Fluidic oscillator design for water removal enhancement in a PEM fuel cell

This research initiative was triggered by the problems of water management of Polymer Electrolyte Membrane Fuel Cell (PEMFC). In low temperature fuel cells such as PEMFC, some of the water produced after the chemical reaction remains in its liquid state. Excess water produced by the fuel cell must be removed from the system to avoid flooding of the gas diffusion layers (GDL). The GDL is responsible for the transport of reactant gas to the active sites and remove the water produced from the sites. If the GDL is flooded, the supply gas will not be able to reach the reactive sites and the fuel cell fails. The choice of water removal method in this research is to exert a variable asymmetrical force on a liquid droplet. As the drop of liquid is subjected to an external vibrational force in the form of periodic wave, it will begin to oscillate. A fluidic oscillator is capable to produce a pulsating flow using simple balance of momentum fluxes between three impinging jets. By connecting the outputs of the oscillator to the gas channels of a fuel cell, a flow pulsation can be imposed on a water droplet formed within the gas channel during fuel cell operation. The lowest frequency produced by this design is approximately 202 Hz when a 20 inches feed-back port length was used and a supply pressure of 5 psig was introduced. This information was found by setting up a fluidic network with appropriate data acquisition. The components include a fluidic amplifier, valves and fittings, flow meters, a pressure gage, NI-DAQ system, Siglab®, Matlab software and four PCB microphones. The operating environment of the water droplet was reviewed, speed of the sound pressure which travels down the square channel was precisely estimated, and measurement devices were carefully selected. Applicable alternative measurement devices and its application to pressure wave measurement was considered. Methods for experimental setup and possible approaches were recommended, with some discussion of potential problems with implementation of this technique. Some computational fluid dynamic was also performed as an approach to oscillator design.

Cladophora, mass transport, and the nearshore phosphorus shunt

Excessive Cladophora growth in the Great Lakes has led to beach fouling and the temporary closure of nuclear power plants and has been associated with avian botulism and the persistence of human pathogens. As the growth-limiting nutrient for Cladophora, phosphorus is the appropriate target for management efforts. Dreissenids (zebra and quagga mussels) have the ability to capture particulate phase phosphorus (otherwise unavailable to Cladophora) and release it in a soluble, available form. The significance of this potential nutrient source is, in part, influenced by the interplay between phosphorus flux from the mussel bed and turbulent mixing in establishing the phosphorus levels to which Cladophora is exposed. It is hypothesized that under quiescent conditions phosphorus will accumulate near the sediment-water interface, setting up vertical phosphorus gradients and favorable conditions for resource delivery to Cladophora. These gradients would be eliminated under conditions of wind mixing, reducing the significance of the dreissenid-mediated nutrient contribution. Soluble reactive phosphorus (SRP) levels were monitored over dreissenid beds (densities on the order of 350•m-2 and 3000∙m-2) at a site 8 m deep in Lake Michigan. Monitoring was based on the deployment of Modified Hesslein Samplers which collected samples for SRP analysis over a distance of 34 cm above the bottom in 2.5 cm intervals. Deployment intervals were established to capture a wind regime (calm, windy) that persisted for an interval consistent with the sampler equilibration time of 7 hours. Results indicate that increased mussel density leads to an increased concentration boundary layer; increased wind speed leads to entrainment of the concentration boundary layer; and increased duration of quiescent periods leads to an increased concentration boundary layer. This concentration boundary layer is of ecological significance and forms in the region inhabited by Cladophora

The effect of demand, tank parameters, and pumping stations on energy use in municipal drinking water distribution systems

Two of the indicators of the UN Millennium Development Goals ensuring environmental sustainability are energy use and per capita carbon dioxide emissions. The increasing urbanization and increasing world population may require increased energy use in order to transport enough safe drinking water to communities. In addition, the increase in water use would result in increased energy consumption, thereby resulting in increased green-house gas emissions that promote global climate change. The study of multiple Municipal Drinking Water Distribution Systems (MDWDSs) that relates various MDWDS aspects--system components and properties--to energy use is strongly desirable. The understanding of the relationship between system aspects and energy use aids in energy-efficient design. In this study, components of a MDWDS, and/or the characteristics associated with the component are termed as MDWDS aspects (hereafter--system aspects). There are many aspects of MDWDSs that affect the energy usage. Three system aspects (1) system-wide water demand, (2) storage tank parameters, and (3) pumping stations were analyzed in this study. The study involved seven MDWDSs to understand the relationship between the above-mentioned system aspects in relation with energy use. A MDWDSs model, EPANET 2.0, was utilized to analyze the seven systems. Six of the systems were real and one was a hypothetical system. The study presented here is unique in its statistical approach using seven municipal water distribution systems. The first system aspect studied was system-wide water demand. The analysis involved analyzing seven systems for the variation of water demand and its impact on energy use. To quantify the effects of water use reduction on energy use in a municipal water distribution system, the seven systems were modeled and the energy usage quantified for various amounts of water conservation. It was found that the effect of water conservation on energy use was linear for all seven systems and that all the average values of all the systems' energy use plotted on the same line with a high R 2 value. From this relationship, it can be ascertained that a 20% reduction in water demand results in approximately a 13% savings in energy use for all seven systems analyzed. This figure might hold true for many similar systems that are dominated by pumping and not gravity driven. The second system aspect analyzed was storage tank(s) parameters. Various tank parameters: (1) tank maximum water levels, (2) tank elevation, and (3) tank diameter were considered in this part of the study. MDWDSs use a significant amount of electrical energy for the pumping of water from low elevations (usually a source) to higher ones (usually storage tanks). The use of electrical energy has an effect on pollution emissions and, therefore, potential global climate change as well. Various values of these tank parameters were modeled on seven MDWDSs of various sizes using a network solver and the energy usage recorded. It was found that when averaged over all seven analyzed systems (1) the reduction of maximum tank water level by 50% results in a 2% energy reduction, (2) energy use for a change in tank elevation is system specific, and (2) a reduction of tank diameter of 50% results in approximately a 7% energy savings. The third system aspect analyzed in this study was pumping station parameters. A pumping station consists of one or more pumps. The seven systems were analyzed to understand the effect of the variation of pump horsepower and the number of booster stations on energy use. It was found that adding booster stations could save energy depending upon the system characteristics. For systems with flat topography, a single main pumping station was found to use less energy. In systems with a higher-elevation neighborhood, however, one or more booster pumps with a reduced main pumping station capacity used less energy. The energy savings for the seven systems was dependent on the number of boosters and ranged from 5% to 66% for the analyzed five systems with higher elevation neighborhoods (S3, S4, S5, S6, and S7). No energy savings was realized for the remaining two flat topography systems, S1, and S2. The present study analyzed and established the relationship between various system aspects and energy use in seven MDWDSs. This aids in estimating the amount of energy savings in MDWDSs. This energy savings would ultimately help reduce Greenhouse gases (GHGs) emissions including per capita CO 2 emissions thereby potentially lowering the global climate change effect. This will in turn contribute to meeting the MDG of ensuring environmental sustainability.

Water versus ice: The competing roles of modern climate and Pleistocene glacial erosion in the Central Alps of Switzerland

Recent studies have identified relationships between landscape form, erosion and climate in regions of landscape rejuvenation, associated with increased denudation. Most of these landscapes are located in non-glaciated mountain ranges and are characterized by transient geomorphic features. The landscapes of the Swiss Alps are likewise in a transient geomorphic state as seen by multiple knickzones. In this mountain belt, the transient state has been related to erosional effects during the Late Glacial Maximum (LGM). Here, we focus on the catchment scale and categorize hillslopes based on erosional mechanisms, landscape form and landcover. We then explore relationships of these variables to precipitation and extent of LGM glaciers to disentangle modern versus palaeo controls on the modern shape of the Alpine landscape. We find that in grasslands, the downslope flux of material mainly involves unconsolidated material through hillslope creep, testifying a transport-limited erosional regime. Alternatively, strength-limited hillslopes, where erosion is driven by bedrock failure, are covered by forests and/or expose bedrock, and they display oversteepened hillslopes and channels. There, hillslope gradients and relief are more closely correlated with LGM ice occurrence than with precipitation or the erodibility of the underlying bedrock. We relate the spatial occurrence of the transport- and strength-limited process domains to the erosive effects of LGM glaciers. In particular, strength-limited, rock dominated basins are situated above the equilibrium line altitude (ELA) of the LGM, reflecting the ability of glaciers to scour the landscape beyond threshold slope conditions. In contrast, transport-limited, soil-mantled landscapes are common below the ELA. Hillslopes covered by forests occupy the elevations around the ELA and are constrained by the tree line. We conclude that the current erosional forces at work in the Central Alps are still responding to LGM glaciation, and that the modern climate has not yet impacted on the modern landscape.

Solute transport in crystalline rocks at Äspö — I: Geological basis and model calibration

Water-conducting faults and fractures were studied in the granite-hosted A¨ spo¨ Hard Rock Laboratory (SE Sweden). On a scale of decametres and larger, steeply dipping faults dominate and contain a variety of different fault rocks (mylonites, cataclasites, fault gouges). On a smaller scale, somewhat less regular fracture patterns were found. Conceptual models of the fault and fracture geometries and of the properties of rock types adjacent to fractures were derived and used as input for the modelling of in situ dipole tracer tests that were conducted in the framework of the Tracer Retention Understanding Experiment (TRUE-1) on a scale of metres. After the identification of all relevant transport and retardation processes, blind predictions of the breakthroughs of conservative to moderately sorbing tracers were calculated and then compared with the experimental data. This paper provides the geological basis and model calibration, while the predictive and inverse modelling work is the topic of the companion paper [J. Contam. Hydrol. 61 (2003) 175]. The TRUE-1 experimental volume is highly fractured and contains the same types of fault rocks and alterations as on the decametric scale. The experimental flow field was modelled on the basis of a 2D-streamtube formalism with an underlying homogeneous and isotropic transmissivity field. Tracer transport was modelled using the dual porosity medium approach, which is linked to the flow model by the flow porosity. Given the substantial pumping rates in the extraction borehole, the transport domain has a maximum width of a few centimetres only. It is concluded that both the uncertainty with regard to the length of individual fractures and the detailed geometry of the network along the flowpath between injection and extraction boreholes are not critical because flow is largely one-dimensional, whether through a single fracture or a network. Process identification and model calibration were based on a single uranine breakthrough (test PDT3), which clearly showed that matrix diffusion had to be included in the model even over the short experimental time scales, evidenced by a characteristic shape of the trailing edge of the breakthrough curve. Using the geological information and therefore considering limited matrix diffusion into a thin fault gouge horizon resulted in a good fit to the experiment. On the other hand, fresh granite was found not to interact noticeably with the tracers over the time scales of the experiments. While fracture-filling gouge materials are very efficient in retarding tracers over short periods of time (hours–days), their volume is very small and, with time progressing, retardation will be dominated by altered wall rock and, finally, by fresh granite. In such rocks, both porosity (and therefore the effective diffusion coefficient) and sorption Kds are more than one order of magnitude smaller compared to fault gouge, thus indicating that long-term retardation is expected to occur but to be less pronounced.

Solute transport in crystalline rocks at Äspö — II: Blind predictions, inverse modelling and lessons learnt from test STT1

Based on the results from detailed structural and petrological characterisation and on up-scaled laboratory values for sorption and diffusion, blind predictions were made for the STT1 dipole tracer test performed in the Swedish A¨ spo¨ Hard Rock Laboratory. The tracers used were nonsorbing, such as uranine and tritiated water, weakly sorbing 22Na+, 85Sr2 +, 47Ca2 +and more strongly sorbing 86Rb+, 133Ba2 +, 137Cs+. Our model consists of two parts: (1) a flow part based on a 2D-streamtube formalism accounting for the natural background flow field and with an underlying homogeneous and isotropic transmissivity field and (2) a transport part in terms of the dual porosity medium approach which is linked to the flow part by the flow porosity. The calibration of the model was done using the data from one single uranine breakthrough (PDT3). The study clearly showed that matrix diffusion into a highly porous material, fault gouge, had to be included in our model evidenced by the characteristic shape of the breakthrough curve and in line with geological observations. After the disclosure of the measurements, it turned out that, in spite of the simplicity of our model, the prediction for the nonsorbing and weakly sorbing tracers was fairly good. The blind prediction for the more strongly sorbing tracers was in general less accurate. The reason for the good predictions is deemed to be the result of the choice of a model structure strongly based on geological observation. The breakthrough curves were inversely modelled to determine in situ values for the transport parameters and to draw consequences on the model structure applied. For good fits, only one additional fracture family in contact with cataclasite had to be taken into account, but no new transport mechanisms had to be invoked. The in situ values for the effective diffusion coefficient for fault gouge are a factor of 2–15 larger than the laboratory data. For cataclasite, both data sets have values comparable to laboratory data. The extracted Kd values for the weakly sorbing tracers are larger than Swedish laboratory data by a factor of 25–60, but agree within a factor of 3–5 for the more strongly sorbing nuclides. The reason for the inconsistency concerning Kds is the use of fresh granite in the laboratory studies, whereas tracers in the field experiments interact only with fracture fault gouge and to a lesser extent with cataclasite both being mineralogically very different (e.g. clay-bearing) from the intact wall rock.

Transport of volatile chlorinated hydrocarbons in unsaturated aggregated media

Transport of volatile hydrocarbons in soils is largely controlled by interactions of vapours with the liquid and solid phase. Sorption on solids of gaseous or dissolved comPounds may be important. Since the contact time between a chemical and a specific sorption site can be rather short, kinetic or mass-transfer resistance effects may be relevant. An existing mathematical model describing advection and diffusion in the gas phase and diffusional transport from the gaseous phase into an intra-aggregate water phase is modified to include linear kinetic sorption on ps-solid and water-solid interfaces. The model accounts for kinetic mass transfer between all three phases in a soil. The solution of the Laplace-transformed equations is inverted numerically. We performed transient column experiments with 1,1,2-Trichloroethane, Trichloroethylene, and Tetrachloroethylene using air-dry solid and water-saturated porous glass beads. The breakthrough curves were calculated based on independently estimated parameters. The model calculations agree well with experimental data. The different transport behaviour of the three compounds in our system primarily depends on Henry's constants.

Transport of 234U in the Opalinus Clay on centimetre to decimetre scales

The Opalinus Clay formation in North Switzerland is a potential host rock for a deep underground radioactive waste repository. The distribution of U-238, U-234 and Th-230 was studied in rock samples of the Opalinus Clay from an exploratory borehole at Benken (Canton of Zurich) using MC-ICP-MS. The aim of U-234 was to assess the in situ, long-term migration behaviour in this rock. Very low hydraulic conductivities of the Opalinus Clay, reducing potential of the pore water and its chemical equilibrium with the host rock are expected to render both U-238 and Th-230 immobile. If U is heterogeneously distributed in the Opalinus Clay, gradients in the supply of U-234 from the rock matrix to the pore water by the decay of U-238 will be established. Diffusive redistribution separates U-234 from its immobile parent U-238 resulting in bulk rock U-234/U-238 activity disequilibria. These may provide a means of estimating the mobility of U-234 in the rock if the diffusion rate of U-234 is significant compared to its decay rate. Sampling was carried out on two scales. Drilling of cm-spaced samples from the drill-core was done to study mobility over short distances and elucidate possible small-scale lithological control. Homogenized 25-cm-long portions of a 2-m-long drill-core section were prepared to provide information on transport over a longer distance. Variations in U and/or Th content on the cm-scale between clays and carbonate-sandy layers are revealed by beta-scanning, which shows that the (dominant) clay is richer in both elements. Samples were digested using aqua regia followed by total HF dissolution, yielding two fractions. in all studied samples U was found to be concentrated in the HF digestion fraction. It has a high U/Th ratio and a study by SEM-EDS points to sub-mu m up to several mu m in size zircon grains as the main U-rich phase. This fraction consistently has U-234/U-238 activity ratios below unity. The minute zircon grains constitute the major reservoir of U in the rock and act as constant rate suppliers of U-234 into the rock matrix and the pore water. The aqua regia leach fraction was found to be enriched in Th, and complementary to the HF fraction, having U-234/U-238 activity ratios above unity. It is believed that these U activity ratios reflect the surplus of having U-234 delivered from the zircon grains. Some cm-spaced samples show bulk rock U-234/U-238 activity ratios that are markedly out of equilibrium. In most of them a striking negative correlation between the total U content and the bulk rock U-234/U-238 activity ratios is observed. This is interpreted to indicate net U-234 transfer from regions of higher supply of U-234 towards those of lower supply which is, in most cases, equivalent to transfer from clayey towards carbonate/sandy portions of the rock. In contrast, the 25 cm averaged samples all have uniform bulk rock U-234/U-238 activity ratios in equilibrium, indicating U immobility in the last 1-1.5 Ma on this spatial scale. It is concluded that the small-scale lithological variations which govern U spatial distribution in the Opalinus Clay are the major factor determining U-234 in situ supply rates, regulating its diffusive fluxes and controlling the observed bulk rock U-234/U-238 activity ratios. A simple box-model is presented to simulate the measured bulk rock U-234/U-238 activity ratios and to give an additional insight into the studied system. (C) 2008 Elsevier Ltd. All rights reserved.

MODELING REACTIVE GAS UPTAKE, TRANSPORT, AND TRANSFORMATION IN AGGREGATED SOILS

Gas diffusion research in soils covers, to a large extent, the transport behavior of practically insoluble gases. We extend the mathematical description of gas transport to include reactive gaseous components that hydrolyze in water such as SO2 and CO2. The path between the free atmosphere and the microporous niches is modeled by assuming penetration through gas-filled macropores, air-water phase transfer, and diffusion and speciation in the liquid phase. For hydrolyzable gases, the rate of mass transfer into and the total absorption capacity of the soil solution may be high. Both the capacity and the transfer rate are influenced by the soil-solution pH; for high pH, they become extremely high for SO2. The soil absorption of such gases is also influenced by soil structure. Well-aerated, near-neutral soils are a potentially important sink for SO2.

Multi-scale micro-structure generation strategy for up-scaling transport in clays

Clays and claystones are used as backfill and barrier materials in the design of waste repositories, because they act as hydraulic barriers and retain contaminants. Transport through such barriers occurs mainly by molecular diffusion. There is thus an interest to relate the diffusion properties of clays to their structural properties. In previous work, we have developed a concept for up-scaling pore-scale molecular diffusion coefficients using a grid-based model for the sample pore structure. Here we present an operational algorithm which can generate such model pore structures of polymineral materials. The obtained pore maps match the rock’s mineralogical components and its macroscopic properties such as porosity, grain and pore size distributions. Representative ensembles of grains in 2D or 3D are created by a lattice Monte Carlo (MC) method, which minimizes the interfacial energy of grains starting from an initial grain distribution. Pores are generated at grain boundaries and/or within grains. The method is general and allows to generate anisotropic structures with grains of approximately predetermined shapes, or with mixtures of different grain types. A specific focus of this study was on the simulation of clay-like materials. The generated clay pore maps were then used to derive upscaled effective diffusion coefficients for non-sorbing tracers using a homogenization technique. The large number of generated maps allowed to check the relations between micro-structural features of clays and their effective transport parameters, as is required to explain and extrapolate experimental diffusion results. As examples, we present a set of 2D and 3D simulations and investigated the effects of nanopores within particles (interlayer pores) and micropores between particles. Archie’s simple power law is followed in systems with only micropores. When nanopores are present, additional parameters are required; the data reveal that effective diffusion coefficients could be described by a sum of two power functions, related to the micro- and nanoporosity. We further used the model to investigate the relationships between particle orientation and effective transport properties of the sample.

Combined effect of heterogeneity, anisotropy and saturation on steady state flow and transport: Structure recognition and numerical simulation

1 Natural soil profiles may be interpreted as an arrangement of parts which are characterized by properties like hydraulic conductivity and water retention function. These parts form a complicated structure. Characterizing the soil structure is fundamental in subsurface hydrology because it has a crucial influence on flow and transport and defines the patterns of many ecological processes. We applied an image analysis method for recognition and classification of visual soil attributes in order to model flow and transport through a man-made soil profile. Modeled and measured saturation-dependent effective parameters were compared. We found that characterizing and describing conductivity patterns in soils with sharp conductivity contrasts is feasible. Differently, solving flow and transport on the basis of these conductivity maps is difficult and, in general, requires special care for representation of small-scale processes.

Combined effects of heterogeneity, anisotropy, and saturation on steady state flow and transport: A laboratory sand tank experiment

Field soils show rather different spreading behavior at different water saturations, frequently caused by layering of the soil material. We performed tracer experiments in a laboratory sand tank. Such experiments complement and help comprehension of field investigations. We estimated, by image analysis, the first two moments of small plumes traveling through a two-dimensional, heterogeneous medium with strongly anisotropic correlation structure. Three steady state regimes were analyzed. Two main conclusions were drawn. First, low saturation led to very large heterogeneity and to strong preferential flow. Thus the description of the flow paths and the prediction of the solute arrival times require, in this case, more accurate knowledge about the topological structure. Second, saturation-dependent macroscopic anisotropy is an essential element of transport in unsaturated media. For this reason, small structural soil features should be properly upscaled to give appropriate effective soil parameters to be input in transport models.

Reconstruction of a flash flood with large wood transport and its influence on hazard patterns in an ungauged mountain basin

The reconstruction of past flash floods in ungauged basins leads to a high level of uncertainty, which increases if other processes are involved such as the transport of large wood material. An important flash flood occurred in 1997 in Venero Claro (Central Spain), causing significant economic losses. The wood material clogged bridge sections, raising the water level upstream. The aim of this study was to reconstruct this event, analysing the influence of woody debris transport on the flood hazard pattern. Because the reach in question was affected by backwater effects due to bridge clogging, using only high water mark or palaeostage indicators may overestimate discharges, and so other methods are required to estimate peak flows. Therefore, the peak discharge was estimated (123 ± 18 m3 s–1) using indirect methods, but one-dimensional hydraulic simulation was also used to validate these indirect estimates through an iterative process (127 ± 33 m3 s–1) and reconstruct the bridge obstruction to obtain the blockage ratio during the 1997 event (~48%) and the bridge clogging curves. Rainfall–Runoff modelling with stochastic simulation of different rainfall field configurations also helped to confirm that a peak discharge greater than 150 m3 s–1 is very unlikely to occur and that the estimated discharge range is consistent with the estimated rainfall amount (233 ± 27 mm). It was observed that the backwater effect due to the obstruction (water level ~7 m) made the 1997 flood (~35-year return period) equivalent to the 50-year flood. This allowed the equivalent return period to be defined as the recurrence interval of an event of specified magnitude, which, where large woody debris is present, is equivalent in water depth and extent of flooded area to a more extreme event of greater magnitude. These results highlight the need to include obstruction phenomena in flood hazard analysis.

Water-soluble fullerene (C60) derivatives as nonviral gene-delivery vectors.

A new class of water-soluble C60 transfecting agents has been prepared using Hirsch-Bingel chemistry and assessed for their ability to act as gene-delivery vectors in vitro. In an effort to elucidate the relationship between the hydrophobicity of the fullerene core, the hydrophilicity of the water-solubilizing groups, and the overall charge state of the C60 vectors in gene delivery and expression, several different C60 derivatives were synthesized to yield either positively charged, negatively charged, or neutral chemical functionalities under physiological conditions. These fullerene derivatives were then tested for their ability to transfect cells grown in culture with DNA carrying the green fluorescent protein (GFP) reporter gene. Statistically significant expression of GFP was observed for all forms of the C60 derivatives when used as DNA vectors and compared to the ability of naked DNA alone to transfect cells. However, efficient in vitro transfection was only achieved with the two positively charged C60 derivatives, namely, an octa-amino derivatized C60 and a dodeca-amino derivatized C60 vector. All C60 vectors showed an increase in toxicity in a dose-dependent manner. Increased levels of cellular toxicity were observed for positively charged C60 vectors relative to the negatively charged and neutral vectors. Structural analyses using dynamic light scattering and optical microscopy offered further insights into possible correlations between the various derivatized C60 compounds, the C60 vector/DNA complexes, their physical attributes (aggregation, charge) and their transfection efficiencies. Recently, similar Gd@C60-based compounds have demonstrated potential as advanced contrast agents for magnetic resonance imaging (MRI). Thus, the successful demonstration of intracellular DNA uptake, intracellular transport, and gene expression from DNA using C60 vectors suggests the possibility of developing analogous Gd@C60-based vectors to serve simultaneously as both therapeutic and diagnostic agents.