Responses of Hyalella azteca and Ceridaphnia dubia to reservoir sediments following Chelated Copper Herbicide Applications

In response to nuisance growths of algae and vascular plants, such as dioecious hydrilla ( Hydrilla verticillata L.f. Royle), copper formulations have been applied in lakes and reservoirs for a number of years. Concerns have arisen regarding the long-term consequences of copper applications and those concerns have appropriately focused on sediment residues. In this study, we evaluated the toxicity of sediments from treated (for a decade) and untreated areas in Lake Murray, South Carolina and estimated the capacity of those sediments to bind additional copper. Two sentinel aquatic invertebrates, Hyalella azteca Saussure and Ceriodaphnia dubia Richard, were used to measure residual toxicity of treated and untreated sediments from the field and after laboratory amendments. (PDF has 5 pages.)

Relative tolerance of mat-forming algae to copper

This study documents the relative tolerance of the common, weedy mat-forming green algae Hydrodictyon , Oedogonium , Pithophora , Rhizoclonium , and Spirogyra to copper. In addition, the copper tolerance of the cyanobacterial (blue-green algal) mat-forming Oscillatoria was assessed.

Microstructure and mechanical properties of copper subjected to high pressure torsion

Experiments were conducted on copper subjected to High Pressure Torsion to investigate the evolution of microstructure and microhardness with shear strain, gamma. Observations have been carried out in the longitudinal section for a proper demonstration of the structure morphology. An elongated dislocation cell/subgrain structure was observed at relatively low strain level. With increasing strain, the elongated subgrains transformed into elongated grains and finally into equiaxed grains with high angle grain boundaries. Measurements showed the hardness increases with increasing gamma then tends to saturations when gamma >5. The variation tendency of microhardness with gamma can be simulated by Voce-type equation.

Hypoxia and Sturgeons: report to the Chesapeake Bay Program Dissolved Oxygen Criteria Team

In this essay, three lines of evidence are developed that sturgeons in the Chesapeake Bay and elsewhere are unusually sensitive to hypoxic conditions: 1. In comparison to other fishes, sturgeons have a limited behavioral and physiological capacity to respond to hypoxia. Basal metabolism, growth, and consumption are quite sensitive to changes in oxygen level, which may indicate a relatively poor ability by sturgeons to oxyregulate. 2. During summertime, temperatures >20 C amplify the effect of hypoxia on sturgeons and other fishes due to a temperature*oxygen "squeeze" (Coutant 1987)- In bottom waters, this interaction results in substantial reduction of habitat; in dry years, nursery habitats in the Chesapeake Bay may be particularly reduced or even eliminated. 3. While evidence for population level effects by hypoxia are circumstantial, there are corresponding trends between the absence of Atlantic sturgeon reproduction in estuaries like the Chesapeake Bay where summertime hypoxia predominates on a system-wide scale. Also, the recent and dramatic recovery of shortnose sturgeon in the Hudson River (4-fold increase in abundance from 1980 to 1995) may have been stimulated by improvement of a large portion of the nursery habitat that was restored from hypoxia to normoxia during the period 1973-1978. (PDF contains 26 pages)

Dissolved oxygen probes: making oxygen measurements routine like temperature, St Petersburg, Florida, January 4-6, 2006: workshop proceedings

The Alliance for Coastal Technologies (ACT) Workshop "Making Oxygen Measurements Routine Like Temperature" was convened in St. Petersburg, Florida, January 4th - 6th, 2006. This event was sponsored by the University of South Florida (USF) College of Marine Science, an ACT partner institution and co-hosted by the Ocean Research Interactive Observatory Networks (ORION). Participants from researcldacademia, resource management, industry, and engineering sectors collaborated with the aim to foster ideas and information on how to make measuring dissolved oxygen a routine part of a coastal or open ocean observing system. Plans are in motion to develop large scale ocean observing systems as part of the US Integrated Ocean Observing System (100s; see http://ocean.us) and the NSF Ocean Observatory Initiative (001; see http://www.orionprogram.org/00I/default.hl). These systems will require biological and chemical sensors that can be deployed in large numbers, with high reliability, and for extended periods of time (years). It is also likely that the development cycle for new sensors is sufficiently long enough that completely new instruments, which operate on novel principles, cannot be developed before these complex observing systems will be deployed. The most likely path to development of robust, reliable, high endurance sensors in the near future is to move the current generation of sensors to a much greater degree of readiness. The ACT Oxygen Sensor Technology Evaluation demonstrated two important facts that are related to the need for sensors. There is a suite of commercially available sensors that can, in some circumstances, generate high quality data; however, the evaluation also showed that none of the sensors were able to generate high quality data in all circumstances for even one month time periods due to biofouling issues. Many groups are attempting to use oxygen sensors in large observing programs; however, there often seems to be limited communication between these groups and they often do not have access to sophisticated engineering resources. Instrument manufacturers also do not have sufficient resources to bring sensors, which are marketable, but of limited endurance or reliability, to a higher state of readiness. The goal of this ACT/ORION Oxygen Sensor Workshop was to bring together a group of experienced oceanographers who are now deploying oxygen sensors in extended arrays along with a core of experienced and interested academic and industrial engineers, and manufacturers. The intended direction for this workshop was for this group to exchange information accumulated through a variety of sensor deployments, examine failure mechanisms and explore a variety of potential solutions to these problems. One anticipated outcome was for there to be focused recommendations to funding agencies on development needs and potential solutions for 02 sensors. (pdf contains 19 pages)

In situ measurement of dissolved inorganic carbon speciation in natural waters, pH, pC02, TA, & TC02, Honolulu, Hawaii, February 16-18, 2005: workshop proceedings

The Alliance for Coastal Technology (ACT) convened a workshop on the in situ measurement of dissolved inorganic carbon species in natural waters in Honolulu, Hawaii, on February 16, 17, and 18, 2005. The workshop was designed to summarize existing technologies for measuring the abundance and speciation of dissolved inorganic carbon and to make strategic recommendations for future development and application of these technologies to coastal research and management. The workshop was not focused on any specific technology, however, most of the attention of the workshop was on in situ pC02 sensors given their recent development and use on moorings for the measurement of global carbon fluxes. In addition, the problems and limitations arising from the long-term deployment of systems designed for the measurement of pH, total dissolved inorganic carbon (DIC), and total alkalinity (TA) were discussed. Participants included researchers involved in carbon biogeochemistry, industry representatives, and coastal resource managers. The primary questions asked during the workshop were: I. What are the major impediments to transform presently used shipboard pC02 measurement systems for use on cost-eficient moorings? 2. What are the major technical hurdles for the in situ measurement of TA and DIC? 3. What specific information do we need to coordinate efforts for proof of concept' testing of existing and new technologies, inter-calibration of those technologies, better software development, and more precise knowledge quantzjjing the geochemistry of dissolved inoeanic carbon species in order to develop an observing system for dissolved inorganic carbon? Based on the discussion resulting from these three questions, the following statements were made: Statement No. 1 Cost-effective, self-contained technologies for making long-term, accurate measurements of the partial pressure of C02 gas in water already exist and at present are ready for deployment on moorings in coastal observing systems. Statement No. 2 Cost-effective, self-contained systems for the measurement of pH, TA, and DIC are still needed to both fully define the carbonate chemistry of coastal waters and the fluxes of carbon between major biogeochemical compartments (e.g., air-sea, shelf-slope, water column-sediment, etc.). (pdf contains 23 pages)

Chemosensory response of marine flagellate towards L- and D- dissolved free amino acids generated during heavy grazing on bacteria

This study investigated the generation of dissolved free amino acids (DFAA) by the bacterivorous flagellate Rhynchomonas nasuta when feeding on abundant prey. Specifically, it examined whether this flagellate protist exhibits a chemosensory response towards those amino acids. The concentrations of glycine and the and D-enantiomers of glutamate, serine, threonine, alanine, and leucine were determined in co-cultures of the flagellate and bacteria. Glycine, L- and D-alanine, and L-serine were found to accumulate under these conditions in amounts that correlated positively with flagellate abundance, suggesting that protists are involved in their generation. Investigations of the chemotactic response of young and old foraging protists to the same amino acids, offered in concentrations similar to those previously generated, showed that glycine elicited the strongest attraction in both age groups. Young protists were strongly attracted to all the assayed amino acids, whereas older protists maintained a high level of attraction only for glycine. These results suggest that glycine generated by protists actively grazing in bacterially enriched patches functions as an infochemical, signaling to foraging protists the presence of available prey in the aquatic environment.

Synthesis Of Plastic Zr-Based Bulk Metallic Glass Matrix Composites By The Copper-Mould Suction Casting And The Bridgman Solidification

Zr-based bulk metallic glass matrix composites with the composition of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.(5) were synthesized by the copper-mould suction casting and the Bridgman solidification. The composite, containing a well-developed flowery beta-Zr dendritic phase, was obtained by the Bridgman solidification with the withdrawal velocity of 0.8 mm/s and the temperature gradient of 45 K/mm, and the ultimate strength of 2050 MPa and fracture plastic strain of 14.6% of the composite were achieved, which was mainly interpreted by the homogeneous dispersion of bcc beta-Zr phase in the glass matrix. Crown Copyright (C) 2008 Published by Elsevier B.V. All rights reserved.

Electron transfer in cytochrome c oxidase : the rate of electron equillibration between cytochrome a and copper A

Intramolecular electron transfer in partially reduced cytochrome c oxidase has been studied by means of perturbed equilibrium techniques. We have prepared a three electron reduced, CO inhibited form of the enzyme in which cytochrome a and copper A are partially reduced an in intramolecular redox equilibrium. When these samples were photolyzed using a nitrogen laser (0.6 µs, 1.0 mJ pulses) changes in absorbance at 598 nm and 830 nm were observed which are consistent with a fast electron from cytochrome a to copper A. The absorbance changes at 598 nm have an apparent rate of 17,200 ± 1,700 s^(-1) (1σ), at pH 7.0 and 25.5 °C. These changes were not observed in either the CO mixed valence or CO inhibited fully reduced forms of the enzyme. The rate is fastest at about pH 8.0, and falls off in either direction, and there is a small, but clear temperature dependence. The process was also observed in the cytochrome c -- cytochrome c oxidase high affinity complex.

This rate is far faster than any rate measured or inferred previously for the cytochrome a -- copper A electron equilibration, but the interpretation of these results is hampered by the fact that the relaxation could only be followed during the time before CO became rebound to the oxygen binding site. The meaning of our our measured rate is discussed, along with other reported rates for this process. In addition, a temperature-jump experiment on the same system is discussed.

We have also prepared a partially reduced, cyanide inhibited form of the enzyme in which cytochrome a, copper A and copper B are partially reduced and in redox equilibrium. Warming these samples produced absorbance changes at 605 nm which indicate that cytochrome a was becoming more oxidized, but there were no parallel changes in absorbance at 830 nm as would be expected if copper A was becoming reduced. We concluded that electrons were being redistributed from cytochrome a to copper B. The kinetics of the absorbance changes at 605 nm were investigated by temperature-jump methods. Although a rate could not be resolved, we concluded that the process must occur with an (apparent) rate larger than 10,000 s^(-1).

During the course of the temperature-jump experiments, we also found that non-redox related, temperature dependent absorbance changes in fully reduced CO inhibited cytochrome c oxidase, and in the cyanide mixed valence enzyme, took place with an (apparent) rate faster that 30,000 s^(-1).

Electrochemical and electron transfer investigations of copper proteins

A study of the pH and temperature dependence of the redox potentials of azurins from five species of bacteria has been performed. The variations in the potentials with pH have been interpreted in terms of electrostatic interactions between the copper site and titrating histidine residues, including the effects of substitutions in the amino acid sequences of the proteins on the electrostatic interactions. A comparison of the observed pH dependences with predictions based on histidine pK_a values known for Pseudomonas aeruginosa (Pae), Alcaligenes denitrificans (Ade), and Alcaligenes faecalis (Afa) azurins indicates that the Pae and Ade redox potentials exhibit pH dependences in line with electrostatic arguments, while Afa azurin exhibits more complex behavior. Redox enthalpies and entropies for four of the azurins at low and high pH values have also been obtained. Based on these results in conjuction with the variable pH experiments, it appears that Bordetella bronchiseptica azurin may undergo a more substantial conformational change with pH than has been observed for other species of azurin.

The temperature dependence of the redox potential of bovine erythrocyte superoxide dismutase (SOD) has been determined at pH 7.0, with potassium ferricyanide as the mediator. The following thermodynamic parameters have been obtained (T = 25°C): E°' = 403±5 mV vs. NHE, ΔG°' = -9.31 kcal/mol, ΔH°' = -21.4 kcal/mol, ΔS°' = -40.7 eu, ΔS°'_(rc) = -25.1 eu. It is apparent from these results that ΔH°', rather than ΔS°', is the dominant factor in establishing the high redox potential of SOD. The large negative enthalpy of reduction may also reflect the factors which give SOD its high specificity toward reduction and oxidation by superoxide.

Application of microwave diagnostics to copper chloride and carbon dioxide lasers

Part A

A problem restricting the development of the CuCl laser has been the decrease in output power with increases of tube temperature above 400°C. At that temperature the CuCl vapor pressure is about .1 torr. This is a small fraction of the buffer gas pressure (He at 10 torr).

The aim of the project was to measure the peak radiation temperature (assumed related to the mean energy of electrons) in the laser discharge as a function of the tube temperature. A 24 gHz gated microwave radiometer was used.

It was found that at the tube temperatures at which the output power began to deteriorate, the electron radiation temperature showed a sharp increase (compared with radiation temperature in pure buffer).

Using the above result, we have postulated that this sudden increase is a result of Penning ionization of the Cu atoms. As a consequence of this process the number of Cu atoms available for lasing decrease.

PART B

The aim of the project was to study the dissociation of CO₂ in the glow discharge of flowing CO₂ lasers.

A TM₀₁₁ microwave (3 gHz) cavity was used to measure the radially averaged electron density n_e and the electron-neutral collision frequency in the laser discharge. An estimate of the electric field is made from these two measurements. A gas chromatograph was used to measure the chemical composition of the gases after going through the discharge. This instrument was checked against a mass spectrometer for accuracy and sensitivity.

Several typical laser mixtures were .used: CO₂-N₂-He (1,3,16), (1,3,0), (1,0,16), (1,2,10), (1,2,0), (1,0,10), (2,3,15), (2,3,0), (2,0,15), (1,3,16)+ H₂O and pure CO₂. Results show that for the conditions studied the dissociation as a function of the electron density is uniquely determined by the STP partial flow rate of CO₂, regardless of the amount of N₂ and/or He present. The presence of water vapor in the discharge decreased the degree of dissociation.

A simple theoretical model was developed using thermodynamic equilibrium. The electrons were replaced in the calculations by a distributed heat source.

The results are analyzed with a simple kinetic model.