Chemical loading into surface water along a hydrological, biogeochemical, and land use gradient: a holistic watershed approach

Identifying the sources and impacts of organic and inorganic contaminants at the watershed scale is a complex challenge because of the multitude of processes occurring in time and space. Investigation of geochemical transformations requires a systematic evaluation of hydrologic, landscape, and anthropogenic factors. The 1160 km2 Boulder Creek Watershed in the Colorado Front Range encompasses a gradient of geology, ecotypes, climate, and urbanization. Streamflow originates primarily as snowmelt and shows substantial annual variation. Water samples were collected along a 70-km transect during spring-runoff and base-flow conditions, and analyzed for major elements, trace elements, bulk organics, organic wastewater contaminants (OWCs), and pesticides. Major-element and trace-element concentrations were low in the headwaters, increased through the urban corridor, and had a step increase downstream from the first major wastewater treatment plant (WWTP). Boron, gadolinium, and lithium were useful inorganic tracers of anthropogenic inputs. Effluent from the WWTP accounted for as much as 75% of the flow in Boulder Creek and was the largest chemical input. Under both hydrological conditions, OWCs and pesticides were detected in Boulder Creek downstream from the WWTP outfall as well as in the headwater region, and loads of anthropogenic-derived contaminants increased as basin population density increased. This report documents a suite of potential endocrine-disrupting chemicals in a reach of stream with native fish populations showing indication of endocrine disruption.     

Calculation and uses of mean sediment quality guideline quotients: a critical review

Fine-grained sediments contaminated with complex mixtures of organic and inorganic chemical contaminants can be toxic in laboratory tests and/or cause adverse impacts to resident benthic communities. Effects-based, sediment quality guidelines (SQGs) have been developed over the past 20 years to aid in the interpretation of the relationships between chemical contamination and measures of adverse biological effects. Mean sediment quality guideline quotients (mSQGQ) can be calculated by dividing the concentrations of chemicals in sediments by their respective SQGs and calculating the mean of the quotients for the individual chemicals. The resulting index provides a method of accounting for both the presence and the concentrations of multiple chemicals in sediments relative to their effects-based guidelines. Analyses of considerable amounts of data demonstrated that both the incidence and magnitude of toxicity in laboratory tests and the incidence of impairment to benthic communities increases incrementally with increasing mSQGQs. Such concentration/response relationships provide a basis for estimating toxicological risks to sediment-dwelling organisms associated with exposure to contaminated sediments with a known degree of accuracy. This sediment quality assessment tool has been used in numerous surveys and studies since 1994. Nevertheless, mean SQGQs have some important limitations and underlying assumptions that should be understood by sediment quality assessors. This paper provides an overview of the derivation methods and some of the principal advantages, assumptions, and limitations in the use of this sediment assessmenttool. Ideally, mean SQGQs should be included with other measures including results of toxicity tests and benthic community surveys to provide a weight of evidence when assessing the relative quality of contaminated sediments.     

Viewing angle enhancement for two- and three-dimensional holographic displays with random superresolution phase masks

Holographic displays employing binary phase modulation have been demonstrated to be attractive on the grounds of efficiency and miniaturization, and they offer a plausible approach to two-dimensional (2D) and three-dimensional (3D) image projection and display. A novel algorithm--one-step phase retrieval--and corresponding hardware architecture have recently been proposed, providing the performance required for real-time holographic display. However, since viewing angle varies inversely with pixel size, very small display pixels are required to achieve a wide field of view. This is particularly problematic for 3D displays, as the requirement for a large display with small pixels has hitherto necessitated an unachievably large electrical bandwidth. We present a novel approach, utilizing fixed random pixelated quaternary phase masks of greater resolution than the displayed hologram, to dramatically increase the viewing angle for 2D and 3D holographic displays without incurring a bandwidth penalty or significantly degrading image quality. Furthermore, an algorithm is presented to generate holograms accounting for the presence of such a phase mask, so that only one mask is required.     

Direct writing of metal nanoparticle films inside sealed microfluidic channels

Herein we demonstrate the ability to pattern Ag nanoparticle films of arbitrary geometry inside sealed PDMS/TiO2/glass microfluidic devices. The technique can be employed with aqueous solutions at room temperature under mild conditions. A 6 nm TiO2 film is first deposited onto a planar Pyrex or silica substrate, which is subsequently bonded to a PDMS mold. UV light is then exposed through the device to reduce Ag+ from an aqueous solution to create a monolayer-thick film of Ag nanoparticles. We demonstrate that this on-chip deposition method can be exploited in a parallel fashion to synthesize nanoparticles of varying size by independently controlling the solution conditions in each microchannel in which the film is formed. The film morphology was checked by atomic force microscopy, and the results showed that the size of the nanoparticles was sensitive to solution pH. Additionally, we illustrate the ability to biofunctionalize these films with ligands for protein capture. The results indicated that this could be done with good discrimination between addressed locations and background. The technique appears to be quite general, and films of Pd, Cu, and Au could also be patterned.     

The RNA-cleaving bipartite DNAzyme is a distinctive metalloenzyme

Much interest has focused on the mechanisms of the five naturally occurring self-cleaving ribozymes, which, in spite of catalyzing the same reaction, adopt divergent strategies. These ribozymes, with the exception of the recently described glmS ribozyme, do not absolutely require divalent metal ions for their catalytic chemistries in vitro. A mechanistic investigation of an in vitro-selected, RNA-cleaving DNA enzyme, the bipartite, which catalyzes the same chemistry as the five natural self-cleaving ribozymes, found a mechanism of significant complexity. The DNAzyme showed a bell-shaped pH profile. A dissection of metal usage indicated the involvement of two catalytically relevant magnesium ions for optimal activity. The DNAzyme was able to utilize manganese(II) as well as magnesium; however, with manganese it appeared to function complexed to either one or two of those cations. Titration with hexaamminecobalt(III) chloride inhibited the activity of the bipartite; this suggests that it is a metalloenzyme that utilizes metal hydroxide as a general base for activation of its nucleophile. Overall, the bipartite DNAzyme appeared to be kinetically distinct not only from the self-cleaving ribozymes but also from other in vitro-selected, RNA-cleaving deoxyribozymes, such as the 8-17, 10-23, and 614.     

Modeling iron binding to organic matter

The aim of the present work is to model iron speciation during its interaction with natural organic matter. Experimental data for iron speciation were achieved with an insolubilised humic acid used as an organic matter analogue for 30microM to 1.8 mM total iron concentrations and 2< or = pH< or = 5.5. IHA was found to be able to impose its redox potential to the solution and therefore the Fe(ll)/Fe(lll) ratio. Model VI and the NICA-Donnan model have been adjusted to experimental results of acid-base titrations, total iron measurements, and redox speciation in solution. They both describe well pH and concentration dependence of iron adsorption. For high iron concentration, Fe(lll) solution activity is limited by precipitation of a poorly ordered Fe oxyhydroxide with a higher solubility (log Ks = 5.6-5.7) than ferryhydrite described in the litterature.     

Ferroelectric-based electrostatic micromotors with nanometer gaps

The design of the capacitive motors that are based on the electrostatic rolling of the thin metallic film on the ferroelectric surface is studied. It is shown that this method of energy conversion allows one to move the main stage of electromechanical energy conversion into the nanometer range when using the materials with high dielectric permeability (more than 500). The analysis of the distribution of the forces and field in the nanometer gap of the electrostatic micromotors is carried out. An experimental investigation of these micromotors is performed.     

Real-time, 3-D ultrasound with multiple transducer arrays

Modifications were made to a commercial real-time, three-dimensional (3-D) ultrasound system for near simultaneous 3-D scanning with two matrix array transducers. As a first illustration, a transducer cable assembly was modified to incorporate two independent, 3-D intra-cardiac echo catheters, a 7 Fr (2.3 mm O.D.) side scanning catheter and a 14 Fr (4.7 mm O.D) forward viewing catheter with accessory port, each catheter using 85 channels operating at 5 MHz. For applications in treatment of atrial fibrillation, the goal is to place the sideviewing catheter within the coronary sinus to view the whole left atrium, including a pulmonary vein. Meanwhile, the forward-viewing catheter inserted within the left atrium is directed toward the ostium of a pulmonary vein for therapy using the integrated accessory port. Using preloaded, phasing data, the scanner switches between catheters automatically, at the push of a button, with a delay of about 1 second, so that the clinician can view the therapy catheter with the coronary sinus catheter and vice versa. Preliminary imaging studies in a tissue phantom and in vivo show that our system successfully guided the forward-viewing catheter toward a target while being imaged with the sideviewing catheter. The forward-viewing catheter then was activated to monitor the target while we mimicked therapy delivery. In the future, the system will switch between 3-D probes on a line-by-line basis and display both volumes simultaneously.     

Surface behaviour of biomaterials: The theta surface for biocompatibility

“Biomaterials” are non-living substances selected to have predictable interactions with contacting biological phases, in applications ranging from medical/dental implants to food processing to control of biofouling in the sea. More than 30 years of empirical observations of the surface behaviours of various materials in biological settings, when correlated with the contact-angle-determined Critical Surface Tensions (CST) for these same materials, support the definition of the “theta surface”. The “theta surface” is that characteristic expression of outermost atomic features least retentive of depositing proteins, and identified by the bioengineering criterion of having measured CST between 20 and 30 mN/m. Biomaterials applications requiring strong bioadhesion must avoid this range, while those requiring easy release of accumulating biomass should have “theta surface” qualities. Selection of blood-compatible materials is a main example. It is forecast that future biomaterials will be safely and effectively translated directly to clinical use, without requiring animal testing, based on laboratory data for CST, protein denaturation, and cell spreading alone.     

Transient reflection of TE-polarized plane waves from a Lorentz-medium half-space

The time-domain reflection coefficient for a plane wave obliquely incident on a Lorentz-medium half-space is determined analytically by inversion of the frequency-domain reflection coefficient. The resulting expression contains only simple functions and a single convolution of these functions. Owing to its simplicity, this form of the reflection coefficient provides insight into its temporal behavior, specifically how the relationship between the damping coefficient and the oscillation frequency determines the shape of the response. The simple form of the reflection coefficient is validated numerically through comparison with the inverse fast Fourier transform of the frequency-domain reflection coefficient.