Aquatic passive sampling of herbicides on naked particle loaded membranes: Accelerated measurement and empirical estimation of kinetic parameters

Water-sampler equilibrium partitioning coefficients and aqueous boundary layer mass transfer coefficients for atrazine, diuron, hexazionone and fluometuron onto C18 and SDB-RPS Empore disk-based aquatic passive samplers have been determined experimentally under a laminar flow regime (Re = 5400). The method involved accelerating the time to equilibrium of the samplers by exposing them to three water concentrations, decreasing stepwise to 50% and then 25% of the original concentration. Assuming first-order Fickian kinetics across a rate-limiting aqueous boundary layer, both parameters are determined computationally by unconstrained nonlinear optimization. In addition, a method of estimation of mass transfer coefficients-therefore sampling rates-using the dimensionless Sherwood correlation developed for laminar flow over a flat plate is applied. For each of the herbicides, this correlation is validated to within 40% of the experimental data. The study demonstrates that for trace concentrations (sub 0.1 mu g/L) and these flow conditions, a naked Empore disk performs well as an integrative sampler over short deployments (up to 7 days) for the range of polar herbicides investigated. The SDB-RPS disk allows a longer integrative period than the C18 disk due to its higher sorbent mass and/or its more polar sorbent chemistry. This work also suggests that for certain passive sampler designs, empirical estimation of sampling rates may be possible using correlations that have been available in the chemical engineering literature for some time.

Hydraulics of skimming flows on stepped chutes: The effects of inflow conditions?

Modern stepped spillways are typically designed for large discharge capacities corresponding to a skimming flow regime for which flow resistance is predominantly form drag. The writer demonstrates that the inflow conditions have some effect on the skimming flow properties. Boundary layer calculations show that the flow properties at inception of free-surface aeration are substantially different with pressurized intake. The re-analysis of experimental results highlights that the equivalent Darcy friction factor is f similar to 0.2 in average on uncontrolled stepped Chute and f similar to 0.1 on stepped chute with pressurized intake. A simple design chart is presented to estimate the residual flow velocity, and the agreement of the calculations with experimental results is deemed satisfactory for preliminary design.

Field observations of instantaneous water slopes and horizontal pressure gradients in the swash-zone

Field observations of instantaneous water surface slopes in the swash zone are presented. For free-surface flows with a hydrostatic pressure distribution the surface slope is equivalent to the horizontal pressure gradient. Observations were made using a novel technique which in its simplest form consists of a horizontal stringline extending seaward from the beach face. Visual observation, still photography or video photography is then sufficient to determine the surface slope where the free-surface cuts the line or between reference points in the image. The method resolves the mean surface gradient over a cross-shore distance of 5 m or more to within +/- 0.001, or 1/20th -1/100th of typical beach gradients. In addition, at selected points and at any instant in time during the swash cycle, the water surface slope can be determined exactly to be dipping either seaward or landward. Close to the location of bore collapse landward dipping water surface slopes of order 0.05-0.1 occur over a very small region (order 0.5 m) at the blunt or convex leading edge of the swash. In the middle and upper swash the water surface slope at this leading edge is usually very close to horizontal or slightly seaward. Behind the leading edge, the water surface slope was observed to be very close to horizontal or dipping seaward at all times throughout the swash uprush. During the backwash the water surface slope was observed to be always dipping seaward, approaching the beach slope, and remained seaward until a new uprush edge or incident bore passed any particular cross-shore location of interest. The observations strongly Suggest that the swash boundary layer is subject to an adverse pressure gradient during uprush and a favourable pressure gradient during the backwash. Furthermore, assuming Euler's equations are a good approximation in the swash, the observations also show that the total fluid acceleration is negative (offshore) for almost the whole of the uprush and for the entire backwash. The observations are contrary to recent work suggesting significant shoreward directed accelerations and pressure gradients occur in the swash (i.e., delta u/delta t > 0 similar to delta p/delta x < 0), but consistent with analytical and numerical solutions for swash uprush and backwash. The results have important implications for sediment transport modelling in the swash zone.

Anisotropy model for mantle convection

The paper presents a new theory for modeling flow in anisotropic, viscous rock. This theory has originally been developed for the simulation of large deformation processes including folding and kinking in multi-layered visco-elastic rock. The orientation of slip planes in the context of crystallographic slip is determined by the normal vector, the so-called director of these surfaces. The model is applied to simulate anisotropic natural mantle convection. We compare the evolution of the director and approximately steady states of isotropic and anisotropic convection. The isotropic case has a simple steady state solution, whereas the orthotropic convection model produces a continuously evolving patterning in tile core of the convection cell which makes only a near-steady condition possible, in which the thermal boundary layer appears to be well aligned with the flow and hence as observed in seismic tomomgraphy strong anistropic.

Exploration of a simple, low cost, micro gas turbine recuperator solution for a domestic combined heat and power unit

For micro gas turbines (MGT) of around 1 kW or less, a commercially suitable recuperator must be used to produce a thermal efficiency suitable for use in UK Domestic Combined Heat and Power (DCHP). This paper uses computational fluid dynamics (CFD) to investigate a recuperator design based on a helically coiled pipe-in-pipe heat exchanger which utilises industry standard stock materials and manufacturing techniques. A suitable mesh strategy was established by geometrically modelling separate boundary layer volumes to satisfy y + near wall conditions. A higher mesh density was then used to resolve the core flow. A coiled pipe-in-pipe recuperator solution for a 1 kW MGT DCHP unit was established within the volume envelope suitable for a domestic wall-hung boiler. Using a low MGT pressure ratio (necessitated by using a turbocharger oil cooled journal bearing platform) meant unit size was larger than anticipated. Raising MGT pressure ratio from 2.15 to 2.5 could significantly reduce recuperator volume. Dimensional reasoning confirmed the existence of optimum pipe diameter combinations for minimum pressure drop. Maximum heat exchanger effectiveness was achieved using an optimum or minimum pressure drop pipe combination with large pipe length as opposed to a large pressure drop pipe combination with shorter pipe length. © 2011 Elsevier Ltd. All rights reserved.

Numerical solution of the Dirichlet initial boundary value problem for the heat equation in exterior 3-dimensional domains using integral equations

A numerical method for the Dirichlet initial boundary value problem for the heat equation in the exterior and unbounded region of a smooth closed simply connected 3-dimensional domain is proposed and investigated. This method is based on a combination of a Laguerre transformation with respect to the time variable and an integral equation approach in the spatial variables. Using the Laguerre transformation in time reduces the parabolic problem to a sequence of stationary elliptic problems which are solved by a boundary layer approach giving a sequence of boundary integral equations of the first kind to solve. Under the assumption that the boundary surface of the solution domain has a one-to-one mapping onto the unit sphere, these integral equations are transformed and rewritten over this sphere. The numerical discretisation and solution are obtained by a discrete projection method involving spherical harmonic functions. Numerical results are included.

Development of effective approaches to the large-scale aerodynamic testing of low-rise buildings

Low-rise buildings are often subjected to high wind loads during hurricanes that lead to severe damage and cause water intrusion. It is therefore important to estimate accurate wind pressures for design purposes to reduce losses. Wind loads on low-rise buildings can differ significantly depending upon the laboratory in which they were measured. The differences are due in large part to inadequate simulations of the low-frequency content of atmospheric velocity fluctuations in the laboratory and to the small scale of the models used for the measurements. A new partial turbulence simulation methodology was developed for simulating the effect of low-frequency flow fluctuations on low-rise buildings more effectively from the point of view of testing accuracy and repeatability than is currently the case. The methodology was validated by comparing aerodynamic pressure data for building models obtained in the open-jet 12-Fan Wall of Wind (WOW) facility against their counterparts in a boundary-layer wind tunnel. Field measurements of pressures on Texas Tech University building and Silsoe building were also used for validation purposes. The tests in partial simulation are freed of integral length scale constraints, meaning that model length scales in such testing are only limited by blockage considerations. Thus the partial simulation methodology can be used to produce aerodynamic data for low-rise buildings by using large-scale models in wind tunnels and WOW-like facilities. This is a major advantage, because large-scale models allow for accurate modeling of architectural details, testing at higher Reynolds number, using greater spatial resolution of the pressure taps in high pressure zones, and assessing the performance of aerodynamic devices to reduce wind effects. The technique eliminates a major cause of discrepancies among measurements conducted in different laboratories and can help to standardize flow simulations for testing residential homes as well as significantly improving testing accuracy and repeatability. Partial turbulence simulation was used in the WOW to determine the performance of discontinuous perforated parapets in mitigating roof pressures. The comparisons of pressures with and without parapets showed significant reductions in pressure coefficients in the zones with high suctions. This demonstrated the potential of such aerodynamic add-on devices to reduce uplift forces.

Observation of manganese nodules and crusts recovered during the CHAIN 115 cruise from Nov 1973 until June 1974 in the Atlantic Ocean

Investigations of piston cores from the Vema Channel and lower flanks of the Rio Grande Rise suggest the presence of episodic flow of deep and bottom water during the Late Pleistocene. Cores from below the present-day foraminiferal lysocline (at ~4000 m) contain an incomplete depositional record consisting of Mn nodules and encrustations, hemipelagic clay, displaced high-latitude diatoms, and poorly preserved heterogeneous microfossil assemblages. Cores from the depth range between 2900 m and 4000 m contain an essentially complete Late Pleistocene record, and consist of well-defined carbonate dissolution cycles with periodicities of ~100,000 years. Low carbonate content and increased dissolution correspond to glacial episodes, as interpreted by oxygen isotopic analysis of bulk foraminiferal assemblages. The absence of diagnostic high-latitude indicators (Antarctic diatoms) within the dissolution cyclss, however, suggests that AABW may not have extended to significantly shallower elevations on the lower flanks of the Rio Grande Rise during the Late Pleistocene. Therefore episodic AABW flow may not necessarily be the mechanism responsible for producing these cyclic events. This interpretation is also supported by the presence of an apparently complete Brunhes depositional record in the same cores, suggesting current velocities insufficient for significant erosion. Fluctuations in the properties and flow characteristics of another water mass, such as NADW, may be involved. The geologic evidence in core-top samples near the present-day AABW/NADW transition zone is consistent with either of two possible interpretations of the upper limit of AABW on the east flank of the channel. The foraminiferal lysocline, at ~4000 m, is near the top of the benthic thermocline and nepheloid layer, and may therefore correspond to the upper limit of relatively corrosive AABW. On the other hand, the carbonate compensation depth (CDD) at ~4250 m, which corresponds to the maximum gradient in the benthic thermocline, is characterized by rapid deposition of relatively fine-grained sediment. Such a zone of convergence and preferential sediment accumulation would be expected near the level of no motion in the AABW/NADW transition zone as a consequence of Ekman-layer veering of the mean velocity vector in the bottom boundary layer. It is possible that both of these interpretations are in part correct. The "level of no motion'' may in fact correspond to the CCD, while at the same time relatively corrosive water of Antarctic origin may mix with overlying NADW and therefore elevate the foraminifera] lysocline to depths above the level of no motion. Closely spaced observations of the hydrography and flow characteristics within the benthic thermocline will be required in order to use sediment parameters as more precise indicators of paleo-circulation.

Critical bed shear stress and threshold of motion of maërl biogenic gravel

Critical bed shear stress for incipient motion has been determined for biogenic free-living coralline algae known as maërl. Maërl from three different sedimentary environments (beach, intertidal, and open marine) in Galway Bay, west of Ireland have been analysed in a rotating annular flume and linear flume. Velocity profile measurements of the benthic boundary layer, using an Acoustic Doppler Velocimeter, have been obtained in four different velocity experiments. The bed shear stress has been determined using three methods: Law of the Wall, Turbulent Kinetic Energy and Reynolds Stress. The critical Shields parameter has been estimated as a non-dimensional mobility number and the results have been compared with the Shields curve for natural sand. Maërl particles fall below this curve because its greater angularity allows grains to be mobilised easier than hydraulically equivalent particles. From previous work, the relationship between grain shape and the settling velocity of maërl suggests that the roughness is greatest for intertidal maërl particles. During critical shear stress determinations, beds of such rough particles exhibited the greatest critical shear stress probably because the particle thalli interlocked and resisted entrainment. The Turbulent Kinetic Energy methodology gives the most consistent results, agreeing with previous comparative studies. Rarely-documented maërl megaripples were observed in the rotating annular flume and are hypothesised to form at velocities ~10 cm s-1 higher than the critical threshold velocity, where tidal currents, oscillatory flow or combined-wave current interaction results in the preferential transport of maërl. A determination of the critical bed shear stress of maërl allows its mobility and rate of erosion and deposition to be evaluated spatially in subsequent applications to biological conservation management.

Investigation expérimentale du décollement dans l’aspirateur d’une turbine bulbe

La présente thèse propose une étude expérimentale du décollement dans le diffuseur d’un modèle de turbine hydroélectrique bulbe. Le décollement se produit quand la turbine est opérée à forte charge et il réduit la section effective de récupération du diffuseur. La diminution de la performance du diffuseur à forte charge engendre une baisse brusque de l’efficacité de la turbine et de la puissance extraite. Le modèle réduit de bulbe est fidèle aux machines modernes avec un diffuseur particulièrement divergent. Les performances de la turbine sont mesurées sur une large gamme de points d’opération pour déterminer les conditions les plus intéressantes pour l’étude du décollement et pour étudier la distribution paramétrique de ce phénomène. La pression est mesurée le long de l’aspirateur par des capteurs dynamiques affleurants alors que les champs de vitesse dans la zone de décollement sont mesurés avec une méthode PIV à deux composantes. Les observations à la paroi sont pour leur part faites à l’aide de brins de laine. Pour un débit suffisant, le gradient de pression adverse induit par la géométrie du diffuseur affaiblit suffisamment la couche limite, entraînant ainsi l’éjection de fluide de la paroi le long d’une large enveloppe tridimensionelle. Le décollement instationnaire tridimensionnel se situe dans la même zone du diffuseur indépendamment du point d’opération. L’augmentation du débit provoque à la fois une extension de la zone de décollement et une augmentation de l’occurrence de ses manifestations. La position et la forme du front de décollement fluctue significativement sans périodicité. L’analyse topologique et celle des tourbillons des champs de vitesse instantanés montrent une topologie du front de décollement complexe qui diffère beaucoup d’une réalisation à l’autre. Bien que l’écoulement soit turbulent, les tourbillons associés aux foyers du front sont clairement plus gros et plus intenses que ceux de la turbulence. Cela suggère que le mécanisme d’enroulement menant aux tourbillons du décollement est clairement distinct des mécanismes de la turbulence.

Effect of boiling on deposition of metallic colloids

In this study the relationship between heterogeneous nucleate boiling surfaces and deposition of suspended metallic colloidal particles, popularly known as crud or corrosion products in process industries, on those heterogeneous sites is investigated. Various researchers have reported that hematite is a major constituent of crud which makes it the primary material of interest; however the models developed in this work are irrespective of material choice. Qualitative hypotheses on the deposition process under boiling as proposed by previous researchers have been tested, which fail to provide explanations for several physical mechanisms observed and analyzed. In this study a quantitative model of deposition rate has been developed on the basis of bubble dynamics and colloid-surface interaction potential. Boiling from a heating surface aids in aggregation of the metallic particulates viz. nano-particles, crud particulate, etc. suspended in a liquid, which helps in transporting them to heating surfaces. Consequently, clusters of particles deposit onto the heating surfaces due to various interactive forces, resulting in formation of porous or impervious layers. The deposit layer grows or recedes depending upon variations in interparticle and surface forces, fluid shear, fluid chemistry, etc. This deposit layer in turn affects the rate of bubble generation, formation of porous chimneys, critical heat flux (CHF) of surfaces, activation and deactivation of nucleation sites on the heating surfaces. Several problems are posed due to the effect of boiling on colloidal deposition, which range from research initiatives involving nano-fluids as a heat transfer medium to industrial applications such as light water nuclear reactors. In this study, it is attempted to integrate colloid and surface science with vapor bubble dynamics, boiling heat transfer and evaporation rate. Pool boiling experiments with dilute metallic colloids have been conducted to investigate several parameters impacting the system. The experimental data available in the literature is obtained by flow experiments, which do not help in correlating boiling mechanism with the deposition amount or structure. With the help of experimental evidences and analysis, previously proposed hypothesis for particle transport to the contact line due to hydrophobicity has been challenged. The experimental observations suggest that deposition occurs around the bubble surface contact line and extends underneath area of the bubble microlayer as well. During the evaporation the concentration gradient of a non-volatile species is created, which induces osmotic pressure. The osmotic pressure developed inside the microlayer draws more particles inside the microlayer region or towards contact line. The colloidal escape time is slower than the evaporation time, which leads to the aggregation of particles in the evaporating micro-layer. These aggregated particles deposit onto or are removed from the heating surface, depending upon their total interaction potential. Interaction potential has been computed with the help of surface charge and van der Waals potential for the materials in aqueous solutions. Based upon the interaction-force boundary layer thickness, which is governed by debye radius (or ionic concentration and pH), a simplified quantitative model for the attachment kinetics is proposed. This attachment kinetics model gives reasonable results in predicting attachment rate against data reported by previous researchers. The attachment kinetics study has been done for different pH levels and particle sizes for hematite particles. Quantification of colloidal transport under boiling scenarios is done with the help of overall average evaporation rates because generally waiting times for bubbles at the same position is much larger than growth times. In other words, from a larger measurable scale perspective, frequency of bubbles dictates the rate of collection of particles rather than evaporation rate during micro-layer evaporation of one bubble. The combination of attachment kinetics and colloidal transport kinetics has been used to make a consolidated model for prediction of the amount of deposition and is validated with the help of high fidelity experimental data. In an attempt to understand and explain boiling characteristics, high speed visualization of bubble dynamics from a single artificial large cavity and multiple naturally occurring cavities is conducted. A bubble growth and departure dynamics model is developed for artificial active sites and is validated with the experimental data. The variation of bubble departure diameter with wall temperature is analyzed with experimental results and shows coherence with earlier studies. However, deposit traces after boiling experiments show that bubble contact diameter is essential to predict bubble departure dynamics, which has been ignored previously by various researchers. The relationship between porosity of colloid deposits and bubbles under the influence of Jakob number, sub-cooling and particle size has been developed. This also can be further utilized in variational wettability of the surface. Designing porous surfaces can having vast range of applications varying from high wettability, such as high critical heat flux boilers, to low wettability, such as efficient condensers.

Simulations of droplet dispersion in the wakes of cylinders and icing tunnel spray bars

Simulations of droplet dispersion behind cylinder wakes and downstream of icing tunnel spray bars were conducted. In both cases, a range of droplet sizes were investigated numerically with a Lagrangian particle trajectory approach while the turbulent air flow was investigated with a hybrid Reynolds-Averaged Navier-Stokes/Large-Eddy Simulations approach scheme. In the first study, droplets were injected downstream of a cylinder at sub-critical conditions (i.e. with laminar boundary layer separation). A stochastic continuous random walk (CRW) turbulence model was used to capture the effects of sub-grid turbulence. Small inertia droplets (characterized by small Stokes numbers) were affected by both the large-scale and small-scale vortex structures and closely followed the air flow, while exhibiting a dispersion consistent with that of a scalar flow field. Droplets with intermediate Stokes numbers were centrifuged by the vortices to the outer edges of the wake, yielding an increased dispersion. Large Stokes number droplets were found to be less responsive to the vortex structures and exhibited the least dispersion. Particle concentration was also correlated with vorticity distribution which yielded preferential bias effects as a function of different particle sizes. This trend was qualitatively similar to results seen in homogenous isotropic turbulence, though the influence of particle inertia was less pronounced for the cylinder wake case. A similar study was completed for droplet dispersion within the Icing Research Tunnel (IRT) at the NASA Glenn Research Center, where it is important to obtain a nearly uniform liquid water content (LWC) distribution in the test section (to recreate atmospheric icing conditions).. For this goal, droplets are diffused by the mean and turbulent flow generated from the nozzle air jets, from the upstream spray bars, and from the vertical strut wakes. To understand the influence of these three components, a set of simulations was conducted with a sequential inclusion of these components. Firstly, a jet in an otherwise quiescent airflow was simulated to capture the impact of the air jet on flow turbulence and droplet distribution, and the predictions compared well with experimental results. The effects of the spray bar wake and vertical strut wake were then included with two more simulation conditions, for which it was found that the air jets were the primary driving force for droplet dispersion, i.e. that the spray bar and vertical strut wake effects were secondary.

The study of the sedimentation mechanism in channels under the impact of tidal currents

The purpose of this research is to study sedimentation mechanism by mathematical modeling in access channels which are affected by tidal currents. The most important factor for recognizing sedimentation process in every water environment is the flow pattern of that environment. It is noteworthy that the flow pattern is affected by the geometry and the shape of the environment as well as the type of existing affects in area. The area under the study in this thesis is located in Bushehr Gulf and the access channels (inner and outer). The study utilizes the hydrodynamic modeling with unstructured triangular and non-overlapping grids, using the finite volume, From method analysis in two scale sizes: large scale (200 m to 7.5km) and small scale (50m to 7.5km) in two different time durations of 15 days and 3.5 days to obtain the flow patterns. The 2D governing equations used in the model are the Depth-Averaged Shallow Water Equations. Turbulence Modeling is required to calculate the Eddy Viscosity Coefficient using the Smagorinsky Model with coefficient of 0.3. In addition to the flow modeling in two different scales and the use of the data of 3.5 day tidal current modeling have been considered to study the effects of the sediments equilibrium in the area and the channels. This model is capable of covering the area which is being settled and eroded and to identify the effects of tidal current of these processes. The required data of the above mentioned models such as current and sediments data have been obtained by the measurements in Bushehr Gulf and the access channels which was one of the PSO's (Port and Shipping Organization) project-titled, "The Sedimentation Modeling in Bushehr Port" in 1379. Hydrographic data have been obtained from Admiralty maps (2003) and Cartography Organization (1378, 1379). The results of the modeling includes: cross shore currents in northern and north western coasts of Bushehr Gulf during the neap tide and also the same current in northern and north eastern coasts of the Gulf during the spring tide. These currents wash and carry fine particles (silt, clay, and mud) from the coastal bed of which are generally made of mud and clay with some silts. In this regard, the role of sediments in the islands of this area and the islands made of depot of dredged sediments should not be ignored. The result of using 3.5 day modeling is that the cross channels currents leads to settlement places in inner and outer channels in tidal period. In neap tide the current enters the channel from upside bend of the two channels and outer channel. Then it crosses the channel oblique in some places of the outer channel. Also the oblique currents or even almost perpendicular current from up slope of inner channel between No. 15 and No. 18 buoys interact between the parallel currents in the channel and made secondary oblique currents which exit as a down-slope current in the channel and causes deposit of sediments as well as settling the suspended sediments carried by these currents. In addition in outer channel the speed of parallel currents in the bend of the channel which is naturally deeper increases. Therefore, it leads to erosion and suspension of sediments in this area. The speed of suspended sediments carried by this current which is parallel to the channel axis decreases when they pass through the shallower part of the channel where it is in the buoys No.7 and 8 to 5 and 6 are located. Therefore, the suspended sediment settles and because of this process these places will be even shallower. Furthermore, the passing of oblique upstream leads to settlement of the sediments in the up-slope and has an additional effect on the process of decreasing the depth of these locations. On the contrary, in the down-slope channel, as the results of sediments and current modeling indicates the speed of current increases and the currents make the particles of down-slope channel suspended and be carried away. Thus, in a vast area of downstream of both channels, the sediments have settled. At the end of the neap tide, the process along with circulations in this area produces eddies which causes sedimentation in the area. During spring some parts of this active location for sedimentation will enter both channels in a reverse process. The above mentioned processes and the places of sedimentation and erosion in inner and outer channels are validated by the sediments equilibrium modeling. This model will be able to estimate the suspended, bed load and the boundary layer thickness in each point of both channels and in the modeled area.

Development of measurement and modeling techniques to quantify atmospheric deposition of persistent, bioaccumulative and toxic chemicals in the Great Lakes

Measurement and modeling techniques were developed to improve over-water gaseous air-water exchange measurements for persistent bioaccumulative and toxic chemicals (PBTs). Analytical methods were applied to atmospheric measurements of hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Additionally, the sampling and analytical methods are well suited to study semivolatile organic compounds (SOCs) in air with applications related to secondary organic aerosol formation, urban, and indoor air quality. A novel gas-phase cleanup method is described for use with thermal desorption methods for analysis of atmospheric SOCs using multicapillary denuders. The cleanup selectively removed hydrogen-bonding chemicals from samples, including much of the background matrix of oxidized organic compounds in ambient air, and thereby improved precision and method detection limits for nonpolar analytes. A model is presented that predicts gas collection efficiency and particle collection artifact for SOCs in multicapillary denuders using polydimethylsiloxane (PDMS) sorbent. An approach is presented to estimate the equilibrium PDMS-gas partition coefficient (Kpdms) from an Abraham solvation parameter model for any SOC. A high flow rate (300 L min-1) multicapillary denuder was designed for measurement of trace atmospheric SOCs. Overall method precision and detection limits were determined using field duplicates and compared to the conventional high-volume sampler method. The high-flow denuder is an alternative to high-volume or passive samplers when separation of gas and particle-associated SOCs upstream of a filter and short sample collection time are advantageous. A Lagrangian internal boundary layer transport exchange (IBLTE) Model is described. The model predicts the near-surface variation in several quantities with fetch in coastal, offshore flow: 1) modification in potential temperature and gas mixing ratio, 2) surface fluxes of sensible heat, water vapor, and trace gases using the NOAA COARE Bulk Algorithm and Gas Transfer Model, 3) vertical gradients in potential temperature and mixing ratio. The model was applied to interpret micrometeorological measurements of air-water exchange flux of HCB and several PCB congeners in Lake Superior. The IBLTE Model can be applied to any scalar, including water vapor, carbon dioxide, dimethyl sulfide, and other scalar quantities of interest with respect to hydrology, climate, and ecosystem science.

Subfilter-scale Stress Modelling for Large Eddy Simulations

A subfilter-scale (SFS) stress model is developed for large-eddy simulations (LES) and is tested on various benchmark problems in both wall-resolved and wall-modelled LES. The basic ingredients of the proposed model are the model length-scale, and the model parameter. The model length-scale is defined as a fraction of the integral scale of the flow, decoupled from the grid. The portion of the resolved scales (LES resolution) appears as a user-defined model parameter, an advantage that the user decides the LES resolution. The model parameter is determined based on a measure of LES resolution, the SFS activity. The user decides a value for the SFS activity (based on the affordable computational budget and expected accuracy), and the model parameter is calculated dynamically. Depending on how the SFS activity is enforced, two SFS models are proposed. In one approach the user assigns the global (volume averaged) contribution of SFS to the transport (global model), while in the second model (local model), SFS activity is decided locally (locally averaged). The models are tested on isotropic turbulence, channel flow, backward-facing step and separating boundary layer. In wall-resolved LES, both global and local models perform quite accurately. Due to their near-wall behaviour, they result in accurate prediction of the flow on coarse grids. The backward-facing step also highlights the advantage of decoupling the model length-scale from the mesh. Despite the sharply refined grid near the step, the proposed SFS models yield a smooth, while physically consistent filter-width distribution, which minimizes errors when grid discontinuity is present. Finally the model application is extended to wall-modelled LES and is tested on channel flow and separating boundary layer. Given the coarse resolution used in wall-modelled LES, near the wall most of the eddies become SFS and SFS activity is required to be locally increased. The results are in very good agreement with the data for the channel. Errors in the prediction of separation and reattachment are observed in the separated flow, that are somewhat improved with some modifications to the wall-layer model.