Water Boundary Layer Research Articles

Thickness and material selection of polymeric passive samplers for polycyclic aromatic hydrocarbons in water: Which more strongly affects sampler properties?

Three configurations of single-phase polymer passive samplers made of polyoxymethylene (POM), silicone rubber, and polyethylene (PE) were simultaneously calibrated in laboratory experiments by determining their partitioning coefficients and the POM diffusion coefficients and by validating a kinetic accumulation model. In addition, the performance of each device was evaluated under field conditions. With the support of the developed model, the device properties are discussed with regard to material selection and polymer thickness. The results show that a sampler's properties, such as its concentration-averaging period and ability to sample a large amount of polycyclic aromatic hydrocarbons, are widely affected by material selection. Sampler thickness also allows modulation of the properties of the device but with a much lower magnitude. Selection of the appropriate polymer and/or thickness allows samplers to be adapted either for quick equilibration or for the kinetic accumulation regime and promotes either membrane or water boundary layer control of the kinetic accumulation. In addition, membrane-controlled or equilibrated compounds are quantified with greater accuracy because they are not corrected by the performance reference compounds approach. However, the averaged concentrations cannot be assessed when compounds reach equilibrium in the sampler, whereas membrane-controlled devices remaining in the kinetic accumulation regime provide averaged concentrations without requiring performance reference compound correction; detection limits are then increased because of the higher mass transfer resistance of the membrane. Environ Toxicol Chem 2016;35:1708-1717. © 2015 SETAC.

Investigating the Material Properties of the Caulobacter Crescentus Adhesive Holdfast

The ability to adhere materials underwater is greatly impeded by the presence of a boundary layer of water between the two adherends, with synthetic adhesives failing due to poor interfacial adhesion. Nature possesses various solutions to this problem, as seen in studied mussels, sandcastle worm and barnacles; however, less complex unicellular organisms such as bacteria are also faced with this problem. One of the primary colonizers of submerged surfaces is the bacteria Caulobacter crescentus, which adheres underwater by means of a secreted adhesive holdfast that possesses the highest measured adhesive strength for any microorganism. Little is known about the material properties of this adhesive. We use a combination of spectroscopic and microscopic techniques to elucidate the chemical components of the holdfast, its structural features as well as its interaction with different surface characteristics. An understanding of these properties will provide design ideas for the fabrication of bio-inspired underwater adhesives with potential applications in areas such as engineering, medicine and biomimetics.

Calibration of a passive sampler based on stir bar sorptive extraction for the monitoring of hydrophobic organic pollutants in water

A passive sampler based on stir bars coated with polydimethylsiloxane (PDMS) was calibrated for the measurement of time-weighted average concentrations of hydrophobic micropollutants, including polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides, in water. Stir bar/water partition coefficients were measured by equilibrating bars with sheets made of silicone rubber material for which partition coefficients had been reported previously. Kinetic parameters characterising the exchange of analytes between stir bars and water were determined under controlled exposure conditions using a passive dosing system. The dosing system consisted of silicone rubber sheets with a large surface area, spiked with analytes. During stir bar sampler exposure, analytes partitioned from dosing sheets to water in the exposure tank and maintained constant exposure concentrations. Reversible and isotropic exchange kinetics of analytes between sampler and water was confirmed by measuring the release of a range of performance reference compounds (PRCs) from stir bars. Application of a two-resistance model confirmed that, except for hexachlorocyclohexane isomers, uptake of the test compounds under the experimental conditions was controlled by diffusion in the water boundary layer. This permits the application of PRCs for in situ calibration of uptake kinetics of test compounds to stir bars.

Scaling down for a broader understanding of underwater adhesives - a case for the Caulobacter crescentus holdfast.

The adhesion of two materials in the presence of water is greatly impeded by a boundary layer of water between the adhesive and the adherend, resulting in adhesive failure of most synthetic adhesives; however, life evolved first in water and there are many aquatic organisms that have to overcome this impediment to underwater adhesion. For example, multicellular aquatic organisms like the mussel, sandcastle worm and the caddisfly larva employ well-studied adhesive mechanisms for sticking in the presence of water. Unicellular organisms such as bacteria also make use of various means for attaching to surfaces, within similar environmental conditions. Prominent among them is the aquatic bacteria, Caulobacter crescentus which utilizes a unique adhesive secretion, the holdfast, to adhere strongly in the presence of water. Here we review the attachment mechanisms of some multicellular aquatic organisms and compare the similarities and differences in the composition and structure of the C. crescentus holdfast, which holds promise as a potential source for bio-inspired synthetic underwater adhesives with prospective applications in medicine, engineering and biomimetics.

Currents and convection cause enhanced gas exchange in the ice–water boundary layer

The presence of sea ice acts as a physical barrier for air–sea exchange. On the other hand it creates additional turbulence due to current shear and convection during ice formation. We present results from a laboratory study that demonstrate how shear and convection in the ice–ocean boundary layer can lead to significant gas exchange. In the absence of wind, water currents beneath the ice of 0.23 m s−1 produced a gas transfer velocity (k) of 2.8 m d−1, equivalent to k produced by a wind speed of 7 m s−1 over the open ocean. Convection caused by air–sea heat exchange also increased k of as much as 131 % compared to k produced by current shear alone. When wind and currents were combined, k increased, up to 7.6 m d−1, greater than k produced by wind or currents alone, but gas exchange forcing by wind produced mixed results in these experiments. As an aggregate, these experiments indicate that using a wind speed parametrisation to estimate k in the sea ice zone may underestimate k by ca. 50 % for wind speeds <8 m s−1.

Quantifying Marine Boundary Layer Water Vapor beneath Low Clouds with Near-Infrared and Microwave Imagery

AbstractThis study investigates the synergy of collocated microwave radiometry and near-infrared imagery to estimate the marine boundary layer water vapor beneath uniform cloud fields. Microwave radiometry provides the total column water vapor, while the near-infrared imagery provides the water vapor above the cloud layers. The difference between the two gives the vapor between the surface and the cloud top, which may be interpreted as the boundary layer water vapor. In combining the two datasets, we apply several flags as well as proximity tests to remove pixels with high clouds and/or intrapixel heterogeneity. Comparisons against radiosonde and ECMWF reanalysis data demonstrate the robustness of these boundary layer water vapor estimates. Last, it is shown that the measured AMSR-MODIS boundary layer water vapor can be analyzed using sea surface temperature and cloud-top pressure information by employing simple equations based on the Clausius–Clapeyron relationship.

Modeling the transport of organic chemicals between polyethylene passive samplers and water in finite and infinite bath conditions.

Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments.

Developmental, nutritional and hormonal anomalies of weightlessness-grown wheat

The behavior of water in weightlessness, as occurs in orbiting spacecraft, presents multiple challenges for plant growth. Soils remain saturated, impeding aeration, and leaf surfaces remain wet, impeding gas exchange. Herein we report developmental and biochemical anomalies of “Super Dwarf” wheat (Triticum aestivum L.) grown aboard Space Station Mir during the 1996–97 “Greenhouse 2” experiment. Leaves of Mir-grown wheat were hyperhydric, senesced precociously and accumulated aromatic and branched-chain amino acids typical of tissues experiencing oxidative stress. The highest levels of stress-specific amino acids occurred in precociously-senescing leaves. Our results suggest that the leaf ventilation system of the Svet Greenhouse failed to remove sufficient boundary layer water, thus leading to poor gas exchange and onset of oxidative stress. As oxidative stress in plants has been observed in recent space-flight experiments, we recommend that percentage water content in apoplast free-spaces of leaves be used to evaluate leaf ventilation effectiveness. Mir-grown plants also tillered excessively. Crowns and culms of these plants contained low levels of abscisic acid but high levels of cytokinins. High ethylene levels may have suppressed abscisic acid synthesis, thus permitting cytokinins to accumulate and tillering to occur.

Moisture sources and synoptic to seasonal variability of North Atlantic water vapor isotopic composition

AbstractThe isotopic composition of near surface (or planetary boundary layer) water vapor on the south coast of Iceland (63.83°N, 21.47°W) has been monitored in situ between November 2011 and April 2013. The calibrated data set documents seasonal variations in the relationship between δ18O and local humidity (ppmv) and between deuterium excess and δ18O. These seasonal variations are attributed to seasonal changes in atmospheric transport. A strong linear relationship is observed between deuterium excess and atmospheric relative humidity calculated at regional sea surface temperature. Surprisingly, we find a similar relationship between deuterium excess and relative humidity as observed in the Bermuda Islands. During days with low amount of isotopic depletion (more enriched values), our data significantly deviate from the global meteoric water line. This feature can be explained by a supply of an evaporative flux into the planetary boundary layer above the ocean, which we show using a 1‐d box model. Based on the close relationship identified between moisture origin and deuterium excess, we combine deuterium excess measurements performed in Iceland and south Greenland with moisture source diagnostics based on back trajectory calculations to establish the distribution of d‐excess moisture uptake values across the North Atlantic. We map high deuterium excess in the Arctic and low deuterium excess for vapor in the subtropics and midlatitudes. This confirms the role of North Atlantic water vapor isotopes as moisture origin tracers.

Stable water isotope and surface heat flux simulation using ISOLSM: Evaluation against in-situ measurements

Summary The stable isotopes of water are useful tracers of water sources and hydrological processes. Stable water isotope-enabled land surface modeling is a relatively new approach for characterizing the hydrological cycle, providing spatial and temporal variability for a number of hydrological processes. At the land surface, the integration of stable water isotopes with other meteorological measurements can assist in constraining surface heat flux estimates and discriminate between evaporation (E) and transpiration (T). However, research in this area has traditionally been limited by a lack of continuous in-situ isotopic observations. Here, the National Centre for Atmospheric Research stable isotope-enabled Land Surface Model (ISOLSM) is used to simulate the water and energy fluxes and stable water isotope variations. The model was run for a period of one month with meteorological data collected from a coastal sub-tropical site near Sydney, Australia. The modeled energy fluxes (latent heat and sensible heat) agreed reasonably well with eddy covariance observations, indicating that ISOLSM has the capacity to reproduce observed flux behavior. Comparison of modeled isotopic compositions of evapotranspiration (ET) against in-situ Fourier Transform Infrared spectroscopy (FTIR) measured bulk water vapor isotopic data (10 m above the ground), however, showed differences in magnitude and temporal patterns. The disparity is due to a small contribution from local ET fluxes to atmospheric boundary layer water vapor (∼1% based on calculations using ideal gas law) relative to that advected from the ocean for this particular site. Using ISOLSM simulation, the ET was partitioned into E and T with 70% being T. We also identified that soil water from different soil layers affected T and E differently based on the simulated soil isotopic patterns, which reflects the internal working of ISOLSM. These results highlighted the capacity of using the isotope-enabled models to discriminate between different hydrological components and add insight into expected hydrological behavior.

Observational Boundary Layer Energy and Water Budgets of the Stratocumulus-to-Cumulus Transition

Abstract The authors estimate summer mean boundary layer water and energy budgets along a northeast Pacific transect from 35° to 15°N, which includes the transition from marine stratocumulus to trade cumulus clouds. Observational data is used from three A-Train satellites, Aqua, CloudSat, and the Cloud–Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO); data derived from GPS signals intercepted by microsatellites of the Constellation Observing System for Meteorology, Ionosphere, and Climate (COSMIC); and the container-ship-based Marine Atmospheric Radiation Measurement Program (ARM) Global Energy and Water Cycle Experiment Cloud System Study/Working Group on Numerical Experimentation (GCSS/WGNE) Pacific Cross-Section Intercomparison (GPCI) Investigation of Clouds (MAGIC) campaign. These are unique satellite and shipborne observations providing the first global-scale observations of light precipitation, new vertically resolved radiation budget products derived from the active sensors, and well-sampled radiosonde data near the transect. In addition to the observations, the European Centre for Medium-Range Weather Forecasts (ECMWF) Interim Re-Analysis (ERA-Interim) fields are utilized to estimate the budgets. Both budgets approach within 3 W m−2 averaged along the transect, although uncertainty estimates from the study are much larger than this residual. A mean entrainment rate along the transect of mm s−1 is also estimated. A gradual transition is observed in the climatological mean from the stratocumulus regime to the cumulus regime characterized by an increase in boundary layer height, latent heat flux, rain, and the horizontal advection of dry air and a decrease in entrainment of warm dry air.

Turbulent Dispersion of a Passive Scalar in a Staggered Array of Cubes

In this article, we report a numerical and experimental study of turbulent dispersion of a passive scalar released from a continuous ground-level point source in a staggered array of 16 × 16 cubical obstacles. Experimental measurements of the flow and dispersion were obtained in a boundary-layer water channel using laser-induced fluorescence (for concentration) and laser Doppler velocimetry (for velocity). Numerical simulations of the flow and scalar fields for this experimental configuration were performed using two in-house computer codes based on the Reynolds-averaged Navier-Stokes (RANS) method. Results of a detailed comparison between water-channel measurements and model predictions of the mean flow, turbulence kinetic energy, mean concentration, and concentration variance are presented. An advanced model for the concentration variance dissipation rate is validated in the new context of plume dispersion within and above a staggered array of cubical obstacles.

Visualization of crystallization of the boundary layer of a water droplet by frustrated total internal reflection of a wide collimated laser beam

This paper presents the results of processing of the experimental data obtained in a study of cooling and crystallization of a thin boundary layer of distilled water by frustrated total internal reflection of a wide collimated laser beam in order to determine the dependence of the temperature of this layer on time.

Use of the GOES-R Split-Window Difference to Diagnose Deepening Low-Level Water Vapor

AbstractThe depth of boundary layer water vapor plays a critical role in convective cloud formation in the warm season, but numerical models often struggle with accurate predictions of above-surface moisture. Satellite retrievals of water vapor have been developed, but they are limited by the use of a model’s first guess, instrument spectral resolution, horizontal footprint size, and vertical resolution. In 2016, Geostationary Operational Environmental Satellite-R (GOES-R), the first in a series of new-generation geostationary satellites, will be launched. Its Advanced Baseline Imager will provide unprecedented spectral, spatial, and temporal resolution. Among the bands are two centered at 10.35 and 12.3 μm. The brightness temperature difference between these bands is referred to as the split-window difference, and has been shown to provide information about atmospheric column water vapor. In this paper, the split-window difference is reexamined from the perspective of GOES-R and radiative transfer model simulations are used to better understand the factors controlling its value. It is shown that the simple split-window difference can provide useful information for forecasters about deepening low-level water vapor in a cloud-free environment.

Ice–water heat exchange during ice growth in Lake Baikal

Using a custom-made thermistor chain frozen into the ice cover we obtained the first detailed information on distribution of temperature within ice and structure of the ice–water boundary layer during ice growth in Lake Baikal. A mathematical model of the heat transport in a multilayer ice–water system (Stefan problem) was developed and verified on results of in situ measurements. Effective coefficients of thermal diffusivity and ice–water heat fluxes were estimated from the inverse solution of the model and compared with direct flux estimates from the flux-gradient method. Both estimations agreed on flux values of 1–10Wm−2 and demonstrated strong synoptic variability in ice–water heat exchange. We estimated the thickness of viscous laminar sublayer under ice, as well as the thickness of the transitional layer on top of the turbulent water column. The thickness of the viscous sublayer of 1–1.5cm in Lake Baikal was several times smaller than values reported previously from small lakes, suggesting high magnitudes of convective velocities and/or of the under-ice currents in Lake Baikal. Significant growth of the thermal diffusivity coefficient with increasing distance from the ice bottom was detected: its value at the top of the transition layer of under ice water was 10–40 times higher compared with its value in viscous laminar sublayer. This is also significantly higher than previous estimations in smaller freshwater lakes.

Non-similar solutions for unsteady flow over a yawed cylinder with non-uniform mass transfer through a slot

Non-similar solutions are found numerically to a system of coupled non-linear partial differential equations indicating, unsteady laminar water boundary layer flow over yawed cylinder using implicit finite difference scheme along with Quasi-linearization technique. The fluid properties such as viscosity and Prandtl number are considered as an inverse function of temperature. Unsteadiness is caused by upstream velocity in and directions and non-uniform mass transfer (suction/injection) which is applied through slot on the surface of the geometry. The effect of yaw angle, variable fluid properties and non-uniform mass transfer on skin friction and heat transfer coefficients is analyzed. It is found that non-uniform slot suction and downstream movement of the slot cause the point of vanishing skin friction moves downstream, but non-uniform slot injection produces the opposite result of that corresponding to the suction case. When the yaw angle increases, both the skin friction coefficient in the – direction and the heat transfer coefficient decrease but the skin friction coefficient in the – direction increases for all times. The effect of the yaw angle is very little on the point of vanishing skin friction.

Calculating the Diffusive Flux of Persistent Organic Pollutants between Sediments and the Water Column on the Palos Verdes Shelf Superfund Site Using Polymeric Passive Samplers

Passive samplers were deployed to the seafloor at a marine Superfund site on the Palos Verdes Shelf, California, USA, and used to determine water concentrations of persistent organic pollutants (POPs) in the surface sediments and near-bottom water. A model of Fickian diffusion across a thin water boundary layer at the sediment-water interface was used to calculate flux of contaminants due to molecular diffusion. Concentrations at four stations were used to calculate the flux of DDE, DDD, DDMU, and selected PCB congeners from sediments to the water column. Three passive sampling materials were compared: PE strips, POM strips, and SPME fibers. Performance reference compounds (PRCs) were used with PE and POM to correct for incomplete equilibration, and the resulting POP concentrations, determined by each material, agreed within 1 order of magnitude. SPME fibers, without PRC corrections, produced values that were generally much lower (1 to 2 orders of magnitude) than those measured using PE and POM, indicating that SPME may not have been fully equilibrated with waters being sampled. In addition, diffusive fluxes measured using PE strips at stations outside of a pilot remedial sand cap area were similar to those measured at a station inside the capped area: 240 to 260 ng cm(-2) y(-1) for p,p'-DDE. The largest diffusive fluxes of POPs were calculated at station 8C, the site where the highest sediment concentrations have been measured in the past, 1100 ng cm(-2) y(-1) for p,p'-DDE.

Satellite retrieval of convective cloud base temperature based on the NPP/VIIRS Imager

AbstractThe advent of the Visible Infrared Imaging Radiometer Suite (VIIRS) onboard the Suomi National Polar‐Orbiting Partnership (NPP) satellite provided a quantum jump in the satellite capabilities of retrieving cloud properties, because it nearly tripled the resolution in the thermal channels (375 m). This allowed us to develop a methodology for retrieving convective cloud base temperature (Tb) and validate it over the Atmospheric System Research Southern Great Plains site for the satellite early afternoon overpass time. The standard error of the Tb retrieval was only 1.1°C. The knowledge of Tb allows the calculation of cloud base height and the depth of the boundary layer, as well as the boundary layer water vapor mixing ratio with an accuracy of about 10%. The feasibility of retrieving cloud base temperature and height is an essential component that is required for retrieving cloud condensation nuclei (CCN) from satellites by using convective clouds as natural CCN chambers.

Ion-Induced Reorientation and Distribution of Pentanone in the Air–Water Boundary Layer

Organic material at the surface of atmospheric aerosols is ubiquitous and plays an important role in Earth's atmosphere. Small ketones, such as 3-pentanone, are found in aerosols and as surface-active species on aerosols. This study uses 3-pentanone as a model ketone to understand how such molecules adsorb at the vapor-water interface on aqueous solutions containing sulfate, carbonate, or chloride ions. By combining surface spectroscopic experiments with computational methods, very detailed information about the molecular bonding, geometries, and surface orientation of 3-pentanone as a function of depth has been obtained. The results show that, for pure water, 3-pentanone resides at the topmost surface of water with the carbonyl pointing into the aqueous phase where it is weakly solvated. For Na2SO4-containing solutions, we found that sulfate ions in the boundary layer provoke changes in the geometry and interfacial position of 3-pentanone that are not seen in solutions containing sodium chloride or sodium carbonate. The results provide important insight into the behavior of ketones in the presence of salts at the surface of aerosols in the atmosphere.

Challenges of Using Polyethylene Passive Samplers to Determine Dissolved Concentrations of Parent and Alkylated PAHs under Cold and Saline Conditions

Passive samplers can be useful tools for determining truly dissolved concentrations of organic contaminants in the water. Polyethylene (PE) samplers were validated for measuring polycyclic aromatic hydrocarbons (PAHs), with a focus on alkylated PAHs that can dominate in an oil spill. Equilibrium partition coefficients between water and PE passive samplers (KPEw) were measured for 41 PAHs both at ambient conditions (20 °C, no salt) and down to -15 °C with up to 245 psu present in ice brine. For each additional alkylated carbon, logKPEw increased by an average of 0.40 (±0.20) log units, close to predictions. The increase per aromatic carbon was only 0.33 (±0.02) log units. Apparent PE-water distributions of pyrene and deuterated pyrene (performance reference compound) were within 0.1 log unit for all experiments at 20 and 2 °C but started to diverge by 0.8 log units at -4 °C (100 psu) and by 3.1 log units at -15 °C (245 psu). The delay in equilibrating PAHs in these experiments was dominated by increases in the water viscosity, which, in turn, affected both the aqueous diffusivities of the PAHs and the thickness of the water boundary layer. In a simulated marine oil spill in the laboratory, PE-based results were within a factor of 2 of conventional sampling results for the most abundant PAHs.