Ba/Ca, Mn/Ca, and Y/Ca) are closely associated with river runoff in the Great Barrier Reef, but considerable uncertainty remains regarding their complex biogeochemical cycling and controlling mechanisms. However, coral-based water quality reconstructions have suffered from a lack of understanding of so-called vital effects and early marine diagenesis. The main challenge is to identify and eliminate the influence of extraneous local factors in order to allow accurate water quality reconstructions and to develop alternate proxies to monitor water pollution. Rare earth elements have great potential as they are self-referencing and reflect basic terrestrial input

Application of dynamic programming to control khuzestan water resources system

USGS Publications Warehouse

Jamshidi, M.; Heidari, M.

1977-01-01

An approximate optimization technique based on discrete dynamic programming called discrete differential dynamic programming (DDDP), is employed to obtain the near optimal operation policies of a water resources system in the Khuzestan Province of Iran. The technique makes use of an initial nominal state trajectory for each state variable, and forms corridors around the trajectories. These corridors represent a set of subdomains of the entire feasible domain. Starting with such a set of nominal state trajectories, improvements in objective function are sought within the corridors formed around them. This leads to a set of new nominal trajectories upon which more improvements may be sought. Since optimization is confined to a set of subdomains, considerable savings in memory and computer time are achieved over that of conventional dynamic programming. The Kuzestan water resources system considered in this study is located in southwest Iran, and consists of two rivers, three reservoirs, three hydropower plants, and three irrigable areas. Data and cost benefit functions for the analysis were obtained either from the historical records or from similar studies. ?? 1977.

Comparing Classical Water Models Using Molecular Dynamics to Find Bulk Properties

ERIC Educational Resources Information Center

Kinnaman, Laura J.; Roller, Rachel M.; Miller, Carrie S.

2018-01-01

A computational chemistry exercise for the undergraduate physical chemistry laboratory is described. In this exercise, students use the molecular dynamics package Amber to generate trajectories of bulk liquid water for 4 different water models (TIP3P, OPC, SPC/E, and TIP4Pew). Students then process the trajectory to calculate structural (radial…

A dynamic simulation based water resources education tool.

PubMed

Williams, Alison; Lansey, Kevin; Washburne, James

2009-01-01

Educational tools to assist the public in recognizing impacts of water policy in a realistic context are not generally available. This project developed systems with modeling-based educational decision support simulation tools to satisfy this need. The goal of this model is to teach undergraduate students and the general public about the implications of common water management alternatives so that they can better understand or become involved in water policy and make more knowledgeable personal or community decisions. The model is based on Powersim, a dynamic simulation software package capable of producing web-accessible, intuitive, graphic, user-friendly interfaces. Modules are included to represent residential, agricultural, industrial, and turf uses, as well as non-market values, water quality, reservoir, flow, and climate conditions. Supplementary materials emphasize important concepts and lead learners through the model, culminating in an open-ended water management project. The model is used in a University of Arizona undergraduate class and within the Arizona Master Watershed Stewards Program. Evaluation results demonstrated improved understanding of concepts and system interactions, fulfilling the project's objectives.

DYNAMIC DEUTERIUM ENRICHMENT IN COMETARY WATER VIA ELEY–RIDEAL REACTIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yao, Yunxi; Giapis, Konstantinos P., E-mail: giapis@cheme.caltech.edu

2017-01-20

The deuterium-to-hydrogen ratio (D/H) in water found in the coma of Jupiter family comet (JFC) 67P/Churyumov–Gerasimenko was reported to be (5.3 ± 0.7) × 10{sup −4}, the highest among comets and three times the value for other JFCs with an ocean-like ratio. This discrepancy suggests the diverse origins of JFCs and clouds the issue of the origin of Earth’s oceanic water. Here we demonstrate that Eley–Rideal reactions between accelerated water ions and deuterated cometary surface analogs can lead to instantaneous deuterium enrichment in water scattered from the surface. The reaction proceeds with H{sub 2}O{sup +} abstracting adsorbed D atoms, formingmore » an excited H{sub 2}DO* state, which dissociates subsequently to produce energetic HDO. Hydronium ions are also produced readily by the abstraction of H atoms, consistent with H{sub 3}O{sup +} detection and abundance in various comets. Experiments with water isotopologs and kinematic analysis on deuterated platinum surfaces confirmed the dynamic abstraction mechanism. The instantaneous fractionation process is independent of the surface temperature and may operate on the surface of cometary nuclei or dust grains, composed of deuterium-rich silicates and carbonaceous chondrites. The requisite energetic water ions have been detected in the coma of 67P in two populations. This dynamic fractionation process may temporarily increase the water D/H ratio, especially as the comet gets closer to the Sun. The magnitude of the effect depends on the water ion energy-flux and the deuterium content of the exposed cometary surfaces.« less

Computational Fluid Dynamic Simulation of Flow in Abrasive Water Jet Machining

NASA Astrophysics Data System (ADS)

Venugopal, S.; Sathish, S.; Jothi Prakash, V. M.; Gopalakrishnan, T.

2017-03-01

Abrasive water jet cutting is one of the most recently developed non-traditional manufacturing technologies. In this machining, the abrasives are mixed with suspended liquid to form semi liquid mixture. The general nature of flow through the machining, results in fleeting wear of the nozzle which decrease the cutting performance. The inlet pressure of the abrasive water suspension has main effect on the major destruction characteristics of the inner surface of the nozzle. The aim of the project is to analyze the effect of inlet pressure on wall shear and exit kinetic energy. The analysis could be carried out by changing the taper angle of the nozzle, so as to obtain optimized process parameters for minimum nozzle wear. The two phase flow analysis would be carried by using computational fluid dynamics tool CFX. It is also used to analyze the flow characteristics of abrasive water jet machining on the inner surface of the nozzle. The availability of optimized process parameters of abrasive water jet machining (AWJM) is limited to water and experimental test can be cost prohibitive. In this case, Computational fluid dynamics analysis would provide better results.

Molecular dynamics of the water liquid-vapor interface

NASA Technical Reports Server (NTRS)

Wilson, M. A.; Pohorille, A.; Pratt, L. R.; MacElroy, R. D. (Principal Investigator)

1987-01-01

The results of molecular dynamics calculations on the equilibrium interface between liquid water and its vapor at 325 K are presented. For the TIP4P model of water intermolecular pair potentials, the average surface dipole density points from the vapor to the liquid. The most common orientations of water molecules have the C2 nu molecular axis roughly parallel to the interface. The distributions are quite broad and therefore compatible with the intermolecular correlations characteristic of bulk liquid water. All near-neighbor pairs in the outermost interfacial layers are hydrogen bonded according to the common definition adopted here. The orientational preferences of water molecules near a free surface differ from those near rigidly planar walls which can be interpreted in terms of patterns found in hexagonal ice 1. The mean electric field in the interfacial region is parallel to the mean polarization which indicates that attention cannot be limited to dipolar charge distributions in macroscopic descriptions of the electrical properties of this interface. The value of the surface tension obtained is 132 +/- 46 dyn/cm, significantly different from the value for experimental water of 68 dyn/cm at 325 K.

Effects of Water-Based Training on Static and Dynamic Balance of Older Women.

PubMed

Bento, Paulo Cesar Barauce; Lopes, Maria de Fátima A; Cebolla, Elaine Cristine; Wolf, Renata; Rodacki, André L F

2015-08-01

The aim of this study was to evaluate the effects of a water-based exercise program on static and dynamic balance. Thirty-six older women were randomly assigned to a water-based training (3 days/week for 12 weeks) or control group. Water level was kept at the level of the xiphoid process and temperature at ∼28-30°C. Each session included aerobic activities and lower limb strength exercises. The medial-lateral, the anterior-posterior amplitude, and displacement of the center of pressure (CP-D) were measured in a quiet standing position (60 sec eyes opened and closed). The dynamic balance and 8-Foot Up-and-Go tests were also applied. Group comparisons were made using two-way analysis of variance (ANOVA) with repeated measures. No differences were found in the center of pressure variables; however, the WBT group showed better performance in the 8 Foot Up-and-Go Test after training (5.61±0.76 vs. 5.18±0.42; p<0.01). The water-based training was effective in improving dynamic balance, but not static balance.

Dynamic contact angle of water-based titanium oxide nanofluid

PubMed Central

2013-01-01

This paper presents an investigation into spreading dynamics and dynamic contact angle of TiO2-deionized water nanofluids. Two mechanisms of energy dissipation, (1) contact line friction and (2) wedge film viscosity, govern the dynamics of contact line motion. The primary stage of spreading has the contact line friction as the dominant dissipative mechanism. At the secondary stage of spreading, the wedge film viscosity is the dominant dissipative mechanism. A theoretical model based on combination of molecular kinetic theory and hydrodynamic theory which incorporates non-Newtonian viscosity of solutions is used. The model agreement with experimental data is reasonable. Complex interparticle interactions, local pinning of the contact line, and variations in solid–liquid interfacial tension are attributed to errors. PMID:23759071

Communication: On the origin of the non-Arrhenius behavior in water reorientation dynamics.

PubMed

Stirnemann, Guillaume; Laage, Damien

2012-07-21

We combine molecular dynamics simulations and analytic modeling to determine the origin of the non-Arrhenius temperature dependence of liquid water's reorientation and hydrogen-bond dynamics between 235 K and 350 K. We present a quantitative model connecting hydrogen-bond exchange dynamics to local structural fluctuations, measured by the asphericity of Voronoi cells associated with each water molecule. For a fixed local structure the regular Arrhenius behavior is recovered, and the global anomalous temperature dependence is demonstrated to essentially result from a continuous shift in the unimodal structure distribution upon cooling. The non-Arrhenius behavior can thus be explained without invoking an equilibrium between distinct structures. In addition, the large width of the homogeneous structural distribution is shown to cause a growing dynamical heterogeneity and a non-exponential relaxation at low temperature.

Nonideality in diffusion of ionic and hydrophobic solutes and pair dynamics in water-acetone mixtures of varying composition.

PubMed

Gupta, Rini; Chandra, Amalendu

2007-07-14

We have performed a series of molecular dynamics simulations of water-acetone mixtures containing either an ionic solute or a neutral hydrophobic solute to study the extent of nonideality in the dynamics of these solutes with variation of composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to change nonmonotonically with the composition of the mixtures showing strong nonideality of their dynamics. Also, the extent of nonideality in the diffusion of these charged solutes is found to be similar to the nonideality that is observed for the diffusion and orientational relaxation of water and acetone molecules in these mixtures which show a somewhat similar changes in the solvation characteristics of charged and dipolar solutes with changes of composition of water-acetone mixtures. The diffusion of the hydrophobic solute, however, shows a monotonic increase with increase of acetone concentration showing its different solvation characteristics as compared to the charged and dipolar solutes. The links between the nonideality in diffusion and solvation structures are further confirmed through calculations of the relevant solute-solvent and solvent-solvent radial distribution functions for both ionic and hydrophobic solutes. We have also calculated various pair dynamical properties such as the relaxation of water-water and acetone-water hydrogen bonds and residence dynamics of water molecules in water and acetone hydration shells. The lifetimes of both water-water and acetone-water hydrogen bonds and also the residence times of water molecules are found to increase steadily with increase in acetone concentration. No maximum or minimum was found in the composition dependence of these pair dynamical quantities. The lifetimes of water-water hydrogen bonds are always found to be longer than that of acetone-water hydrogen bonds in these mixtures. The residence times of water molecules are also found to follow a

Structural dynamics of supercooled water from quasielastic neutron scattering and molecular simulations.

PubMed

Qvist, Johan; Schober, Helmut; Halle, Bertil

2011-04-14

One of the outstanding challenges presented by liquid water is to understand how molecules can move on a picosecond time scale despite being incorporated in a three-dimensional network of relatively strong H-bonds. This challenge is exacerbated in the supercooled state, where the dramatic slowing down of structural dynamics is reminiscent of the, equally poorly understood, generic behavior of liquids near the glass transition temperature. By probing single-molecule dynamics on a wide range of time and length scales, quasielastic neutron scattering (QENS) can potentially reveal the mechanistic details of water's structural dynamics, but because of interpretational ambiguities this potential has not been fully realized. To resolve these issues, we present here an extensive set of high-quality QENS data from water in the range 253-293 K and a corresponding set of molecular dynamics (MD) simulations to facilitate and validate the interpretation. Using a model-free approach, we analyze the QENS data in terms of two motional components. Based on the dynamical clustering observed in MD trajectories, we identify these components with two distinct types of structural dynamics: picosecond local (L) structural fluctuations within dynamical basins and slower interbasin jumps (J). The Q-dependence of the dominant QENS component, associated with J dynamics, can be quantitatively rationalized with a continuous-time random walk (CTRW) model with an apparent jump length that depends on low-order moments of the jump length and waiting time distributions. Using a simple coarse-graining algorithm to quantitatively identify dynamical basins, we map the newtonian MD trajectory on a CTRW trajectory, from which the jump length and waiting time distributions are computed. The jump length distribution is gaussian and the rms jump length increases from 1.5 to 1.9 Å as the temperature increases from 253 to 293 K. The rms basin radius increases from 0.71 to 0.75 Å over the same range. The

Structural dynamics of supercooled water from quasielastic neutron scattering and molecular simulations

NASA Astrophysics Data System (ADS)

Qvist, Johan; Schober, Helmut; Halle, Bertil

2011-04-01

One of the outstanding challenges presented by liquid water is to understand how molecules can move on a picosecond time scale despite being incorporated in a three-dimensional network of relatively strong H-bonds. This challenge is exacerbated in the supercooled state, where the dramatic slowing down of structural dynamics is reminiscent of the, equally poorly understood, generic behavior of liquids near the glass transition temperature. By probing single-molecule dynamics on a wide range of time and length scales, quasielastic neutron scattering (QENS) can potentially reveal the mechanistic details of water's structural dynamics, but because of interpretational ambiguities this potential has not been fully realized. To resolve these issues, we present here an extensive set of high-quality QENS data from water in the range 253-293 K and a corresponding set of molecular dynamics (MD) simulations to facilitate and validate the interpretation. Using a model-free approach, we analyze the QENS data in terms of two motional components. Based on the dynamical clustering observed in MD trajectories, we identify these components with two distinct types of structural dynamics: picosecond local (L) structural fluctuations within dynamical basins and slower interbasin jumps (J). The Q-dependence of the dominant QENS component, associated with J dynamics, can be quantitatively rationalized with a continuous-time random walk (CTRW) model with an apparent jump length that depends on low-order moments of the jump length and waiting time distributions. Using a simple coarse-graining algorithm to quantitatively identify dynamical basins, we map the Newtonian MD trajectory on a CTRW trajectory, from which the jump length and waiting time distributions are computed. The jump length distribution is Gaussian and the rms jump length increases from 1.5 to 1.9 Å as the temperature increases from 253 to 293 K. The rms basin radius increases from 0.71 to 0.75 Å over the same range. The

Proline induced disruption of the structure and dynamics of water.

PubMed

Yu, Dehong; Hennig, Marcus; Mole, Richard A; Li, Ji Chen; Wheeler, Cheryl; Strässle, Thierry; Kearley, Gordon J

2013-12-21

We use quasi-elastic neutron scattering spectroscopy to study the diffusive motion of water molecules at ambient temperature as a function of the solute molar fraction of the amino acid, proline. We validate molecular dynamics simulations against experimental quasielastic neutron scattering data and then use the simulations to reveal, and understand, a strong dependence of the translational self-diffusion coefficient of water on the distance to the amino acid molecule. An analysis based on the juxtaposition of water molecules in the simulation shows that the rigidity of proline imposes itself on the local water structure, which disrupts the hydrogen-bond network of water leading to an increase in the mean lifetime of hydrogen bonds. The net effect is some distortion of the proline molecule and a slowing down of the water mobility.

Dynamic Behaviour and Seismic Response of Ground Supported Cylindrical Water Tanks

NASA Astrophysics Data System (ADS)

Asha, Joseph; Glory, Joseph

2018-05-01

Liquid storage tank such as in water distribution systems, petroleum plants etc., constitute a vital component of life line systems. Reducing earthquake effects on liquid storage tanks, to minimize the environmental and economic impact of these effects, have always been an important engineering concern. In this paper, the dynamic behavior of cylindrical ground supported concrete water tanks with different aspect ratios is investigated using finite element software ANSYS. The natural frequencies and modal responses are obtained for impulsive and convective modes of vibration. The natural frequency of vibration of the tank is observed to be the lowest at maximum water depth. The fundamental impulsive frequency increases as water level reduces and for water level less than 1/3 of tank height, there is significantly no change in impulsive frequency. The effect of wall flexibility on dynamic behavior of the tank is investigated by performing the modal analysis of flexible and rigid tanks. For a partially filled tank, the results of the present study are of significant relevance. The response of the tank to the transient loading as horizontal ground motion of El Centro earthquake is studied for various water heights. As the height of water on the tank increases, the ultimate maximum seismic response parameters are also observed to be increased. The location of maximum hoop stress varies in accordance with the variations in input ground motion and water fill condition whereas shear and bending moment are maximum at the base.

System Dynamics to Climate-Driven Water Budget Analysis in the Eastern Snake Plains Aquifer

NASA Astrophysics Data System (ADS)

Ryu, J.; Contor, B.; Wylie, A.; Johnson, G.; Allen, R. G.

2010-12-01

Climate variability, weather extremes and climate change continue to threaten the sustainability of water resources in the western United States. Given current climate change projections, increasing temperature is likely to modify the timing, form, and intensity of precipitation events, which consequently affect regional and local hydrologic cycles. As a result, drought, water shortage, and subsequent water conflicts may become an increasing threat in monotone hydrologic systems in arid lands, such as the Eastern Snake Plain Aquifer (ESPA). The ESPA, in particular, is a critical asset in the state of Idaho. It is known as the economic lifeblood for more than half of Idaho’s population so that water resources availability and aquifer management due to climate change is of great interest, especially over the next few decades. In this study, we apply system dynamics as a methodology with which to address dynamically complex problems in ESPA’s water resources management. Aquifer recharge and discharge dynamics are coded in STELLA modeling system as input and output, respectively to identify long-term behavior of aquifer responses to climate-driven hydrological changes.

Microscopic dynamics of water around unfolded structures of barstar at room temperature

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pal, Somedatta; Chakraborty, Kaushik; Khatua, Prabir

2015-02-07

The breaking of the native structure of a protein and its influences on the dynamic response of the surrounding solvent is an important issue in protein folding. In this work, we have carried out atomistic molecular dynamics simulations to unfold the protein barstar at two different temperatures (400 K and 450 K). The two unfolded forms obtained at such high temperatures are further studied at room temperature to explore the effects of nonuniform unfolding of the protein secondary structures along two different pathways on the microscopic dynamical properties of the surface water molecules. It is demonstrated that though the structuralmore » transition of the protein in general results in less restricted water motions around its segments, but there are evidences of formation of new conformational motifs upon unfolding with increasingly confined environment around them, thereby resulting in further restricted water mobility in their hydration layers. Moreover, it is noticed that the effects of nonuniform unfolding of the protein segments on the relaxation times of the protein–water (PW) and the water–water (WW) hydrogen bonds are correlated with hindered hydration water motions. However, the kinetics of breaking and reformation of such hydrogen bonds are found to be influenced differently at the interface. It is observed that while the effects of unfolding on the PW hydrogen bond kinetics seem to be minimum, but the kinetics involving the WW hydrogen bonds around the protein segments exhibit noticeably heterogeneous characteristics. We believe that this is an important observation, which can provide valuable insights on the origin of heterogeneous influence of unfolding of a protein on the microscopic properties of its hydration water.« less

Arsenic in ground water of the United States: occurrence and geochemistry

USGS Publications Warehouse

Welch, Alan H.; Westjohn, D.B.; Helsel, Dennis R.; Wanty, Richard B.

2000-01-01

Concentrations of naturally occurring arsenic in ground water vary regionally due to a combination of climate and geology. Although slightly less than half of 30,000 arsenic analyses of ground water in the United States were 1 μg/L, about 10% exceeded 10 μg/L. At a broad regional scale, arsenic concentrations exceeding 10 μg/L appear to be more frequently observed in the western United States than in the eastern half. Arsenic concentrations in ground water of the Appalachian Highlands and the Atlantic Plain generally are very low ( 1 μg/L). Concentrations are somewhat greater in the Interior Plains and the Rocky Mountain System. Investigations of ground water in New England, Michigan, Minnesota, South Dakota, Oklahoma, and Wisconsin within the last decade suggest that arsenic concentrations exceeding 10 μg/L are more widespread and common than previously recognized.Arsenic release from iron oxide appears to be the most common cause of widespread arsenic concentrations exceeding 10 μg/L in ground water. This can occur in response to different geochemical conditions, including release of arsenic to ground water through reaction of iron oxide with either natural or anthropogenic (i.e., petroleum products) organic carbon. Iron oxide also can release arsenic to alkaline ground water, such as that found in some felsic volcanic rocks and alkaline aquifers of the western United States. Sulfide minerals are both a source and sink for arsenic. Geothermal water and high evaporation rates also are associated with arsenic concentrations 10g/L in ground and surface water, particularly in the west.Arsenic release from iron oxide appears to be the most common cause of widespread arsenic concentrations exceeding 10 µg/L a ground water. This can occur in response to different geochemical conditions, including release of arsenic to ground water through reaction of iron oxide with either natural or anthropogenic (i.e., petroleum products) organic carbon. Iron oxide also can

Water infiltration in prewetted porous media: dynamic capillary pressure and Green-Ampt modeling

NASA Astrophysics Data System (ADS)

Hsu, S.; Hilpert, M.

2013-12-01

Recently, an experimental study has shown that the modified Green-Ampt (GA) model, which accounts for a velocity-dependent capillary pressure, can describe water infiltration in dry sand columns better than the classical GA model. Studies have also shown that the initial water content of prewetted porous media affects the dynamic capillary pressure during infiltration. In this study, we performed a series of downward water infiltration experiments in prewetted sand columns for four different initial water contents: 0%, 3.3%, 6.5%, and 13.8%. We also used three different ponding heights: 10 cm, 20 cm, and 40 cm. As expected, an increase in ponding height resulted in a monotonic increase in cumulative infiltration. However, we found anomalous behavior, in that the cumulative infiltration did not monotonically decrease as the initial water content increased. When modeling the experiments with the modified GA approach, we linked this anomalous behavior to the reduction factor in the model for dynamic capillary pressure that is a function of initial water content.

Geochemical Analyses of Rock, Sediment, and Water from the Region In and Around the Tuba City Landfill, Tuba City, Arizona

USGS Publications Warehouse

Johnson, Raymond H.; Wirt, Laurie

2009-01-01

The Tuba City Landfill (TCL) started as an unregulated waste disposal site in the 1940s and was administratively closed in 1997. Since the TCL closure, radionuclides have been detected in the shallow ground water. In 2006, the Bureau of Indian Affairs (BIA) contracted with the U.S. Geological Survey (USGS) to better understand the source of radionuclides in the ground water at the TCL compared to the surrounding region. This report summarizes those data and presents interpretations that focus on the geochemistry in the rocks and water from the Tuba City region. The TCL is sited on Navajo Sandstone above the contact with the Kayenta Formation. These formations are not rich in uranium but generally are below average crustal abundance values for uranium. Uranium ores in the area were mined nearby in the Chinle Formation and processed at the Rare Metals mill (RMM). Regional samples of rock, sediment, leachates, and water were collected in and around the TCL site and analyzed for major and minor elements, 18O, 2H, 3H, 13C, 14C,34S, 87Sr, and 234U/238U, as appropriate. Results of whole rock and sediment samples, along with leachates, suggest the Chinle Formation is a major source of uranium and other trace elements in the area. Regional water samples indicate that some of the wells within the TCL site have geochemical signatures that are different from the regional springs and surface water. The geochemistry from these TCL wells is most similar to leachates from the Chinle Formation rocks and sediments. Isotope samples do not uniquely identify TCL-derived waters, but they do provide a useful indicator for shallow compared to deep ground-water flow paths and general rock/water interaction times. Information in this report provides a comparison between the geochemistry within the TCL and in the region as a whole.

MICROFRACTURE SURFACE GEOCHEMISTRY AND ADHERENT MICROBIAL POPULATION METABOLISM IN TCE-CONTAMINATED COMPETENT BEDROCK

EPA Science Inventory

A TCE-contaminated competent bedrock site in Portsmouth, NH was used to determine if a relation existed between microfracture (MF) surface geochemistry and the ecology and metabolic activity of attached microbes relative to terminal electron accepting processes (TEAPs) and TCE bi...

Water drop dynamics on a granular layer

NASA Astrophysics Data System (ADS)

Llorens, Coraline; Biance, Anne-Laure; Ybert, Christophe; Pirat, Christophe; Liquids; Interfaces Team

2015-11-01

Liquid drop impacts, either on a solid surface or a liquid bath, have been studied for a while and are still subject of intense research. Less is known concerning impacts on granular layers that are shown to exhibit an intermediate situation between solid and liquid. In this study, we focus on water drop impacts on granular matter made of micrometer-sized spherical glass beads. In particular, we investigate the overall dynamics arising from the interplay between liquid and grains throughout the impact. Depending on the relevant parameters (impact velocity, drop and grain sizes, as well as their wetting properties), various behaviors are evidenced. In particular, the behavior of the beads at the liquid-gas interface (ball-bearing vs imbibition) is shown to greatly affect the spreading dynamics of the drop, as well as satellite droplets formation, beads ejection, and the final crater morphology.

Dynamic properties of individual water molecules in a hydrophobic pore lined with acyl chains: a molecular dynamics study.

PubMed

Qi, Z; Sokabe, M

1998-03-30

Recently, a certain class of synthetic molecules has been shown to form ion channels, the pore of which is lined with hydrophobic acyl chains [M. Sokabe, in: F. Oosawa, H. Hayashi, T. Yoshioka (Eds.), Transmembrane Signaling and Sensation, JSSP/VNU Science Press BV, Tokyo, 1984, p. 119; F. Hayashi, M. Sokabe, M. Takagi, K. Hayashi, U. Kishimoto, Biochim. Biophys. Acta, 510 (1978) 305; M.J. Pregel, L. Jullien, J. Canceill, L. Lacombe, J.M. Lehn, J. Chem. Soc. Perkin Trans., 2 (1995) 417; Y. Tanaka, Y. Kobuke, M. Sokabe, Angew. Chem. Int. Ed. Engl., 34 (1995) 693; M. Sokabe, Z. Qi, K. Donowaki, H. Ishida, K. Okubo, Biophys. J., 70 (1996) A201; H. Ishida, K. Donowaki, Y. Inoue, Z. Qi, M. Sokabe, Chem. Lett. (1997) p. 953]. As an initial step towards understanding the physical mechanisms of ion permeation across such a hydrophobic pore, systematic molecular dynamics simulations were performed to investigate dynamic and energetic properties of water molecules inside the pore using a dimer of alanine-N'-acylated cyclic peptide as a channel model. Dynamic energy profiles for water molecules indicated that the energy barrier at the middle region of the pore is approximately 2-3 kcal/mol higher than that in the cap water region which was defined as a vicinity region of the channel entrance. Energetics analyses demonstrated that the mutual interactions among intrapore water molecules are the major factor to give favorable interaction (negative energy contribution) for themselves. The pore, despite being lined with acyl chains, has a favorable van der Waals interaction with intrapore water molecules. These results may help to explain why water-filled channels can be formed by the hydrophobic helices in natural channels.

Characterization of bacterial community dynamics in a full-scale drinking water treatment plant.

PubMed

Li, Cuiping; Ling, Fangqiong; Zhang, Minglu; Liu, Wen-Tso; Li, Yuxian; Liu, Wenjun

2017-01-01

Understanding the spatial and temporal dynamics of microbial communities in drinking water systems is vital to securing the microbial safety of drinking water. The objective of this study was to comprehensively characterize the dynamics of microbial biomass and bacterial communities at each step of a full-scale drinking water treatment plant in Beijing, China. Both bulk water and biofilm samples on granular activated carbon (GAC) were collected over 9months. The proportion of cultivable cells decreased during the treatment processes, and this proportion was higher in warm season than cool season, suggesting that treatment processes and water temperature probably had considerable impact on the R2A cultivability of total bacteria. 16s rRNA gene based 454 pyrosequencing analysis of the bacterial community revealed that Proteobacteria predominated in all samples. The GAC biofilm harbored a distinct population with a much higher relative abundance of Acidobacteria than water samples. Principle coordinate analysis and one-way analysis of similarity indicated that the dynamics of the microbial communities in bulk water and biofilm samples were better explained by the treatment processes rather than by sampling time, and distinctive changes of the microbial communities in water occurred after GAC filtration. Furthermore, 20 distinct OTUs contributing most to the dissimilarity among samples of different sampling locations and 6 persistent OTUs present in the entire treatment process flow were identified. Overall, our findings demonstrate the significant effects that treatment processes have on the microbial biomass and community fluctuation and provide implications for further targeted investigation on particular bacteria populations. Copyright © 2016. Published by Elsevier B.V.